WO2024071250A1

WO2024071250A1 - Diamondoid compound and method for producing same

Info

Publication number: WO2024071250A1
Application number: PCT/JP2023/035279
Authority: WO
Inventors: 八木亜樹子岩田; 空駆吉原; 祥史遠山; 健一郎伊丹
Original assignee: 国立大学法人東海国立大学機構
Priority date: 2022-09-27
Filing date: 2023-09-27
Publication date: 2024-04-04

Abstract

This diamondoid compound is a new compound represented by general formula (1) [in the formula, ring A¹ represents an aliphatic ring having two or more rings, R¹ represents a hydrogen atom, an alkyl group, a cycloalkyl group, or an adamantyl group, and n represents an integer of 0-3].

Description

Diamondoid compounds and methods for producing same

The present invention relates to diamondoid compounds and methods for producing the same.

Adamantane is called the smallest diamondoid compound because it is a cage-shaped compound with 10 carbon atoms arranged in a similar manner to the diamond structure. In addition to adamantane, diamondoid compounds with carbon atoms arranged in a similar manner to the diamond structure include higher diamondoid compounds such as diamantane, triamantane, and tetraamantane, which are extensions of the carbon skeleton of adamantane, and it is known that very small amounts of these compounds are isolated from crude oil (see, for example, Non-Patent Document 1).

These higher diamondoid compounds are even smaller than nanodiamonds, and are known to have high melting points, negative electron affinities, and different band gaps and reactivity depending on their structure.

While intensive research has been conducted over the past 20 years and various functionalizations have been achieved, the precise synthesis of novel high-order diamond compounds has not been reported.

The main method for obtaining diamondoid compounds is isolation from crude oil. Although diamondoid compounds such as adamantane and diamantane are commercially available, it has been difficult to obtain higher diamondoid compounds such as triamantane and tetramantane. Furthermore, there is no method for synthesizing diamondoid compounds with structures other than those that have already been isolated, which has hindered the development of the chemistry and applications of diamondoid compounds.

The present invention was made in consideration of the above problems, and aims to synthesize a new diamondoid compound.

The inventors conducted intensive research to solve the above problems and discovered that various diamondoid compounds can be synthesized by condensing an adamantane compound with an aromatic compound and then hydrogenating the resultant in the presence of a specific catalyst. Based on this knowledge, the inventors conducted further intensive research and completed the present invention. The present invention encompasses the following configurations.

Section 1. General formula (1):

[In the formula, ring ^A1 represents an aliphatic ring having two or more rings; ^R1 represents a hydrogen atom, an alkyl group, a cycloalkyl group, or an adamantyl group; and n represents an integer of 0 to 3.]
A diamondoid compound represented by the formula:

Section 2. General formula (1A):

[In the formula, ring ^A2 and ring ^A3 are the same or different and represent an aliphatic ring. ^R1a , ^R1b , and ^R1c are the same or different and represent a hydrogen atom, an alkyl group, a cycloalkyl group, or an adamantyl group. ^R2a and ^R3a are the same or different and represent a hydrogen atom, a hydroxyl group, an alkyl group, an alkoxy group, a cycloalkyl group, an amino group, or an adamantyl group. ^R2a and ^R3a may be joined together to form an aliphatic ring.]
Or general formula (1B):

[Wherein, ring ^A4 and ring ^A5 are the same or different and represent an aliphatic ring. ^R1a , ^R1b and ^R1c are the same or different and represent a hydrogen atom, an alkyl group, a cycloalkyl group, or an adamantyl group. ^R4a and ^R5a are the same or different and represent a hydrogen atom, a hydroxyl group, an alkyl group, an alkoxy group, a cycloalkyl group, an amino group, or an adamantyl group. ^R4a and ^R5a may be joined together to form an aliphatic ring.]
Item 2. The diamondoid compound according to item 1, which is a compound represented by the formula:

Section 3. General formula (1A1):

[In the formula, R ^2a , R ^2b , R ^2c , R ^2d , R ^3a , R 3b , R ^3c and R ^3d ^are the same or different and represent a hydrogen atom, a hydroxyl group, an alkyl group, an alkoxy group, a cycloalkyl group, an amino group, or an adamantyl group. R ^2a and R ^2b , R ^2b and R ^2c , R ^2c and R ^2d , R ^3a and R ^3b , R ^3b and R ^3c , R ^3c and R ^3d , and R ^2a and R ^3a may be joined together to form an aliphatic ring at least at one position.]
Or general formula (1B1):

[In the formula, R ¹ and n are the same as above. R ^4a , R ^4b , R ^4c , R ^5a , R ^5b and R ^5c are the same or different and represent a hydrogen atom, a hydroxyl group, an alkyl group, an alkoxy group, a cycloalkyl group, an amino group, or an adamantyl group. R ^4a and R ^4b , R ^4b and R ^4c , R ^5a and R ^5b , R ^5b and R ^5c , and R ^4a and R ^5a may be joined together to form an aliphatic ring at least at one position.]
Item 3. The diamondoid compound according to item 1 or 2, which is a compound represented by the formula:

Section 4. General formula (1A'):

[In the formula, ring ^A2 and ring ^A3 are the same or different and represent an aliphatic ring. ^R1a , ^R1b , ^R1c , ^R1d , ^R1e , and ^R1f are the same or different and represent a hydrogen atom, an alkyl group, a cycloalkyl group, or an adamantyl group.]
Or general formula (1B'):

[In the formula, ring ^A4 and ring ^A5 are the same or different and represent an aliphatic ring. ^R1a , ^R1b , ^R1c , ^R1d , ^R1e , and ^R1f are the same or different and represent a hydrogen atom, an alkyl group, a cycloalkyl group, or an adamantyl group.]
Item 3. The diamondoid compound according to item 1 or 2, which is a compound represented by the formula:

Section 5. General formula (1A'1):

[In the formula, R ^2b , R ^2c , R ^2d , R ^3b , R ^3c and R ^3d are the same or different and each represents a hydrogen atom, a hydroxyl group, an alkyl group, an alkoxy group, a cycloalkyl group, an amino group, or an adamantyl group. R ^2b and R ^2c , R ^2c and R ^2d , R ^3b and R ^3c , and R ^3c and R ^3d may be joined together at least at one position to form an aliphatic ring.]
Or general formula (1B'1):

[In the formula, R ^4b , R ^4c , R ^5b and R ^5c are the same or different and each represents a hydrogen atom, a hydroxyl group, an alkyl group, an alkoxy group, a cycloalkyl group, an amino group, or an adamantyl group. R ^4b and R ^4c , and R ^5b and R ^5c may be joined together at least at one position to form an aliphatic ring.]
Item 5. The diamondoid compound according to any one of items 1 to 4, which is a compound represented by the formula:

Item 6. A method for producing the diamondoid compound according to any one of items 1 to 5, comprising the steps of:
(II) General formula (2):

[In the formula, R ¹ and n are the same as defined above. Ring A ¹ ' represents an aromatic ring corresponding to ring A ^1. ]
The method includes a step of hydrogenating an adamantane-fused aromatic compound represented by the following formula (1):
The method of the present invention, wherein the catalyst comprises a catalyst containing rhodium and platinum, and a catalyst containing scandium.

Item 7. The method according to Item 6, wherein the Lewis acid catalyst has an element of Group 3, Group 13, or Group 14 of the periodic table as the active center.

Item 8. The method according to item 6 or 7, wherein step (II) is carried out in the presence of an organic solvent.

Item 9. The method according to Item 8, wherein the organic solvent is an alkane.

Item 10. The adamantane-fused aromatic compound is
(IA) General formula (4):

[In the formula, ring A ¹ ' represents an aromatic ring corresponding to ring A ¹ and ring A ¹ '. X ¹ represents a halogen atom.]
and then reacting an aromatic compound represented by the general formula (5A) or (5B):

[In the formula, R ¹ and n are the same as above.]
and reacting the compound with an adamantanone compound represented by the formula:
General formula (6):

[In the formula, A ¹ ″, R ¹ and n are the same as defined above.]
and (IB) a step of reacting the adamantane-containing arene compound obtained in the step (IA) with a Brønsted acid and/or a Lewis acid.

Item 11. The method according to Item 10, wherein the nucleophile is an organolithium compound and/or an organomagnesium compound.

Item 12. The aromatic compound represented by the general formula (4) is
General formula (4A):

[In the formula, ^X1 is the same as defined above. Ring ^A2' and ring ^A3' may be the same or different and each represent an aromatic ring. ^R2a and ^R3a may be the same or different and each represent a hydrogen atom, a hydroxyl group, an alkyl group, an alkoxy group, a cycloalkyl group, an amino group, or an adamantyl group. ^R2a and ^R3a may be joined together to form an aromatic ring.]
Or general formula (4B):

[In the formula, ring ^A4 and ring ^A5 are the same or different and represent an aromatic ring. ^X2 represents a halogen atom. ^R4a and ^R5a are the same or different and represent a hydrogen atom, a hydroxyl group, an alkyl group, an alkoxy group, a cycloalkyl group, an amino group, or an adamantyl group. ^R4a and ^R5a may be joined together to form an aromatic ring.]
Item 12. The method according to item 10 or 11, wherein the compound is represented by the formula:

The present invention makes it possible to precisely synthesize a variety of new diamondoid compounds.

In this specification, "containing" is a concept that encompasses all of "comprise," "consist essentially of," and "consist of."

In addition, in this specification, when a numerical range is indicated as "A to B," it means A or more and B or less.

1. Diamondoid Compound The diamondoid compound of the present invention has the general formula (1):

[In the formula, ring ^A1 represents an aliphatic ring having two or more rings; ^R1 represents a hydrogen atom, an alkyl group, a cycloalkyl group, or an adamantyl group; and n represents an integer of 0 to 3.]
It is a compound represented by the formula:

The alkyl group represented by ^R1 is not particularly limited, and either a linear alkyl group or a branched alkyl group can be used. Examples of the alkyl group include alkyl groups having 1 to 6 carbon atoms (particularly 1 to 4 carbon atoms), such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, and a tert-butyl group.

These alkyl groups may also have a substituent. Examples of the substituent that the alkyl group may have include a hydroxyl group, an alkoxy group as described below, a cycloalkyl group as described below, an amino group as described below, and an adamantyl group. When the alkyl group has a substituent, the number of the substituents may be, for example, 1 to 6, and particularly 1 to 3.

The cycloalkyl group represented by R ¹ is not particularly limited, and examples thereof include cycloalkyl groups having 3 to 10 carbon atoms (particularly 4 to 8 carbon atoms), such as cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, and cycloheptyl group.

These cycloalkyl groups may also have a substituent. Examples of the substituent that the cycloalkyl group may have include a hydroxyl group, the alkyl groups described above, the alkoxy groups described below, the amino groups described below, and an adamantyl group. When the cycloalkyl group has a substituent, the number of the substituents may be, for example, 1 to 6, and particularly 1 to 3.

The adamantyl group represented by R ¹ is not particularly limited, and examples thereof include a 1-adamantyl group and a 2-adamantyl group.

These adamantyl groups may also have a substituent. Examples of the substituent that the adamantyl group may have include a hydroxyl group, the alkyl group described above, the alkoxy group described below, the cycloalkyl group described above, the amino group described below, and the adamantyl group described above. When the adamantyl group has a substituent, the number of the substituents may be, for example, 1 to 6, and particularly 1 to 3.

The number of ^R1 is not particularly limited and can be, for example, an integer of 0 to 3, preferably an integer of 0 to 2, and more preferably 0 or 1. The substitution position when ^R1 is present is not particularly limited and various substitution positions can be adopted. For example, when ^R1 is 3, the adamantane ring portion is represented by the general formula (7):

[In the formula, R ^1a , R ^1b and R ^1c are the same or different and each represents a hydrogen atom, an alkyl group, a cycloalkyl group, or an adamantyl group.]
It is also possible to use a structure represented by the following formula:

In the general formula (7), the alkyl group, cycloalkyl group and adamantyl group represented by R ^1a , R ^1b and R ^1c may be the same as those described above. The same applies to the type and number of the substituents.

In addition, the ring ^A1 is not particularly limited as long as it is an aliphatic ring having two or more rings, and various aliphatic rings can be used. As the aliphatic ring, any of an aliphatic hydrocarbon ring and a heteroaliphatic ring can be used, and it can be a ring in which two or more (e.g., 2 to 1000 rings, particularly 2 to 100 rings) of a cycloalkane ring (cyclohexane ring), an adamantane ring, a heteroaliphatic ring (piperidine ring, tetrahydropyran ring, pyrrolidine ring, tetrahydrofuran ring, tetrahydrothiophene ring, etc.) are combined, such as, for example,

These include:

The above-mentioned ring A ¹ may have a substituent. Examples of the substituent that the ring A ¹ may have include a hydroxyl group, the above-mentioned alkyl group, the below-mentioned alkoxy group, the above-mentioned cycloalkyl group, the below-mentioned amino group, and an adamantyl group. When the ring A ¹ has a substituent, the number of the substituents may be, for example, 1 to 6, and particularly 1 to 3.

From the above, the diamondoid compound of the present invention is classified according to the structure of ring ^A1 and has the general formula (1A):

[Wherein, ring ^A4 and ring ^A5 are the same or different and represent an aliphatic ring. ^R1a , ^R1b and ^R1c are the same or different and represent a hydrogen atom, an alkyl group, a cycloalkyl group, or an adamantyl group. ^R4a and ^R5a are the same or different and represent a hydrogen atom, a hydroxyl group, an alkyl group, an alkoxy group, a cycloalkyl group, an amino group, or an adamantyl group. ^R4a and ^R5a may be joined together to form an aliphatic ring.]
The compound may also be represented by the following formula:

In the general formulae (1A) and (1B), the alkyl group, cycloalkyl group and adamantyl group represented by R ^1a , R ^1b and R ^1c may be the same as those described above. The same applies to the types and numbers of the substituents.

In the general formula (1A), the alkyl group, cycloalkyl group and adamantyl group represented by ^R2a and ^R3a may be the same as those described above. The same applies to the type and number of the substituents.

In general formula (1A), the alkoxy group represented by R ^2a and R ^3a is not particularly limited, and examples thereof include alkoxy groups having 1 to 6 carbon atoms (particularly 1 to 4 carbon atoms), such as a methoxy group, an ethoxy group, an n-propyloxy group, an isopropyloxy group, an n-butyloxy group, an isobutyloxy group, a sec-butyloxy group, and a tert-butyloxy group.

These alkyl groups may also have a substituent. Examples of the substituent that the alkoxy group may have include a hydroxyl group, the alkyl group described above, the alkoxy group described above, the cycloalkyl group described above, the amino group described below, and an adamantyl group. When the alkoxy group has a substituent, the number of the substituents may be, for example, 1 to 6, and particularly 1 to 3.

In general formula (1A), the amino groups represented by R ^2a and R ^3a may also have a substituent. Examples of the substituent that the amino group may have include a hydroxyl group, the above alkyl group, the above alkoxy group, the above cycloalkyl group, and an adamantyl group. When the amino group has a substituent, the number of the substituents may be, for example, 1 to 6, and particularly 1 to 3.

In the general formula (1B), the alkyl group, alkoxy group, cycloalkyl group, amino group and adamantyl group represented by ^R4a and ^R5a may be the same as those described above. The same applies to the type and number of the substituents.

In general formula (1A), the aliphatic ring represented by ring ^A2 and ring ^A3 is not particularly limited, and may be either an aliphatic hydrocarbon ring or a heteroaliphatic ring. The aliphatic ring may be a cycloalkane ring (cyclohexane ring), an adamantane ring, a heteroaliphatic ring (piperidine ring, tetrahydropyran ring, pyrrolidine ring, tetrahydrofuran ring, etc.), or a ring using two or more (e.g., 1 to 1000 rings, particularly 1 to 100 rings), for example:

These include:

The aliphatic rings represented by the rings ^A2 and ^A3 may have a substituent. Examples of the substituent that the aliphatic rings represented by the rings ^A2 and ^A3 may have include a hydroxyl group, a halogen atom described below, the alkyl group, the alkoxy group, the cycloalkyl group, the amino group, the adamantyl group, etc. When the ring ^A1 has a substituent, the number of the substituents may be, for example, 1 to 6, particularly 1 to 3.

In the general formula (1B), the aliphatic rings represented by ring ^A4 and ring ^A5 can be those described above for ring ^A2 and ring ^A3 . The same applies to the types and numbers of the substituents.

In addition, in general formula (1A), ^R2a and ^R3a may be joined together to form an aliphatic ring. In this case, the aliphatic ring formed may be the same as that described above for ring ^A2 and ring ^A3 . The same applies to the type and number of the substituents.

In addition, in general formula (1B), ^R4a and ^R5a may combine together to form an aliphatic ring. In this case, the aliphatic ring formed may be the same as that described above for ring ^A2 and ring ^A3 . The same applies to the type and number of the substituents.

From the above, when ring ^A2 and ring ^A3 in general formula (1A), and ring ^A4 and ring ^A5 in general formula (1B) are all cyclohexane rings, the diamondoid compound of the present invention is represented by general formula (1A1):

[In the formula, R ^4a , R ^4b , R ^4c , R ^5a , R ^5b and R ^5c are the same or different and each represents a hydrogen atom, a hydroxyl group, an alkyl group, an alkoxy group, a cycloalkyl group, an amino group, or an adamantyl group. R ^4a and R ^4b , R ^4b and R ^4c , R ^5a and R ^5b , R ^5b and R ^5c , and R ^4a and R ^5a may be joined together to form an aliphatic ring at least at one position.]
It is also possible to use a compound represented by the following formula:

In the general formula (1A1), the alkyl group, alkoxy group, cycloalkyl group, amino group and adamantyl group represented by ^R2a , ^R2b , ^R2c , ^R2d , ^R3a , ^R3b , ^R3c and ^R3d may be the same as those described above. The same applies to the type and number of the substituents.

In the general formula (1B1), the alkyl group, alkoxy group, cycloalkyl group, amino group and adamantyl group represented by R ^4a , R ^4b , R ^4c , R ^5a , R ^5b and R ^5c may be the same as those described above. The same applies to the types and numbers of the substituents.

In ^addition , in general formula (1A1), ^R2a and ^R2b , ^R2b and R2c, ^R2c and ^R2d , ^R3a and ^R3b , ^R3b and ^R3c , ^R3c and ^R3d , and ^R2a and ^R3a can be joined together at least one position to form an aliphatic ring. The aliphatic ring formed in this case can be the one described in the above ring ^A2 and ring ^A3 . The same applies to the type and number of the substituent.

In addition, in general formula (1B1), ^R4a and ^R4b , ^R4b and ^R4c , ^R5a and ^R5b , ^R5b and ^R5c , and ^R4a and ^R5a can be joined together at least one position to form an aliphatic ring. The aliphatic ring formed in this case can be the one described above for ring ^A2 and ring ^A3 . The same applies to the type and number of the substituent.

In addition, when ring ^A1 is an aliphatic ring to which an adamantane ring is condensed, the diamondoid compound of the present invention can be said to be a compound having two or more adamantane rings. In this case, the diamondoid compound of the present invention can be, for example, a compound represented by the general formula (1A'):

[In the formula, ring ^A4 and ring ^A5 are the same or different and represent an aliphatic ring. ^R1a , ^R1b , ^R1c , ^R1d , ^R1e , and ^R1f are the same or different and represent a hydrogen atom, an alkyl group, a cycloalkyl group, or an adamantyl group.]
It is also possible to use a compound represented by the following formula:

In the general formula (1A'), the alkyl group, cycloalkyl group and adamantyl group represented by R ^1a , R ^1b , R ^1c , R ^1d , R ^1e and R ^1f may be the same as those described above. The same applies to the type and number of the substituents.

In the general formula (1B'), the alkyl group, cycloalkyl group and adamantyl group represented by R ^1a , R ^1b , R ^1c , R ^1d , R ^1e and R ^1f may be the same as those described above. The same applies to the type and number of the substituents.

In the general formula (1A'), the aliphatic rings represented by ring ^A2 and ring ^A3 can be those described for ring ^A2 and ring ^A3 in the general formula (1A) above. The same applies to the types and numbers of the substituents.

In the general formula (1B'), the aliphatic rings represented by ring ^A4 and ring ^A5 can be those described for ring ^A2 and ring ^A3 in the general formula (1A) above. The same applies to the types and numbers of the substituents.

In addition, when ring ^A1 is an aliphatic ring condensed with an adamantane ring, and ring ^A2 and ring ^A3 in general formula (1A), and ring ^A4 and ring ^A5 in general formula (1B) are all cyclohexane rings, the diamondoid compound of the present invention can be said to be a compound in which two or more adamantane rings are condensed to a structure in which at least four aliphatic rings are condensed.In this case, the diamondoid compound of the present invention is represented by general formula (1A'1):

[In the formula, R ^4b , R ^4c , R ^5b and R ^5c are the same or different and each represents a hydrogen atom, a hydroxyl group, an alkyl group, an alkoxy group, a cycloalkyl group, an amino group, or an adamantyl group. R ^4b and R ^4c , and R ^5b and R ^5c may be joined together at least at one position to form an aliphatic ring.]
The compound may also be represented by the following formula:

In the general formula (1A'1), the alkyl group, alkoxy group, cycloalkyl group, amino group and adamantyl group represented by ^R2b , ^R2c , ^R2d , ^R3b , ^R3c and ^R3d may be the same as those described above. The same applies to the type and number of the substituents.

In the general formula (1B'1), the alkyl group, alkoxy group, cycloalkyl group, amino group and adamantyl group represented by ^R4b , ^R4c , ^R5b and ^R5c may be the same as those described above. The same applies to the type and number of the substituents.

In addition, in general formula (1A'1), ^R2b and ^R2c , ^R2c and ^R2d , ^R3b and ^R3c , and ^R3c and ^R3d can be joined together at least one position to form an aliphatic ring. The aliphatic ring formed in this case can be the same as that described above for ring ^A2 and ring ^A3 . The same applies to the type and number of substituents.

In addition, in general formula (1B'1), R ^4b and R ^4c , and R ^5b and R ^5c can be joined together at least one position to form an aliphatic ring. The aliphatic ring formed in this case can be one described above for ring A ² and ring A ^3. The same applies to the type and number of the substituents.

The diamondoid compounds of the present invention that satisfy the above conditions are specifically

These include:

These diamondoid compounds of the present invention can be used in applications generally used for nanodiamonds and known diamondoid compounds, such as electron emission materials, power semiconductors, organic electronics, and bioactive substances that take advantage of their low toxicity and novel structure. Specifically, they can be used for applications such as photoresist materials for fine semiconductors, heat conductive materials (such as heat conductive nanowires), heat conductive films, power semiconductor devices, diamond synthesis seed materials, diamond semiconductors, industrial diamonds, biologically active substances, drug discovery, and highly flexible materials.

2. Method for Producing Diamondoid Compound The diamondoid compound of the present invention can be produced, for example, by
(II) General formula (2):

[In the formula, R ¹ and n are the same as defined above. Ring A ¹ ' represents an aromatic ring corresponding to ring A ^1. ]
The adamantane-fused aromatic compound represented by the following formula (1) can be produced by a production method including a step of hydrogenating an adamantane-fused aromatic compound represented by the following formula (1): in the presence of a catalyst. The catalyst used in this step contains a catalyst containing rhodium and platinum, and a catalyst containing scandium.

(2-1) Adamantane-fused aromatic compound In the general formula (1), R ¹ and n can be as described above. In other words, the structure of the adamantane ring portion in the adamantane-fused aromatic compound can be the same as the structure of the adamantane ring portion in the diamondoid compound of the present invention.

In addition, in formula (1), ring A ¹ ' represents an aromatic ring corresponding to ring A ¹ described above.

That is, the ring A ^1' is not particularly limited as long as it is an aromatic ring having two or more rings, and various aromatic rings can be adopted. The aromatic ring can be a ring obtained by combining two or more (e.g., 2 to 1000, particularly 2 to 100) aromatic hydrocarbon rings (such as a benzene ring) and heteroaromatic rings (such as a pyridine ring, a pyrazine ring, a pyrrole ring, a furan ring, a thiophene ring, an imidazole ring, a pyrazole ring, an oxazole ring, a thiazole ring, etc.). The ring A ^1' can also be a structure consisting of only the aromatic rings described above, or a ring obtained by combining a total of two or more (e.g., 2 to 1000, particularly 2 to 100) of the aromatic rings and the aliphatic rings described above.

That is, ring A ^1′ is, for example,

These include:

The above-mentioned ring A ^1' may have a substituent. Examples of the substituent that the ring A ^1' may have include the above-mentioned halogen atom, the above-mentioned alkyl group, the above-mentioned cycloalkyl group, the above-mentioned adamantyl group, etc. When the ring A ^1' has a substituent, the number of the substituents may be, for example, 1 to 6, particularly 1 to 3.

For this reason, adamantane-fused aromatic compounds are classified according to the structure of ring ^A1' and are represented by the general formula (2A):

[In the formula, R ^1a , R ^1b and R ^1c are the same as defined above. Ring A ^2′ and ring A ^3′ are aromatic rings corresponding to ring A ² and ring A ³ , respectively.]
Or general formula (2B):

[In the formula, R ^1a , R ^1b and R ^1c are the same as defined above. Ring A ^4′ and ring A ^5′ represent aromatic rings corresponding to ring A ⁴ and ring A ⁵ , respectively.]
The compound may also be represented by the following formula:

In general formula (2A), the aromatic rings represented by ring A2 ^' and ring A3 ^' are not particularly limited, and may be a ring using a single aromatic hydrocarbon ring (such as a benzene ring) and a heteroaromatic ring (such as a pyridine ring, a pyrazine ring, a pyrrole ring, a furan ring, a thiophene ring, an imidazole ring, a pyrazole ring, an oxazole ring, a thiazole ring, etc.), or two or more (e.g., 1 to 1000, particularly 1 to 100) of them. Ring A2 ^' and ring A3 ^' may also be a structure consisting of only the aromatic ring described above, or may be a ring combining a total of two or more (e.g., 2 to 1000, particularly 2 to 100) of the aromatic ring and the aliphatic ring described above.

Examples of the aromatic ring represented by ring A2 ^' and ring A3 ^' include

These include:

The aromatic rings represented by the rings A2 ^' and ^{A3' may have a substituent. Examples of the substituents that the aromatic rings represented by the rings A2' and A3} ^' may have include the above-mentioned halogen atoms, alkyl groups, cycloalkyl groups, and adamantyl groups. When the rings ^A2' ^and A3 ^' have a substituent, the number of the substituents may be, for example, 1 to 6, and particularly 1 to 3.

In the general formula (2B), the aromatic rings represented by ring ^A4' and ring A5 ^' may be those described above for ring ^A2' and ring A3 ^' . The same applies to the types and numbers of the substituents.

When ring A ^2′ and ring A ^3′ in general formula (2A) and ring A ^4′ and ring A ^5′ in general formula (2B) are all benzene rings, the adamantane-fused aromatic compound can be represented by general formula (2A1):

[In the formula, R ^2a , R ^2b , R ^2c , R ^2d , R ^3a , R ^3b , R ^3c and R ^3d are the same as above.]
Or general formula (2B1):

[In the formula, R ^4a , R ^4b , R ^4c , R ^5a , R ^5b and R ^5c are the same as above.]
It is also possible to use a compound represented by the following formula:

Furthermore, when ring A ^1′ is an aromatic ring to which an adamantane ring is fused, the adamantane-fused aromatic compound can be said to be a compound having two or more adamantane rings. In this case, the adamantane-fused aromatic compound can be, for example, a compound represented by the general formula (2A′):

[In the formula, ring A ^2′ , ring A ^3′ , R ^1a , R ^1b , R ^1c , R ^1d , R ^1e and R ^1f are the same as defined above.]
Or general formula (2B'):

[In the formula, ring A ^4′ , ring A ^5′ , R ^1a , R ^1b , R ^1c , R ^1d , R ^1e and R ^1f are the same as defined above.]
It is also possible to use a compound represented by the following formula:

In addition, when ring ^A1' is an aromatic ring fused with an adamantane ring, and ring A2 ^' and ring A3 ^' in general formula (2A) and ring ^A4' and ring A5 ^' in general formula (2B) are all benzene rings, the adamantane-fused aromatic compound can be said to be a compound in which two or more adamantane rings are fused to a structure in which at least four rings are fused. In this case, the adamantane-fused aromatic compound is represented by general formula (2A'1):

[In the formula, R ^2b , R ^2c , R ^2d , R ^3b , R ^3c and R ^3d are the same as above.]
Or general formula (2B'1):

[In the formula, R ^4b , R ^4c , R ^5b and R ^5c are the same as above.]
The compound may also be represented by the following formula:

Specific examples of adamantane-fused aromatic compounds that satisfy the above conditions are:

These include:

The method for producing such adamantane-fused aromatic compounds will be described in detail later.

(2-2) Catalyst In the present invention, the catalyst used in the step (II) contains a catalyst containing rhodium and platinum, and a Lewis acid catalyst.

Catalyst containing rhodium and platinum In the catalyst containing rhodium and platinum, the molar ratio of rhodium and platinum is not particularly limited, but from the viewpoints of reaction conversion rate, yield, selectivity, etc., the catalyst contains preferably 0.10 to 2.00 mol of platinum per mol of rhodium, more preferably 0.15 to 1.00 mol, and even more preferably 0.20 to 0.50 mol.

The catalyst containing rhodium and platinum is not particularly limited as long as it contains rhodium and platinum, but it is preferable that the rhodium and platinum are supported on a carrier.

Such a carrier is not particularly limited, but from the viewpoint of reaction conversion rate, yield, selectivity, etc., a carrier containing polysilane and alumina (composite carrier) is preferable.

There are no particular limitations on the polysilane, and examples of the polysilane that can be used include polydialkylsilanes such as polydimethylsilane and polydiethylsilane; polyalkylarylsilanes such as polymethylphenylsilane and polyethylphenylsilane; and known or commercially available products can be used.

There are no particular limitations on the alumina, and any publicly known or commercially available product can be used.

When rhodium and platinum are supported on a carrier, there are no particular limitations on the amount supported, but for example, it is preferable that rhodium is 0.04 to 5.00 mmol/g (particularly 0.05 to 2.00 mmol/g) and platinum is 0.005 to 0.05 mmol/g (particularly 0.01 to 0.04 mmol/g).

Such rhodium and platinum-containing catalysts can be publicly known or commercially available products, or can be synthesized by the method described in J. Am. Chem. Soc. 2018, 140, 11325-11334.

The amount of the catalyst containing rhodium and platinum used is not particularly limited, but from the viewpoint of reaction conversion rate, yield, selectivity, etc., it is preferably 0.05 to 1 mol, more preferably 0.06 to 0.5 mol, even more preferably 0.07 to 0.3 mol, and particularly preferably 0.08 to 2 mol per 1 mol of the raw material adamantane fused aromatic compound.

Lewis Acid Catalyst In the present invention, the use of both a catalyst containing rhodium and platinum and a Lewis acid catalyst can synergistically improve the catalytic activity.

The Lewis acid catalyst used in the present invention is not particularly limited, but from the viewpoint of reaction conversion rate, yield, selectivity, etc., it is preferable that the Lewis acid catalyst has an element of Group 3, Group 13, or Group 14 of the periodic table as the active center.

Examples of elements in Group 3, 13, or 14 of the periodic table include scandium (Sc), zinc (Zn), yttrium (Y), indium (In), lanthanum (La), cerium (Ce), praseodymium (Pr), neodymium (Nd), samarium (Sm), europium (Eu), gadolinium (Gd), terbium (Tb), dysprosium (Dy), holmium (Ho), erbium (Er), thulium (Tm), ytterbium (Yb), and lutetium (Lu). Among these, rare earth elements (elements in Group 3 of the periodic table) are preferred, and scandium is more preferred.

Furthermore, by employing a strong electron-withdrawing group, the catalytic activity of the Lewis acid can be increased. Examples of electron-withdrawing groups used for this purpose include the trifluoromethanesulfonyl group (hereinafter sometimes referred to as the "OTf group"), the methanesulfonyl group, various substituted benzenesulfonyl groups, and the trifluoroacetyl group.

Specific examples of Lewis acid catalysts that can be used in the present invention include scandium(III) trifluoromethanesulfonate, zinc(II) trifluoromethanesulfonate, indium(III) trifluoromethanesulfonate, ytterbium(III) trifluoromethanesulfonate, etc., with scandium(III) trifluoromethanesulfonate, indium(III) trifluoromethanesulfonate, ytterbium(III) trifluoromethanesulfonate, etc. being preferred, with scandium(III) trifluoromethanesulfonate, ytterbium(III) trifluoromethanesulfonate, etc. being more preferred, with scandium(III) trifluoromethanesulfonate being even more preferred. These Lewis acid catalysts can be used alone or in combination of two or more.

The amount of Lewis acid catalyst used is not particularly limited, but from the viewpoint of reaction conversion rate, yield, selectivity, etc., it is preferably 0.05 to 1 mol, more preferably 0.06 to 0.5 mol, even more preferably 0.07 to 0.3 mol, and particularly preferably 0.08 to 2 mol per 1 mol of the raw material adamantane-fused aromatic compound.

(2-3) Solvent In the present invention, the step (II) can usually be carried out in an organic solvent.

There are no particular limitations on the organic solvents that can be used, but from the standpoint of reaction conversion rate, yield, selectivity, etc., alkanes are preferred, and specific examples include hexane, heptane, and octane. These organic solvents can be used alone or in combination of two or more types.

The amount of these organic solvents used is not particularly limited and can be the amount of solvent.

(2-4) Hydrogenation In the present invention, in the step (II), the adamantane-fused aromatic compound can usually be hydrogenated by contacting a hydrogen-containing gas such as hydrogen gas with the adamantane-fused aromatic compound.

Specifically, the atmosphere in the system can be a hydrogen-containing gas atmosphere such as hydrogen gas. In this case, the pressure of the hydrogen-containing gas atmosphere such as hydrogen gas is not particularly limited, but from the viewpoint of the conversion rate, yield, selectivity, etc. of the reaction, it is preferably 0.1 to 10 MPa, more preferably 0.2 to 5 MPa, and even more preferably 0.3 to 2 MPa.

(2-5) Other Conditions This reaction can be carried out usually at 80 to 200° C., preferably 100 to 150° C. In addition, this reaction can be carried out usually for 1 to 200 hours, preferably 10 to 150 hours, more preferably 50 to 100 hours.

After the reaction is completed, the diamondoid compound of the present invention can be obtained by purifying it by a conventional method as necessary. Specifically, for example, an organic solvent (such as ethyl acetate) can be added to the reaction mixture to dissolve the organic matter in the organic layer, and then the metal catalyst can be adsorbed by silica gel and purified by gel filtration chromatography.

3. Method for Producing Adamantane-Fused Aromatic Compound The adamantane-fused aromatic compound used as a raw material in the above step (II) is, for example,
(IA) General formula (4):

[In the formula, ring A ^1″ represents an aromatic ring corresponding to ring A ¹ and ring A ¹ ′, and X ¹ represents a halogen atom.]
and then reacting an aromatic compound represented by the general formula (5A) or (5B):

(3-1) Step (IA)
Aromatic Compound (General Formula (4))
In the general formula (4), examples of the halogen atom represented by X ¹ include a chlorine atom, a bromine atom, and an iodine atom.

In addition, in formula (4), ring A ^1″ represents an aromatic ring corresponding to ring A ¹ and ring A ¹ ′.

In other words, ring ^A1" is not particularly limited as long as it is an aromatic ring having two or more rings, and various aromatic rings can be adopted. The aromatic ring can be a ring obtained by combining two or more (e.g., 2 to 1000 rings, particularly 2 to 100 rings) aromatic hydrocarbon rings (such as a benzene ring) and heteroaromatic rings (such as a pyridine ring, a pyrazine ring, a pyrrole ring, a furan ring, a thiophene ring, an imidazole ring, a pyrazole ring, an oxazole ring, a thiazole ring, etc.). Ring A1 ^" can also have a structure consisting of only the above-mentioned aromatic ring, or can be a ring obtained by combining a total of two or more (e.g., 2 to 1000 rings, particularly 2 to 100 rings) of the above-mentioned aromatic rings and the above-mentioned aliphatic rings.

That is, ring A ^1″ is, for example,

These include:

The above-mentioned ring ^A1" may also have a substituent. Examples of the substituent that ring A1 ^" may have include the above-mentioned halogen atoms, the above-mentioned alkyl groups, the above-mentioned cycloalkyl groups, the above-mentioned adamantyl groups and adamantanonyl groups. When ring A1 ^" has a substituent, the number of the substituents may be, for example, 1 to 6, particularly 1 to 3.

From the above, the aromatic compounds used as raw materials are specifically:

These include:

The aromatic compounds used as raw materials can be publicly known or commercially available products.

The nucleophile is not particularly limited, and any nucleophile capable of inducing the Friedel-Crafts reaction can be used. Among them, organolithium compounds, organomagnesium compounds, etc. are preferred from the viewpoints of the conversion rate, yield, selectivity, etc. of the reaction.

The organolithium compound is not particularly limited, and known compounds can be used, such as alkyllithiums such as methyllithium, ethyllithium, n-propyllithium, isopropyllithium, n-butyllithium, sec-butyllithium, tert-butyllithium, n-pentyllithium, and n-hexyllithium; cycloalkyllithiums such as cyclohexyllithium; and aryllithiums such as phenyllithium. These organolithium compounds can be used alone or in combination of two or more. Of these, in this step, alkyllithiums are preferred, and n-butyllithium is more preferred, from the standpoint of reaction conversion rate, yield, selectivity, and the like.

Examples of organic magnesium compounds include alkyl magnesium halides such as methyl magnesium chloride, methyl magnesium bromide, n-butyl magnesium chloride, n-butyl magnesium bromide, n-hexyl magnesium chloride, and n-hexyl magnesium bromide; phenyl magnesium chloride, phenyl magnesium bromide, 4-n-butylphenyl magnesium chloride, and 4-n-butylphenyl magnesium bromide.

These nucleophiles can be used alone or in combination of two or more.

The amount of nucleophile used is not particularly limited, but from the viewpoint of reaction conversion rate, yield, selectivity, etc., it is preferably 0.2 to 5.0 moles, more preferably 0.3 to 3.0 moles, and even more preferably 0.5 to 2.0 moles per mole of the aromatic compound raw material. When multiple nucleophiles are used, it is preferable to adjust the total amount so that it is within the above range.

Adamantanone Compound (General Formula (5A) or (5B))
Specific examples of the adamantanone compound that can be used include:

These include:

The amount of the adamantanone compound used is not particularly limited, but from the viewpoint of reaction conversion rate, yield, selectivity, etc., it is preferably 0.2 to 5.0 moles, more preferably 0.3 to 3.0 moles, and even more preferably 0.5 to 2.0 moles per mole of the aromatic compound as the raw material.

Solvent In the present invention, step (IA) can usually be carried out in an organic solvent.

The organic solvent that can be used is not particularly limited, but from the viewpoints of the conversion rate, yield, selectivity, etc. of the reaction, hydrocarbons, ethers, etc. are preferred. Examples of the hydrocarbons include aliphatic saturated hydrocarbons such as pentane, hexane, heptane, etc.; and aromatic hydrocarbons such as benzene. Examples of the ethers include 1,4-dioxane, tetrahydrofuran, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, etc. Among these, from the viewpoints of the conversion rate, yield, selectivity, etc. of the reaction, ethers are preferred, and tetrahydrofuran is more preferred. These organic solvents can be used alone or in combination of two or more kinds.

Other Conditions In this step, the reaction between the aromatic compound as a raw material and the nucleophile can be carried out usually at −120 to −30° C., preferably −100 to −50° C., and the subsequent reaction with the adamantanone compound can be carried out usually at 0 to 70° C., preferably 10 to 50° C. Furthermore, in this step, the reaction between the aromatic compound as a raw material and the nucleophile can be carried out usually for 1 minute to 10 hours, preferably 5 minutes to 5 hours, more preferably 10 minutes to 3 hours, and the subsequent reaction with the adamantanone compound can be carried out usually for 1 to 100 hours, preferably 2 to 50 hours, more preferably 5 to 30 hours.

After this step is completed, the adamantane-containing arene compound can be obtained by purifying it by a conventional method as necessary. Specifically, for example, an organic solvent (such as ethyl acetate) can be added to the reaction mixture to dissolve the organic matter in the organic layer, and then the metal compound can be adsorbed by silica gel and purified by gel filtration chromatography.

(3-2) Step (IB)
Adamantane-containing arene compound (general formula (6))
The adamantane-containing arene compound is a compound obtained by the above-mentioned general formula (IA), specifically,

These include:

Bronsted acid and/or Lewis acid There is no particular limitation on the Bronsted acid and/or Lewis acid, and various acids can be used. For example,
Inorganic acids such as sulfuric acid, nitric acid, phosphoric acid, polyphosphoric acid, hydrogen fluoride (HF), hydrofluoric acid, hydrochloric acid, hydrogen bromide, hydrogen iodide, hypochlorous acid, chlorous acid, chloric acid, perchloric acid, perbromic acid, and periodic acid;
Sulfonic acids such as fluorosulfonic acid, chlorosulfonic acid, methanesulfonic acid, ethanesulfonic acid, trifluoromethanesulfonic acid, difluoromethanesulfonic acid, trichloromethanesulfonic acid, perfluorobutanesulfonic acid, perfluorooctane sulfonic acid, benzenesulfonic acid, toluenesulfonic acid, and nitrobenzenesulfonic acid;
Mono- or polycarboxylic acids such as formic acid, acetic acid, propionic acid, monochloroacetic acid, dichloroacetic acid, trichloroacetic acid, fluoroacetic acid, difluoroacetic acid, trifluoroacetic acid, glycolic acid, lactic acid, benzoic acid, oxalic acid, and succinic acid;
Lewis acids such as _SO3 , _BF3 , _BCl3 , B( _OCH3 ) ₃ , _AlCl3 , _AlBr3 , _SbF3 , _SbCl3 , _SbF5 , _PF3 , _PF5 , _AsF3 , _AsCl3 , _AsF5 , _TiCl4 , _NbF5 , _TaF5 ;
Examples of the acid include acids composed of Lewis acid and hydrogen halide, such as HBF ₄ , HPF ₆ , HAsF ₆ , HSbF ₆ , and HSbCl _6. These acids can be used alone or in combination of two or more. Among them, from the viewpoint of reaction conversion rate, yield, selectivity, etc., Bronsted acid is preferred, mono- or polycarboxylic acid is more preferred, mono- or polyfluoroacetic acid is even more preferred, and trifluoroacetic acid is particularly preferred. In this specification, the term refers to a compound that is not an acid according to the Bronsted definition, but is an acid according to the Lewis definition.

The amount of Bronsted acid and/or Lewis acid used is not particularly limited, but from the viewpoint of reaction conversion rate, yield, selectivity, etc., it is preferably 0.2 to 5.0 moles, more preferably 0.3 to 3.0 moles, and even more preferably 0.5 to 2.0 moles per mole of the raw material adamantane-containing arene compound. When the Bronsted acid and/or Lewis acid is liquid, the amount used can be the amount of solvent. When multiple Bronsted acids and/or Lewis acids are used, it is preferable to adjust the total amount to be within the above range.

Solvent In the present invention, step (IB) can usually be carried out in an organic solvent.

The organic solvents that can be used are not particularly limited, but from the viewpoints of the conversion rate, yield, selectivity, etc. of the reaction, hydrocarbons, halogenated hydrocarbons, ethers, etc. are preferred. Examples of the hydrocarbons include aliphatic hydrocarbons such as pentane, hexane, and heptane, and aromatic hydrocarbons such as benzene, toluene, and xylene. Examples of the halogenated hydrocarbons include chloroform, dichloroethane, trichloroethane, chlorobenzene, and dichlorobenzene. Examples of the ethers include 1,4-dioxane, tetrahydrofuran, ethylene glycol dimethyl ether, and ethylene glycol diethyl ether. Among them, from the viewpoints of the conversion rate, yield, selectivity, etc. of the reaction, halogenated hydrocarbons are preferred, and dichloroethane is more preferred. These organic solvents can be used alone or in combination of two or more.

Other Conditions This step can be carried out usually at 40 to 100° C., preferably 50 to 90° C. In addition, this step can be carried out usually for 5 minutes to 10 hours, preferably 10 minutes to 8 hours, more preferably 30 minutes to 5 hours.

After this step is completed, the adamantane-fused aromatic compound can be obtained by purifying it by a conventional method as necessary. Specifically, for example, an organic solvent (such as ethyl acetate) can be added to the reaction mixture to dissolve the organic matter in the organic layer, and then impurities can be adsorbed by silica gel and purified by gel filtration chromatography.

The present invention will be specifically explained below with reference to examples, but the present invention is not limited in any way.

Unless otherwise specified, all reagents including dehydrated solvents were used as commercially available products without purification. Azulene, quinoline-8-boronic acid, 2-bromobiphenyl, 1-iodo-2-bromobenzene, 4-bromo-9,9-dimethyl-9H-fluorene, 4-bromo-9,9-diphenyl-9H-fluorene, 4-bromo-9,9'-spirobifluorene, 4-bromo-9-phenyl-9H-carbazole, 1-bromonaphthalene, 1-bromopyrene, 3-bromofluoranthene, 1,4-dibromonaphthalene, and 2-adamantanone were purchased from Tokyo Chemical Industry Co., Ltd. [IrCl(cod)] ₂ , [Ir(OMe)(cod)] ₂ , Pd(OAc) ₂ , pyrene-1-boronic acid, _B2pin2 , _PtBu3 , _Cs2CO3 , _K3PO4 , and _NOSbF6 were purchased from Sigma-Aldrich Co. LLC. _1,1,2,2 -Tetrachloroethane, _cyclohexane , and _hexane were purchased from Fujifilm Wako Pure Chemical Industries, Ltd. 2,2'-Dibromobiphenyl, 2-Bromo-2'-chloro-1,1'-biphenyl, 2-Bromo-1,1'-binaphthalene, 3-Bromo-4-phenylthiophene, and 3-Bromo-2,2'-bithiophene were synthesized according to procedures reported in the literature. All reactions were carried out under _N2 gas atmosphere in flame-dried glassware and dehydrated solvents using standard vacuum line techniques. Toluene, tetrahydrofuran (THF), and diethyl ether (Et ₂ O) used in the reactions were purified by passing through a solvent purification system (Glass Contour). All steps and purification procedures were carried out in air using reagent grade solvents. "rt" means 25°C. Analytical thin-layer chromatography (TLC) was performed using E. Merck silica gel 60 F254 precoated plates (0.25 mm). Chromatograms were analyzed with a UV lamp (254 nm or 365 nm). Flash column chromatography was performed on a Biotage Isolera equipped with KANTO Silica Gel 60N (spherical, neutral, 40-100 μm) or a Biotage SNAP Cartridge KP-Sil column. Preparative recycling gel permeation chromatography (GPC) was performed on a JAI LC-9260 II NEXT instrument equipped with a JAIGEL-2HR column using chloroform as the eluent. High resolution mass spectrometry (HRMS) was obtained on a JEOL JMS-T100TD (Direct Analysis in Real Time, DART), a JEOL JMS-T100GCV (Direct EI), and a Bruker Daltonics compact (ESI). Electron paramagnetic resonance (EPR) spectra were recorded on a JEOL ESR JES TE-200 instrument using a quartz Schlenk tube filled with argon. Nuclear magnetic resonance (NMR) spectra were recorded on a JEOL ECS-600 ( ^1H 600MHz, ^13C 150MHz) spectrometer or a JEOL ECS-500 ( ^1H 500MHz, ^13C 125MHz) spectrometer. ^1H NMR chemical shifts are expressed in parts per million (ppm) relative to _CDCl3 (7.26 ppm), _CD2Cl2 ( _5.34 ppm), or tetrachloroethane (TCE) _-d2 (5.94 ppm). ^13C NMR chemical shifts are expressed in ppm relative to _CDCl3 (77.16 ppm), _Cl2CDCl2 (73.78 ppm), or _CD2Cl2 (53.84 ppm). Data are reported as chemical shift, multiplicity (s = singlet, d = _doublet , dd = doublet of _doublets , t = triplet, td = triplet of doublets, q = quartet, dq = doublet of quartet, m = multiplet, brs = broad singlet, brd = broad doublet), coupling constant (Hz), and integration.

Synthesis Example 1

Synthesis of 2-(2-azulenyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (compound S1) Azulene (7.8 mmol, 1.00 g), cyclooctadiene iridium chloride dimer ([IrCl(cod)] ₂ ) (0.19 mmol, 131 mg, 3 mol%), 2,2'-bipyridyl (0.39 mmol, 60.4 mg, 6 mol%), and bis( _pinacolato )diboron ( _B2pin2 ) (4.3 mmol, 1.09 g, 0.55 equiv.) were added to a dry 100 mL two-neck flask. The flask was degassed, and then cyclohexane (50 mL) was added. The reaction mixture was stirred at 80°C for 29 h. After cooling to room temperature, water was added to the reaction mixture to quench the reaction, and the organic layer was extracted three times with ethyl acetate. The combined organic layers were dried _over _Na2SO4 and concentrated in vacuo. The crude product was purified by silica gel column chromatography (eluent: hexane/ethyl acetate = 100:0 to 80:20) to give 2-(2-azulenyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (compound S1) as a blue solid (971 mg, 57%). The ^1H NMR spectrum of compound S1 was consistent with the reported data.

Synthesis of 2-(2-bromophenyl)-azulene (compound S2) Compound S1 (2.68 mmol, 680 mg), 1-iodo-2-bromobenzene (5.35 mmol, 1.51 g, 2.0 equiv.), tris(dibenzylideneacetone)dipalladium(0) chloroform adduct (Pd ₂ (dba) ₃ ·CHCl ₃ ) (0.26 mmol, 282 mg, 10 mol%), and Cs ₂ CO ₃ (8.04 mmol, 2.62 g, 3.0 equiv.) were added to a dry 100 mL three-neck flask under open conditions. The flask was filled with argon, sealed, and placed in a glove box. A flask was charged with tri-tert-butylphosphine (P ^t Bu ₃ ) (0.26 mmol, 54.1 mg, 10 mol%), followed by the addition of toluene (15 mL), 1,4-dioxane (5 mL), and H ₂ O (5 mL). The reaction mixture was stirred at 100° C. for 19 h. After cooling to room temperature, the reaction mixture was quenched by adding water, and the organic layer was extracted three times with ethyl acetate. The combined organic layers were dried over Na ₂ SO ₄ and concentrated under vacuum. The crude product was purified by silica gel column chromatography (eluent: hexane) to obtain 2-(2-bromophenyl)azulene (compound S2) as a blue solid (462 mg, 62%).
^1H NMR (600 MHz, _CDCl3 ) δ8.38 (d, J = 9.6 Hz, 2H), 7.74 (dd, J = 8.4, 1.2 Hz, 1H), 7.65 (s, 2H), 7.57-7.62 (m, 2H), 7.41 (td, J = 6.0, 1.2 Hz, 1H), 7.19-7.23 (m, 3H).
^13C NMR (150 MHz, _CDCl3 ) δ 149.70, 140.14, 138.70, 137.30, 136.99, 133.82, 132.57, 128.91, 127.56, 123.68, 122.86, 118.41.
HRMS (DART, positive) m/z calcd for _C16H12Br _[ M+H] ⁺ : m/z 283.01169. Found: m/z 283.01170.

Synthesis Example 2

Synthesis of 2-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)pyrene (compound S3) To a dry 100 mL two-neck flask was added pyrene (1.0 mmol, 202 mg, 1.0 equiv.), cyclooctadienemethoxyiridium(I) dimer ([Ir(OMe)(cod)] ₂ ) (50 μmol, 33.1 mg, 5 mol%), 4,4'-di-tert-butyl-2,2'-bipyridyl (dtbpy, 100 μmol, 26.8 mg, 10 mol%), and bis( _pinacolato )diboron ( _B2pin2 ) (1.1 mmol, 279 mg, 1.1 equiv.). The flask was degassed and then cyclohexane (20 mL) was added. The reaction mixture was stirred at 80 °C for 16 h. After cooling to room temperature, the reaction mixture was quenched by adding water, and the organic layer was extracted with ethyl acetate three times. The combined organic layers were dried over Na ₂ SO ₄ and concentrated in vacuo. The crude product was purified by silica gel column chromatography (eluent: hexane/ethyl acetate = 100 : 0 to 80 : 20) to give 4,4,5,5-tetramethyl-2-(2-pyrenyl)-1,3,2-dioxaborolane (compound S3) as a white solid (236 mg, 72%). The ¹ H NMR spectrum of compound S3 was consistent with the reported data.

Synthesis of 2-(2-bromophenyl)pyrene (compound S4) To a dry 100 mL three-neck flask were added 1-bromo-2-iodobenzene (1.00 mmol, 282 mg, 1.0 equiv.), 2-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)pyrene (1.0 mmol, 328 mg, 1.0 equiv.), palladium acetate (30 μmol, 8.98 mg, 3 mol%), triphenylphosphine (90 μmol, 31.5 mg, 9 mol%), and K ₂ CO ₃ (3.00 mmol, 414 mg, 3.0 equiv.). The flask was degassed, followed by the addition of toluene (4.0 mL), ethanol (1.0 mL), and H ₂ O (1.0 mL). The reaction mixture was stirred at 80° C. for 15 h. After cooling to room temperature, water was added to the reaction mixture to quench the reaction, and the organic layer was extracted with ethyl _acetate three times. The combined organic layers were dried over _Na2SO4 and concentrated in vacuum. The crude product was purified by silica gel column chromatography (eluent: hexane/ _CHCl3 = 100:0 to 90:10) and recrystallized from hot ethanol to give 2-(2-bromophenyl)pyrene (compound S4) as a white solid (279 mg, 78%).
^1H NMR (600 MHz, _CDCl3 ) δ 8.20-8.23 (m, 4H), 8.11 (d, J = 1.2 Hz, 4H), 8.03 (t, J = 7.8 Hz, 1H), 7.78 (dd, J = 7.8, 1.2 Hz, 1H), 7.56 (dd, J = 7.2, 1.2 Hz, 1H), 7.46 (td, J = 7.8, 1.2 Hz, 1H), 7.30 (td, J = 7.8, 1.8 Hz, 1H).
^13C NMR (150 MHz, _CDCl3 ) δ 143.04, 138.93, 133.34, 132.18, 131.39, 131.02, 129.08, 127.96, 127.60, 126.19, 126.02, 125.30, 124.73, 124.09, 123.25.
HRMS (DART, positive) m/z calcd for _C22H14 _[ M+H] ⁺ : m/z 357.02734. Found: m/z 357.02735.

Synthesis Example 3

Synthesis of 1-(2-bromophenyl)pyrene (compound S5) 1-Bromo-2-iodobenzene (800 μmol, 226 mg, 1.0 equiv.), pyrene-1-boronic acid (880 μmol, 216 mg, 1.1 equiv.), palladium acetate (Pd(OAc) ₂ ) (40 μmol, 8.98 mg, 5 mol%), triphenylphosphine (PPh ₃ ) (120 μmol, 31.5 mg, 15 mol%), and Na ₂ CO ₃ (2.40 mmol, 254 mg, 3.0 equiv.) were added to a 100 mL two-neck flask. After degassing the flask, toluene (8.0 mL) and H ₂ O (4.0 mL) were added. The reaction mixture was stirred at 80° C. for 18 h. After cooling to room temperature, water was added to the reaction mixture to quench the reaction, and the organic layer was extracted three times with ethyl acetate. The combined organic layers were dried _over _Na2SO4 and concentrated in vacuo. The crude product was purified by silica gel column chromatography (eluent: hexane) to give 1-(2-bromophenyl)pyrene (compound S5) as a white solid (228 mg, 80%). The ^1H NMR spectrum of compound S5 was consistent with the reported data.

Synthesis Example 4

Synthesis of 8-(2-bromophenyl)quinoline (compound S6) To a dry 100 mL two-neck flask were added quinoline-8-boronic acid (960 μmol, 167.1 mg, 1.2 equiv.), 1-bromo- _{2-iodobenzene (800 μmol, 226.3 mg, 1.0 equiv.), [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium(II) dichloromethane adduct (PdCl2(dppf)·CH2Cl2) (40 μmol, 32.4 mg, 5 mol%), and Na2CO3} ₍ _2.40 _mmol _, 253.1 mg, 3.0 equiv.). The flask was degassed, followed by the addition of toluene (3.0 mL), ethanol (0.5 mL), and _H2O (0.5 mL). The reaction mixture was stirred at 80° C. for 18 h. After cooling to room temperature, water was added to the reaction mixture to quench the reaction, and the organic layer was extracted with ethyl _acetate three times. The combined organic layers were dried over _Na2SO4 and concentrated in vacuum. The crude product was purified by silica gel column chromatography (eluent: hexane/ethyl acetate = 100:0 to 95:5) to obtain 8-(2-bromophenyl)quinoline (compound S6) as a white solid (182 mg, 80%).
^1H NMR (600 MHz, _CDCl3 ) δ 8.92 (dd, J = 4.2, 1.8 Hz, 1H), 8.21 (dd, J = 8.4, 1.8 Hz, 1H), 7.90 (dd, J = 7.8, 1.8 Hz, 1H), 7.73 (dd, J = 7.2, 1.2 Hz, 1H), 7.60-7.65 (m, 2H), 7.39-7.44 (m, 3H), 7.28-7.31 (m, 1H).
^13C NMR (150 MHz, _CDCl3 ) δ 150.62, 146.43, 141.13, 140.69, 136.25, 132.80, 132.06, 130.80, 129.18, 128.56, 128.36, 127.09, 126.03, 124.47, 121.22.
HRMS ( _DART , positive) m/z calcd for _C15H11BrN [M+H] ⁺ : m/z 284.00694. Found: m/z 284.00708.

Synthesis Example 5

Synthesis of 4-protoadamantanone A dry 500 mL three-neck flask equipped with a magnetic stir bar was charged with lead(IV) acetate (Pb(OAc) ₄ ) (60.0 g, 115 mmol, 1.8 equiv.), 1-adamantanol (10.0 g, 65.7 mmol, 1.0 equiv.), iodine (29.2 g, 115 mmol, _1.8 equiv.), and anhydrous benzene (300 mL). The reaction mixture was stirred at 73 °C for 4 h. After cooling to room temperature, the mixture was neutralized with aqueous _NaHCO3 . The organic layer was washed with aqueous _Na2S2O3 , dried over _Na2SO4 _, and concentrated under _vacuum . The crude product obtained was used without purification.

The crude product, methanol (300 mL), and potassium hydroxide (22.1 g, 394 mmol, 6.0 equiv.) were added to a 300 mL round-bottom flask equipped with a magnetic stir bar. The reaction mixture was stirred at 85 °C for 16 h. After cooling to room temperature, the organic layer was extracted five times with diethyl ether, dried over _Na2SO4 , and concentrated in vacuum. The crude product was purified by silica gel column chromatography (eluent: hexane/ethyl acetate = 90:10 to 80:20) to give compound 1 ( _5.63 g, 57%). The ^1H NMR spectrum of compound 1 was consistent with the reported data.
^1H NMR (600 MHz, _CDCl3 ) δ2.72-2.76 (m, 1H), 2.61 (q, J = 6.0 Hz, 2H), 2.54 (dd, J = 18.0, 3.0 Hz, 1H), 2.41 (t, J = 3.6 Hz, 1H), 2.23-2.31 (m, 2H), 1.92-1.99 (m, 2H), 1.80 (dd, J = 12.0, 2.4 Hz, 1H), 1.67-1.71 (m, 3H), 1.63 (dd, J = 11.4, 2.4 Hz, 1H), 1.53 (dq, J = 13.1, 2.4 Hz, 1H).
^13C NMR (150 MHz, _CDCl3 ) δ 216.73, 51.25, 45.15, 41.50, 38.26, 37.50, 37.38, 37.28, 49.96 39.26.

Synthesis Examples 6-1 to 6-17, 6-30, 6-31, 6-34, and 6-36

ⁿ BuLi refers to n-butyl lithium. THF refers to tetrahydrofuran.

(Step IA)
At room temperature (25°C), an aromatic compound (0.3 mmol, 1.0 equivalent) was placed in a dried 50 mL two-neck flask, and after nitrogen replacement, dehydrated tetrahydrofuran (THF; 3 mL) was added. The solution was cooled to -78°C, and then normal butyl lithium ( ^nBuLi ; 1.6 mol/L, normal hexane solution, 0.33 mmol, 1.1 equivalent) was slowly added dropwise and stirred for 1 hour. To the reaction solution, solid 4-protoadamantanone (compound 1; 0.33 mmol, 1.1 equivalent) was added at -78°C under _N2 gas flow, and the temperature was raised to room temperature (25°C) and stirred for 12 hours. Thereafter, the reaction solution was cooled to 0°C, and the reaction was stopped by adding methanol. Thereafter, the obtained reaction solution was subjected to extraction operation using ethyl acetate three times, and the obtained organic layer was dried over magnesium sulfate, and the solvent was distilled off under reduced pressure. The obtained crude product was used in the next step without purification.

(Step IB)
The obtained compound was placed in a dried Schlenk tube at room temperature (25°C), and after nitrogen replacement, 1,2-dichloroethane (1.5mL) and trifluoroacetic acid (1.5mL) were added. After heating to 75°C and stirring for 3 hours, a saturated aqueous solution of sodium bicarbonate was added dropwise at room temperature (25°C) to stop the reaction. An extraction operation using ethyl acetate was performed three times, and the obtained organic layer was dried with sodium sulfate, and the solvent was distilled off under reduced pressure. The crude product was purified by silica gel column chromatography (developing solvent: hexane). Subsequently, purification was performed using gel filtration chromatography to obtain the target compound.

Synthesis Examples 6-18 to 6-29, 6-32, 6-33, and 6-35

(Step IA)
At room temperature (25°C), an aromatic compound (0.3 mmol, 1.0 equivalent) was placed in a dried 50 mL two-neck flask, and after nitrogen replacement, dehydrated tetrahydrofuran (THF; 3 mL) was added. After cooling the solution to -78°C, normal butyl lithium ( ^nBuLi ; 1.6 mol/L, normal hexane solution, 0.33 mmol, 1.1 equivalent) was slowly added dropwise and stirred for 1 hour. To the reaction solution, solid 4-protoadamantanone (compound 1; 0.33 mmol, 1.1 equivalent) was added at -78°C under _N2 gas flow, and the temperature was raised to room temperature (25°C) and stirred for 12 hours. Thereafter, the reaction solution was cooled to 0°C, and the reaction was stopped by adding methanol. Thereafter, the obtained reaction solution was subjected to extraction operation using ethyl acetate three times, and the obtained organic layer was dried with magnesium sulfate, and the solvent was distilled off under reduced pressure. Thereafter, the next step was carried out without purification.

(Step IB)
The obtained crude product was placed in a dried Schlenk tube at room temperature (25°C), and after nitrogen replacement, 1,1,2,2-tetrachloroethane (1.5mL) and trifluoroacetic acid (1.5mL) were added. After heating to 75°C and stirring for 3 hours, a saturated aqueous solution of sodium bicarbonate was added dropwise at room temperature (25°C) to stop the reaction. An extraction operation using ethyl acetate was performed three times, and the obtained organic layer was dried with sodium sulfate, and the solvent was distilled off under reduced pressure. The crude product was purified by silica gel column chromatography (developing solvent: hexane). Subsequently, purification was performed by gel filtration chromatography (developing solvent: CHCl ₃ ) to obtain the target compound.

The raw material compounds used in Synthesis Examples 6-1 to 6-36 are as follows:

The intermediate (adamantane-containing arene compound) obtained by carrying out step IA using the above-mentioned compound as a raw material compound is as follows.

The intermediates (adamantane-fused arene compounds) obtained by carrying out steps IA and IB similarly using the above compounds as raw materials are as follows. The yields listed under each compound are the total yields of steps IA and IB.

Synthesis Example 6-1: 10,11,12,13,14,14a-hexahydro-9H-8b,12:10,14-dimethanocycloocta[l]phenanthrene Synthesis method: Synthesis method A. 2-Bromobiphenyl was used. Yield 49.1 mg, yield 57%, white solid.
^1H NMR (600 MHz, _CD2Cl2 ) δ 7.83-7.81 (m, 1H), 7.78-7.80 (m, 1H) _, 7.44-7.40 (m, 2H), 7.34-7.27 (m, 4H), 2.96 (s, 1H), 2.77 (q, J = 3.0 Hz, 1H), 2.58 (dt, J = 12.0, 2.4 Hz, 1H), 2.25 (t, J = 3.0 Hz, 1H), 2.07-2.11 (m, 1H), 1.86-1.96 (m, 3H), 1.76-1.85 (m, 3H), 1.68 (dq, J = 12.6, 3.0 Hz, 1H), 1.58 (dt, J = 12.6, 1.2 Hz, 1H), 1.27-1.30 (m, 1H).
^13C NMR (150 MHz, _CDCl3 ) δ 145.02, 137.94, 134.16, 133.00, 128.06, 127.74, 126.64, 126.37, 125.77, 124.22, 123.92, 123.87, 45.76, 41.42, 38.68, 37.90, 37.63, 35.77, 30.68, 28.90, 28.51, 28.41.
HRMS (DART, positive) m/z calcd for _C22H21 [MH _] ⁺ : m/z 285.16378. Found: m/z 285.16426.

Synthesis Example 6-2: 4-bromo-10,11,12,13,14,14a-hexahydro-9H-8b,12:10,14-dimethanocycloocta[l]phenanthrene Synthesis method: Synthesis method A. 2,2'-dibromo-1,1'-biphenyl was used. Yield 64.7 mg, yield 59%, white solid.
^1H NMR (600 MHz, _CD2Cl2 ) δ 8.26 (dd, J = 6.6, 1.2 Hz, _1H ), 7.59 (td, J = 7.8, 1.2 Hz, 1H), 7.42 (dd, J = 6.6, 1.2Hz, 1H), 7.38 (d, J = 7.8 Hz, 1H), 7.33 (td, J = 7.2, 1.8 Hz, 1H), 7.26, (td, J = 7.2, 1.2 Hz, 1H), 7.15 (t, J = 8.4 Hz, 1H), 2.78 (s, 1H), 2.69 (d, J = 2.4 Hz, 1H), 2.55 (dt, J = 12.0, 2.4 Hz, 1H), 2.24 (t, J = 3.0 Hz, 1H), 2.07 (dq, J = 9.6, 2.4 Hz, 1H), 1.91-1.93 (m, 1H), 1.68-1.83 (m, 6H), 1.52 (d, J = 12.0 Hz, 1H), 1.38 (dd, J = 7.8, 2.4 Hz, 1H).
^13C NMR (150 MHz, _CDCl3 ) δ 146.13, 142.26, 134.71, 132.97, 131.77, 129.04, 128.40, 128.05, 125.20, 125.03, 123.54, 120.23, 46.43, 41.96, 37.77, 37.59, 37.57, 35.54, 30.67, 30.47, 29.54, 28.70, 28.09.
HRMS (DART, positive) m/z calcd for _C22H20Br [MH _] ⁺ : m/z 363.07429. Found: m/z 363.07532.

Synthesis Example 6-3: 4-chloro-10,11,12,13,14,14a-hexahydro-9H-8b,12:10,14-dimethanocycloocta[l]phenanthrene Synthesis method: Synthesis method A. 2-bromo-2'-chloro-1,1'-biphenyl was used. Yield 24.8 mg, yield 31%, white solid.
^1H NMR (600 MHz, _CDCl3 ) δ 8.28 (dd, J = 7.8, 1.2 Hz, 1H), 7.42 (dd, J = 7.8, 1.2 Hz, 1H), 7.37 (d, J = 7.8 Hz, 1H), 7.34-7.31 (m, 2H), 7.28 (td, J = 7.8, 1.2 Hz, 1H), 7.21 (t, J = 7.8 Hz, 1H), 2.80 (s, 1H), 2.70 (d, J = 3,0 Hz, 1H), 2.54 (dt, J = 12.0, 2.4 Hz, 1H), 2.25 (s, 1H), 2.07 (dq, J = 12.6, 3.0 Hz, 1H), 1.92 (d, J = 12.6 Hz, 1H), 1.73-1.84 (m, 6H), 1.51 (d, J = 12.6 Hz, 1H), 1.37 (d, J = 13.2, 1H).
^13C NMR (150 MHz, _CDCl3 ) δ 146.21, 142.08, 132.93, 131.10, 130.86, 129.46, 128.91, 128.36, 127.73, 125.25, 124.62, 123.64, 46.25, 42.00, 37.78, 37.66, 37.61, 35.58, 30.62, 29.49, 28.73, 28.14.
HRMS (DART, positive) m/z calcd for _C22H20Cl [ _MH ] ⁺ : m/z 319.12480. Found: m/z 319.12505.

Synthesis Example 6-4: 2,7-dichloro-10,11,12,13,14,14a-hexahydro-9H-8b,12:10,14-dimethanocycloocta[l]phenanthrene Synthesis method: Synthesis method A. 2-Bromo-2,2'-dichloro-1,1'-biphenyl was used. Yield 33.0 mg, yield 31%, white solid.
^1H NMR (600 MHz, _CD2Cl2 ) δ 7.71 (d, J = 9.0 Hz, _1H ), 7.67 (d, J = 8.4 Hz, 1H), 7.39 (d, J = 2.4 Hz, 1H), 7.37 (s, 1H), 7.25-7.29 (m, 2H), 2.93 (s, 1H), 2.69 (d, J = 3.0 Hz, 1H), 2.49 (dt, J = 10.2 Hz, 1H), 2.26 (t, J = 2.4 Hz, 1H), 2.07-2.10 (m, 1H), 1.74-1.93 (m, 6H), 1.65 (dq, J = 12.6, 3.0 Hz, 1H), 1.58-1.61 (m, 2H), 1.27 (dq, J = 12.6, 1.8 Hz, 1H).
^13C NMR (150 MHz, _CDCl3 ) δ 146.60, 139.74, 134.20, 134.08, 131.82, 130.62, 126.84, 126.69, 126.24, 125.51, 125.11, 124.58, 45.64, 42.22, 38.45, 37.59, 37.34, 36.04, 30.48, 28.65, 28.44, 28.16 (one sp3 carbon atom was overlapping with others.)
HRMS (DART _{, positive) m/z calcd for C22H20Cl2} _[ _M ] ⁺ : m/z 354.09421. Found: m/z 354.09401.

Synthesis Example 6-5: 6,7,8,9,10,10a-hexahydro-5H-4b,8:6,10-dimethanocycloocta[3,4]naphtho[2,1-a]azulene Synthesis method: Synthesis method A. Compound S2 was used, and the scale was 75 μmol. Yield: 5.8 mg, yield 23%, blue solid.
^1H NMR (600 MHz, _CDCl3 ) δ 8.53 (d, J = 10.2 Hz, 1H), 8.20 (d, J = 9.0 Hz, 1H), 7.91 (dd, J = 5.4, 1.8 Hz, 1H), 7.69 (s, 1H), 7.46 (dd, J = 6.0, 1.2 Hz, 1H), 7.41 (t, J = 3.6 Hz, 1H), 7.30-7.39 (m, 2H), 7.00-7.06 (m, 2H), 3.63 (s, 1H), 3.45 (q, J = 3.0 Hz, 1H), 2.61 (dt, J = 12.0, 1.8 Hz, 1H), 2.29 (t, J = 6.0 Hz, 1H), 2.02-2.10 (m, 4H), 1.82-1.87 (m, 4H), 1.69 (d, J = 12.0 Hz, 1H), 1.31 (d, J = 10.8 Hz, 1H).
^13C NMR (150 MHz, _CDCl3 ) δ 146.58, 146.42, 142.48, 136.05, 135.13, 134.02, 131.61, 129.09, 127.18, 126.64, 126.15, 125.78, 124.09, 123.16, 122.34, 111.97, 47.37, 40.77, 40.43, 38.06, 38.03, 37.44, 31.85, 30.14, 28.97, 28.74.
HRMS (DART, positive) m/z calcd for _C26H25 _[ M+H] ⁺ : m/z 337.19508. Found: m/z 337.19458.

Synthesis Example 6-6: 12c,13,15,16,17,18-Hexahydro-14H-13,17:15,18a-dimethanobenzo[g]cycloocta[p]chrysene Synthesis method: Synthesis method A. 9-(2-bromophenyl)phenanthrene was used. Yield 60.3 mg, yield 52%, white solid.
^1H NMR (600 MHz, _CD2Cl2 ) δ 8.69 (d, J = 8.4 Hz, _1H ), 8.65 (d, J = 7.2 Hz, 1H), 8.46 (d, J = 7.2 Hz, 1H), 7.91 (d, J = 8.4 Hz, 1H), 7.63-7.66 (m, 1H), 7.57-7.61 (m, 3H), 7.50 (td, J = 7.2, 1.8 Hz, 1H), 7.45 (d, J = 7.8 Hz, 1H), 7.33 (td, J = 7.8, 1.2 Hz, 1H), 7.22-7.27 (m, 1H), 3.41 (s, 1H), 3.17 (d, J = 3.0 Hz, 1H), 2.61 (dt, J = 12.0, 2.4 Hz, 1H), 2.32 (d, J = 3.0 Hz, 1H), 2.18 (d, J = 12.0 Hz, 2H), 2.10 (dq, J = 13.2, 2.4 Hz, 1H), 2.02 (dd, J = 12.0, 2.4 Hz, 1H), 1.76 (s, 2H), 1.59 (t, J = 1.8 Hz, 1H), 1.45 (d, J = 13.2, 1.8 Hz, 1H), 1.27 (dd, J = 12.6, 3.0 Hz, 1H), 0.90 (d, J = 13.8 Hz, 1H).
^13C NMR (150 MHz, _CDCl3 ) δ 145.12, 135.07, 133.59, 133.54, 130.95, 130.80, 130.39, 129.38, 128.86, 127.17, 126.66, 126.40, 125.98, 125.71, 125.59, 125.47, 125.33, 123.67, 123.32, 122.55, 47.16, 41.25, 40.59, 38.60, 37.42, 36.49, 32.88, 30.98, 29.03, 27.04.
HRMS (EI, positive) m/z calcd for _C30H24 [M _] ⁺ : m/z 386.20345. Found: m/z 386.20250.

Synthesis Example 6-7: 1,3,4,5,6,18b-hexahydro-2H-1,5:3,6a-dimethanodibenzo[c,g]cycloocta[l]phenanthrene Synthesis method: Synthesis method A. 2-Bromo-1,1'-binaphthalene was used, 0.8 mmol scale. Yield 133.0 mg, yield 43%, white solid.
^1H NMR (600 MHz, _CD2Cl2 ) δ 7.89-7.92 (m, 4H), 7.70-7.72 (m, 2H) _, 7.36-7.42 (m, 2H), 7.14-7.18 (m, 2H), 3.03 (s, 1H), 2.89 (d, J = 3.0 Hz, 1H), 2.68 (dt, J = 12.0, 3.0 Hz 1H), 2.28 (t, J = 3.0 Hz, 1H), 2.10 (dq, J = 12.0, 2.4 Hz, 1H), 1.98 (d, J = 13.2 Hz, 1H), 1.83-1.87 (m, 3H), 1.71-1.74 (m, 2H), 1.65 (d, J = 13.2 Hz, 1H), 1.54-1.55 (m, 1H), 1.50 (d, J = 13.2 Hz, 1H).
^13C NMR (150 MHz, _CDCl3 ) δ 145.01, 138.50, 132.54, 130.94, 130.65, 130.48, 129.74, 128.05, 127.96, 127.90, 127.81, 127.51, 124.96, 124.92, 124.72, 124.60, 124.03, 122.26, 46,66, 42.43, 37.98, 37.80, 37.05, 36.49, 31.17, 29.56, 29.06, 27.98.
HRMS (DART, positive) m/z calcd for _C30H27 _[ M+H] ⁺ : m/z 387.21073. Found: m/z 387.21131.

Synthesis Example 6-8: 6b,7,9,10,11,12-Hexahydro-8H-7,11:9,12a-dimethanodibenzo[m,pqr]cycloocta[k]tetraphene Synthesis method: Synthesis method A. Compound S5 was used. Yield 45.2 mg, yield 37%, white solid.
^1H NMR (600 MHz, _CDCl3 ) δ 8.72 (d, J = 9.6 Hz, 1H), 8.21 (s, 1H), 8.13-8.15 (m, 2H), 8.06 (s, 1H), 8.04 (d, J = 3.0 Hz, 2H), 7.96-7.98 (m, 2H), 7.57 (dd, J = 7.2, 1.8 Hz, 1H), 7.39-7.43 (m, 2H), 3.22 (s, 1H), 3.09 (d, J = 2.4 Hz, 1H), 2.64 (dt, J = 7.2, 2.4 Hz, 1H), 2.33 (t, J = 3.0 Hz, 1H), 2.17-2.20 (m, 1H), 2.06-2.08 (m, 1H), 2.00-2.02 (m, 1H), 1.78-1.84 (m, 3H), 1.69-1.72 (m, 2H), 1.53-1.57 (m, 1H), 1.44 (d, J = 6.6 Hz, 1H).
^13C NMR (150 MHz, _CDCl3 ) δ 146.93, 137.48, 133.10, 131.50, 130.98, 130.83, 130.73, 130.63, 127.79, 127.71, 127.25, 127.01, 126.97, 126.35, 125.84, 125.72, 125.22, 125.02, 124.66, 124.45, 124.08, 122.36, 46.67, 41.96, 38.00, 37.74, 35.55, 30.84, 29.85, 28.89, 28.13.
HRMS (DART, positive) m/z calcd for _C32H27 _[ M+H] ⁺ : m/z 411.21073. Found: m/z 411.21043.

Synthesis Example 6-9: 12,13,14,15,16,16a-hexahydro-11H-10b,14: 12,16-dimethanobenzo[pqr]cycloocta[f]picene Synthesis method: Synthesis method A. Compound S4 was used. Yield 60.4 mg, yield 49%, white solid.
^1H NMR (600 MHz, _CDCl3 ) δ 8.58 (s, 1H), 8.19 (d, J = 9.6 Hz, 1H), 8.10-8.14 (m, 3H), 8.02 (d, J = 9.0 Hz, 1H), 7.93-7.96 (m, 2H), 7.68-7.70 (m, 1H), 7.46-7.47 (m, 1H), 7.36-7.38 (m, 2H), 3.86 (s, 1H), 3.56 (d, J = 3.0 Hz, 1H), 2.64 (dt, J = 12.0, 2.4 Hz, 1H), 2.35 (t, J = 3.0 Hz, 1H), 2.22-2.26 (m, 2H), 2.10 (d, J = 2.4 Hz, 1H), 2.00 (d, J = 13.2 Hz, 1H), 1.75 (s, 2H), 1.59 (s, 1H), 1.39 (d, J = 13.2 Hz, 1H), 1.27 (dd, J = 10.2, 2.4 Hz, 1H), 0.91 (d, J = 12.6 Hz, 1H).
^13C NMR (150 MHz, _CDCl3 ) δ 144.83, 134.64, 134.17, 133.78, 131.46, 130.70, 130.18, 128.41, 127.81, 127.72, 127.12, 127.04, 126.90, 125.79, 125.54, 125.33, 125.20, 125.15, 125.10, 124.85, 122.53, 119.95, 47.43, 41.88, 41.06, 38.72, 37.22, 36.57, 33.27, 30.93, 28.78, 27.27.
HRMS (DART, positive) m/z calcd for _C32H27 _[ M+H] ⁺ : m/z 411.21073. Found: m/z 411.21062.

Synthesis Example 6-10: 7b,8,10,11,12,13-Hexahydro-9H-8,12:10,13a-dimethanocycloocta[3,4]naphtho[1,2-c]thiophene Synthesis method: Synthesis method A (reaction solvent in step I was changed to dehydrated diethyl ether). 3-Bromo-4-phenylthiophene was used. Yield 49.1 mg, yield 57%, white solid.
^1H NMR (600 MHz, _CD2Cl2 ) δ 7.68 (dd, J = 6.0, 1.8 Hz, _1H ), 7.51 (d, J = 3.0 Hz, 1H), 7.37 (d, J = 7.2 Hz, 1H), 7.24-7.30 (m, 2H), 7.03 (d, J = 3.0 Hz, 1H), 2.91 (s, 1H), 2.72 (d, J = 3.0 Hz, 1H), 2.40-2.43 (dt, J = 12.0, 3.0 Hz 1H), 2.19 (d, J = 3.0 Hz, 1H), 2.06-2.09 (m, 1H), 1.98 (dq, J = 6.0, 1.8 Hz, 1H), 1.91-1.97 (m, 2H), 1.78-1.84 (m, 3H), 1.66 (dq, J = 12.0, 3.0 Hz, 1H), 1.60 (d, J = 12.0 Hz 1H), 1.30 (dq, J = 12.0, 1.8 Hz, 1H).
^13C NMR (150 MHz, _CDCl3 ) δ 148.13, 137.10, 136.48, 132.06, 127.35, 126.25, 126.13, 124.02, 118.24, 117.45, 47.18, 42.06, 39.81, 38.14, 37.34, 36.08, 30.69, 28.59, 28.38.
HRMS (DART, positive) m/z calcd for _C28H26N _[ M+H] ⁺ : m/z 293.13585. Found: m/z 293.13595.

Synthesis Example 6-11: 2,3,4,5,6,6a-hexahydro-1H-2,6:4,16b-dimethanocycloocta[3,4]naphtho[2,1-h]quinoline Synthesis method: Synthesis method A. Compound S6 was used. Yield 37.9 mg, yield 37%, white solid.
^1H NMR (600 MHz, _CDCl3 ) δ 8.97 (dd, J = 6.0, 1.8 Hz, 1H), 8.70 (dd, J = 7.8, 1.8 Hz, 1H), 8.16 (dd, J = 4.8, 1.8 Hz, 1H), 7.76 (d, J = 8.4 Hz, 1H), 7.69 (d, J = 8.4 Hz, 1H), 7.44 (d, J = 8.4 Hz, 1H), 7.35-7.40 (m, 3H), 3.06 (s, 1H), 2.88 (d, J = 2.4 Hz, 1H), 2.60 (dt, J = 6.0, 2.4 Hz, 1H), 2.29 (t, J = 3.0 Hz, 1H), 2.11 (dq, J = 7.2, 3.0 Hz, 1H), 1.98-2.01 (m, 1H), 1.94 (dq, J = 10.4, 1.8Hz, 1H), 1.68-1.87 (m, 5H), 1.55 (s, 1H), 1.35 (d, J = 12.0 Hz, 1H).
^13C NMR (150 MHz, _CDCl3 ) δ 149.45, 145.91, 145.63,140.48, 136.21, 131,96, 131.65, 127.95, 127.68, 126.89, 125.55, 124.67, 123.13, 120.41, 46.55, 41.85, 37.92, 37.69, 37.61, 35.15, 31.15, 29.45, 28.84, 28.03.
HRMS (DART, positive) m/z calcd for _C25H24N [M+H] ⁺ : m/z 338.19032. Found _: m/z 354.19078.

Synthesis Example 6-12: 5,6,7,8,9,9a-hexahydro-4H-3b,7:5,9-dimethanocycloocta[5,6]benzo[2,1-b:3,4-b']dithiophene Synthesis method: Synthesis method A (the reaction solvent in step I was dehydrated diethyl ether). 3-Bromo-2,2'-bithiophene was used. Yield 35.8 mg, yield 40%, brown solid.
^1H NMR (600 MHz, _CDCl3 ) δ 7.11 (d, J = 5.4 Hz, 1H), 7.07 (d, J = 4.8 Hz, 1H), 6.97 (d, J = 4.8 Hz, 1H), 6.96 (d, J = 4.8 Hz, 1H), 2.99 (s, 1H), 2.55 (q, J = 3.0 Hz, 1H), 2.33 (dt, J = 12.0, 2.4 Hz, 1H), 2.20 (t, J = 3.0 Hz, 1H), 1.98-2.03 (m, 2H), 1.91 (dd, J = 12.0, 2.4 Hz, 2H), 1.76-1.83 (m, 4H), 1.64-1.67 (m, 1H), 1.30 (d, J = 12.6 Hz, 1H).
^13C NMR (150 MHz, _CDCl3 ) δ 145.15, 138.39, 130.67, 129.97, 125.59, 124.26, 121.77, 121.50, 47.58, 41.49, 38.07, 37.81, 37.29, 36.89, 31.62, 30.24, 29.04, 27.67.
HRMS (DART, positive) m/z calcd for _C18H19S2 _[ M+H] ⁺ : m/z 299.09220. Found: _m /z 299.09219.

Synthesis Example 6-13: 10,11,12,13,14,14a-hexahydro-9H-8b,12: 10,14-dimethanocycloocta[5,6]benzo[1,2,3,4-ghi]perylene Synthesis method: Synthesis method A. 2-Bromo-1,1'-binaphthalene was used, 0.8 mmol scale. Yield 21.2 mg, 7%, yellow solid.
^1H NMR (600 MHz, _CDCl3 ) δ 8.16-8.18 (m, 2H), 7.67 (t, J = 7.8 Hz, 2H), 7.74 (t, J = 7.8 Hz, 2H), 7.52 (t, J = 8.4 Hz, 2H), 7.43 (td, J = 7.8, 1.2 Hz, 2H), 3.24 (s, 1H), 2.84 (d, J = 3.0 Hz, 1H), 2.63 (d, J = 12.0 Hz, 1H), 2,32 (d, J = 3.0 Hz, 1H), 2.05-2.10 (m, 3H), 1.92-1.97 (m, 2H), 1.84-1.86 (m, 2H), 1.78-1.82 (m, 1H), 1.69 (d, J = 13.2 Hz, 1H), 1.26 (d, J = 12.6 Hz, 1H).
^13C NMR (150 MHz, _CD2Cl2 ) δ 141.24, 134.29, 133.40, 133.32, 131.58, 131.33, 128.49 _, 128.35, 128.25, 127.74, 127.71, 127.55, 126.33, 126.28, 126.10, 124.79, 123.13, 120.44, 120.28, 46.85, 41.05, 38.26, 38.01, 37.63, 36.28, 31.51, 29.44, 28.58, 28.28.
HRMS (EI, positive) m/z calcd for _C30H24 [M _] ⁺ : m/z 384.18780. Found: m/z 384.18730.

Synthesis Example 6-14: 5-phenyl-10,11,12,13,14,14a-hexahydro-9H-8b,12:10,14-dimethanocycloocta[l]phenanthrene Synthesis method: Synthesis method A. 1-Bromo-2,3-diphenylbenzene was used. Yield 33.2 mg, yield 31%, white solid.
^1H NMR (600 MHz, _CDCl2CDCl2 ) δ 7.38-7.48 (m, 2H), 7.17-7.32 (m, 7H) _, 7.06 (td, J = 6.6, 1.8 Hz, 1H), 6.79 (dd, J = 6.6, 1.8 Hz, 1H), 6.69 (t, J = 7.8 Hz, 1H), 2.98 (s, 1H), 2.69 (d, J = 2.4 Hz, 1H), 2.52 (dt, J = 12.0, 2.4 Hz, 1H), 2.21 (bs, 1H), 2.02 (dd, J = 10.8, 1.8 Hz, 1H), 1.72-1.92 (m, 6H), 1.48 (d, J = 12.6 Hz, 2H), 1.27 (d, J = 12.0 Hz, 1H).
^13C NMR (150 MHz, _CDCl3 ) δ 147.31, 144.17, 139.94, 138.96, 133.00, 132.10, 130.73, 130.16, 127.49, 126.60, 126.56, 125.40, 124.47, 123.36, 45.50, 42.50, 37.99, 37.78, 36.75, 30.66, 29.15, 28.75, 28.42 (four sp2 carbon atoms and one sp3 carbon atom were overlapping with others.).
HRMS (DART, positive) m/z calcd for _C28H25 [MH _] ⁺ : m/z 361.19556. Found: m/z 361.19483.

Synthesis Example 6-15: 12,13,14,15,16,16a-hexahydro-11H-10b,14: 12,16-dimethanobenzo[e]cycloocta[l]pyrene Synthesis method: Synthesis method A. 1-Bromo-2,3-diphenylbenzene was used. Yield 16.1 mg, yield 15%, white solid.
^1H NMR (600 MHz, _CDCl3 ) δ 8.64-8.67 (m, 2H), 8.51-8.53 (m, 2H), 7.62-7.68 (m, 6H), 3.34 (s, 1H), 2.93 (d, J = 3.0 Hz, 1H), 2.73 (dt, J = 12.0, 2.4 Hz, 1H), 2.35 (d, J = 2.4 Hz, 1H), 2.12-2.20 (m, 3H), 2.03 (dt, J = 12.0, 3.0 Hz, 1H), 1.80-1.90 (m, 4H), 1.69 (d, J = 12.6 Hz, 1H), 1.28 (dd, J = 12.0, 1.8 Hz, 1H).
^13C NMR (150 MHz, _CDCl3 ) δ 144.75, 137.34, 130.15, 129.20, 129.01, 127.46, 127.18, 127.14, 127.11, 127.05, 125.82, 124.05, 123.59, 123.57, 121.93, 120.87, 120.68, 46.49, 41.18, 40.09, 37.93, 37.58, 36.39, 31.14, 28.99, 28.67, 28.45 (one sp2 carbon atom was overlapping with others).
HRMS (DART, positive) m/z calcd for _C28H25 _[ M+H] ⁺ : m/z 361.19508. Found: m/z 361.19483.

Synthesis Example 6-16: 5-(phenanthren-9-yl)-10,11,12,13,14,14a-hexahydro-9H-8b,12: 10,14-dimethanocycloocta[l]phenanthrene Synthesis method: Synthesis method A. 1-Bromo-3-(9-phenanthrene)-2-phenylbenzene was used. Yield 26.4 mg, 19%, white solid. The product was obtained as a 1:1 mixture with rotamers.
^1H NMR (600 MHz, _CDCl2CDCl2 ) δ 8.78 (d, J = 7.8 Hz, 1H), 8.66-8.69 (m, 2H) _, 8.56 (d, J = 8.4 Hz, 1H), 8.14 (d, J = 8.4 Hz, 1H), 7.99 (s, 1H), 7.96 (d, J = 7.2 Hz, 1H), 7.71 (t, J = 7.2 Hz, 1H), 7.58-7.65 (m, 5H), 7.17-7.53 (m, 14H), 7.31-7.40 (m, 4H), 7.06 (m, 2H), 6.94 (t, J = 7.2 Hz, 1H), 6.84 (t, J = 7.8 Hz, 1H), 6.77 (d, J = 7.8 Hz, 1H), 6.43 (t, J = 7.8 Hz, 1H), 6.31 (t, J = 7.8 Hz, 1H), 2.91 (s, 1H), 2.87 (s, 1H), 2.80 (d, J = 11.4 Hz, 2H), 2.51 (d, J = 9.0 Hz, 2H), 2.24 (brs, 2H), 1.78-2.10 (m, 16H), 1.55-1.59 (m, 2H), 1.48 (t, J = 11.4 Hz, 2H).
^13C NMR (150 MHz, _CDCl3 ) δ 145.96, 145.33, 141.75, 140.65, 140.22, 139.58, 137.79, 137.55, 134.96, 132.87, 132.47, 132.33, 131.87, 131.44, 131.13, 130.28, 130.16, 129.78, 129.59, 128.89, 128.73, 128.22, 127.90, 127.74, 127.70, 127.34, 127.08, 126.99, 126.90, 126.70, 126.65, 126.52, 126.42, 126.34, 126.28, 126.03, 125.80, 125.27, 125.21, 125.04, 123.28, 123.23, 122.80, 122.58, 122.54, 46.46, 46.16, 42.23, 42.04, 38.16, 38.01, 37.87, 37.78, 37.53, 35.63, 35.50, 30.95, 30.81, 29.51, 29.36, 28.97, 28.94, 28.57, 28.48 (seven sp2 carbon atoms and one sp3 carbon atom were overlapping with others.).
HRMS (DART, positive) m/z calcd for _C36H30 [M] ⁺ : m/z _462.23475 . Found: m/z 462.23445.

Synthesis Example 6-17: 13,14,15,16,17,17a-hexahydro-12H-11b,15: 13,17-dimethanotribenzo[f,ij,no]cycloocta[l]tetraphene Synthesis method: Synthesis method A. 1-Bromo-3-(9-phenanthrene)-2-phenylbenzene was used. Yield 8.3 mg, yield 6%, white solid.
^1H NMR (600 MHz, _CDCl3 ) δ 8.77 (dd, J = 8.4, 1.2 Hz, 1H), 8.70-8.73 (m, 3H), 8.55-8.57 (m, 2H), 7.61-7.69 (m, 8H), 3.36 (s, 1H), 2.99 (d, J = 2.4 Hz, 1H), 2.79 (dt, J = 12.0, 2.4 Hz, 1H), 2.40 (t, J = 1.8 Hz, 1H), 2.17-2.27 (m, 3H), 2.08 (d, J = 12.6 Hz, 1H), 1.98 (dd, J = 12.6, 2.4 Hz, 1H), 1.87-1.93 (m, 3H), 1.74 (d, J = 13.2 Hz, 1H), 1.34 (dd, J = 12.6, 1.2 Hz, 1H).
^13C NMR (150 MHz, _CDCl3 ) δ 144.31, 137.11, 130.98, 129.58, 129.24, 129.09, 128.49, 128.36, 127.78, 127.66, 127.60, 127.05, 126.68, 126.57, 126.38, 123.68, 123.31, 121.23, 46.45, 41.59, 39.39, 38.04, 37.71, 36.22, 31.35, 29.10, 28.74, 28.66 (eight sp2 carbon atoms were overlapping with others.).
HRMS (DART, positive) m/z calcd for _C36H28 _[ M] ⁺ : m/z 460.21910. Found: m/z 460.22123.

Synthesis Example 6-18: 8,9,10,11,12,12a-Hexahydro-7H-6b,10:8,12-dimethanocycloocta[a]acenaphthylene Synthesis method: Synthesis method B. 1-Bromonaphthalene was used. Yield 18.7 mg, yield 24%, colorless oil.
^1H NMR (600 MHz, _CDCl3 ) δ 7.59 (dd, J = 7.8, 1.8 Hz, 2H), 7.41-7.45 (m, 2H), 7.23 (dd, J = 6.6, 1.2 Hz, 1H), 7.17 (d, J = 6.0 Hz, 1H), 3.51 (s, 1H), 2.77 (d, J = 2.4 Hz, 1H), 2.47 (dt, J = 12.0, 1.8 Hz, 1H), 2.21-2.27 (m, 2H), 2.03 (dq, J = 12.6, 2.4 Hz, 1H), 1.80-1.93 (m, 6H), 1.66 (dt, J = 12.0, 1.2 Hz, 1H), 1.32 (dt, J = 13.2, 2.4 Hz, 1H).
^13C NMR (150 MHz, _CDCl3 ) δ 152.71, 145.26, 137.11, 132.12, 127.48, 127.46, 123.06, 122.87, 117.54, 116.58, 57.65, 47.08, 44.71, 39.40, 39.04, 37.29, 31.90, 29.37, 28.93, 28.04.
HRMS (DART, positive) m/z calcd for _C20H19 [MH] ⁺ : m/z 259.14813. Found: m/ _z 259.14792.

Synthesis Example 6-19: 4-bromo-8,9,10,11,12,12a-hexahydro-7H-6b,10:8,12-dimethanocycloocta[a]acenaphthylene Synthesis method: Synthesis method B. 1,4-Dibromonaphthalene was used. Yield 55.2 mg, yield 55%, white solid.
^1H NMR (600 MHz, _CD2Cl2 ) δ 7.74 (dt, J = 7.2, 1.2 Hz, 1H), 7.64 (s, J = 7.2 Hz, _1H ), 7.54-7.56 (m, 1H), 7.29 (dd, J = 6.0, 1.2 Hz, 1H), 7.05 (d, J = 7.2 Hz, 1H), 3.50 (s, 1H), 2.75 (d, J = 2.4 Hz, 1H), 2.45 (dt, J = 12.0, 2.4 Hz, 1H), 2.24 (t, J = 3.0 Hz, 1H), 2.18-2.21 (m, 1H), 2.02-2.05 (m, 1H), 1.80-1.92 (m, 6H), 1.65-1.68 (m, 1H), 1.24 (dq, J = 10.4, 2.4 Hz, 1H).
^13C NMR (150 MHz, _CDCl3 ) δ 152.68, 145.52, 138.27, 131.58, 130.60, 128.76, 122.34, 118.56, 117.67, 117.48, 57.698, 46.87, 44.78, 39.24, 38.88, 37.19, 31.81, 29.29, 28.92, 28.01.
HRMS (DART, positive) m/z calcd for _C20H18Br [MH _] ⁺ : m/z 337.05864. Found: m/z 337.06045.

Synthesis Example 6-20: 6b,7,9,10,11,12-Hexahydro-8H-7,11:9,12a-dimethanocycloocta[4,5]cyclopenta[1,2,3-cd]pyrene Synthesis method: Synthesis method B. 1-Bromopyrene was used. Yield 52.1 mg, yield 52%, white solid.
^1H NMR (600 MHz, _CDCl3 ) δ 8.10-8.12 (m, 2H), 8.03-8.05 (m, 2H), 7.92-7.97 (m, 2H), 7.84 (dd, J = 7.2, 1.2 Hz, 1H), 7.68 (s, 1H), 3.82 (s, 1H), 2.92 (d, J = 3.0 Hz, 1H), 2.64 (dt, J = 12.0, 2.4 Hz, 1H), 2.40 (dq, J = 12.0, 2.4 Hz, 1H), 2.34 (t, J = 3.0 Hz, 1H), 2.09 (qdJ = 12.6, 3.0 Hz 1H), 1.97-2.01 (m, 2H), 1.88-1.92 (m, 4H), 1.79 (d, J = 12.6 Hz, 1H), 1.53-1.55 (m, 1H).
^13C NMR (150 MHz, _CDCl3 ) δ 151.52, 141.80, 134.71, 133.33, 131.32, 128.86, 126.79, 126.53, 126.23, 124.83, 124.51, 124.25, 123.29, 120.02, 116.33, 58.80, 48.05, 44.50, 39.43, 39.04, 37.44, 32.08, 29.44, 29.38, 28.33 (one sp2 carbon atom was overlapping with others).
HRMS (DART, positive) m/z calcd for _C26H23 [M+H ^]+ _: 335.17943, found: 335.17893.

Synthesis Example 6-21: 8,9,10,11,12,12a-hexahydro-7H-6b,10: 8,12-dimethanocycloocta[4,5]cyclopenta[1,2,3-cd]fluoranthene Synthesis method: Synthesis method B. 3-Bromofluoranthene was used. Yield 47.2 mg, yield 47%, white solid.
^1H NMR (600 MHz, _CD2Cl2 ) δ 7.86-7.93 (m, _4H ), 7.34-7.39 (m, 3H), 7.32 (d, J = 7.0 Hz, 1H), 3.74 (s, 1H), 2.86 (d, J = 2.4 Hz, 1H), 2.57 (dt, J = 12.0, 2.4 Hz, 1H), 2.29 (dq, J = 12.0, 3.0 Hz 1H), 2.26 (t, J = 2.4 Hz, 1H), 2.05 (dq, J = 12.0, 2.4 Hz, 1H), 1.96 (d, J = 12.6 Hz, 1H), 1.80-1.87 (m, 6H), 1.28 (d, J = 13.2 Hz, 1H).
^13C NMR (150 MHz, _CDCl3 ) δ 152.90, 145.70, 140.73, 134.57, 133.56, 133.45, 132.20, 126.97, 122.21, 121.57, 119.50, 118.50, 60.10, 50.22, 45.76, 39.44, 39.29, 37.17, 32.26, 29.98, 29.15, 28.60 (four sp2 carbon atoms were overlapping with others).
HRMS (DART, positive) m/z calcd for _C26H23 _[ M+H] ⁺ : m/z 335.17943. Found: m/z 335.17893.

Synthesis Example 6-22: 4-(naphthalen-1-yl)-8,9,10,11,12,12a-hexahydro-7H-6b,10:8,12-dimethanocycloocta[a]acenaphthylene Synthesis method: Synthesis method B. 4-Bromo-1,1'-binaphthalene was used. Yield 48.7 mg, 42%, white solid. The product was obtained as a 1:1 mixture with rotamers.
^1H NMR (600 MHz, _CD2Cl2 ) δ 7.93-7.96 (m, 2x2H), 7.57-7.61 (m, 2x1H) _, 7.53-7.55 (m, 2x1H), 7.45-7.50 (m, 2x2H), 7.43 (d, J = 6.6 Hz, 2x1H), 7.23-7.33 (m, 2x4H), 7.06-7.08 (m, 2x1H), 3.62 (s, 1H), 3.57 (s, 1H), 2.80 (d, J = 2.4 Hz, 2x1H), 2.55-2.57 (m, 2x1H), 2.27-2.31 (m, 2x2H), 2.08 (dt, J = 12.6, 3.0 Hz, 2×1H), 1.84-1.99 (m, 2×6H), 1.80 (t, J = 13.2 Hz, 1H), 1.76 (d, J = 13.2 Hz, 1H), 1.47 (d, J = 12.6 Hz, 1H), 1.37 (d, J = 12.6 Hz, 1H).
^13C NMR (150 MHz, _CDCl3 ) δ 152.45, 145.32, 138.49, 138.41, 137.15, 137.07, 134.68, 134.60, 133.75, 132.94, 131.74, 129.23, 129.18, 128.25, 128.23, 128.07, 127.99, 127.76, 127.53, 127.46, 126.86, 125.90, 125.85, 125.81, 125.52, 122.08, 117.73, 117.61, 116.48, 116.35, 57.82, 46.91, 44.91, 44.86, 39.45, 39.13, 37.35, 37.33, 31.91, 29.44, 29.01, 28.98, 28.10 (ten sp2 carbon signals and seven sp3 carbon signals were overlapping with others).
HRMS (DART, positive) m/z calcd for _C30H27 _[ M+H] ⁺ : m/z 387.21073. Found: m/z 387.21074.

Synthesis Example 6-23: 7,8,9,10,11,11a-hexahydro-6H-5b,9: 7,11-dimethanocycloocta[4,5]cyclopenta[1,2,3-cd]perylene Synthesis method: Synthesis method B. 4-Bromo-1,1'-binaphthalene was used. Yield 23.2 mg, 20%, yellow solid.
^1H NMR (600 MHz, _CDCl3 ) δ 8.10 (t, J = 7.8 Hz, 2H), 8.04-8.07 (m, 2H), 7.61 (d, J = 8.4 Hz, 2H), 7.43 (td, J = 12.6, 2.4 Hz, 2H), 7.25 (dd, J = 5.4, 1.8 Hz, 1H), 7.19 (d, J = 7.2 Hz, 1H), 3.48 (s, 1H), 2.76 (d, J = 2.4 Hz, 1H), 2.46 (d, J = 12.0 Hz, 1H), 2.22-2.27 (m, 2H), 2.03 (dq, J = 8.4, 1.2 Hz, 1H), 1.80-1.93 (m, 6H), 1.70 (d, J = 13.2 Hz, 1H), 1.39 (dd, J = 13.2, 1.2 Hz, 1H).
^13C NMR (150 MHz, _CDCl3 ) δ 152.38, 144.99, 137.99, 135.50, 131.66, 129.56, 128.72, 128.60, 127.55, 127.52, 126.48, 120.76, 120.69, 119.42, 119.01, 118.01, 58.08, 47.71, 44.71, 39.33, 38.94, 37.24, 32.05, 29.30, 29.07, 28.08 (four sp2 carbon signals were overlapping with others).
HRMS (DART, positive) m/z calcd for _C30H25 _[ M+H] ⁺ : m/z 385.19508. Found: m/z 385.19567.

Synthesis Example 6-24: 10,11,12,13,14,14a-Hexahydro-9H-8b,12:10,14-dimethanocycloocta[e]pyrene Synthesis method: Synthesis method B. 4-Bromophenanthrene was used. Yield 23.1 mg, yield 24%, white solid.
^1H NMR (600 MHz, _CDCl3 ) δ 7.74-7.76 (m, 4H), 7.57-7.62 (m, 4H), 3.38 (s, 1H), 2.94 (d, J = 3.0 Hz, 1H), 2.74 (dt, J = 12.0, 3.0 Hz, 1H), 2.36 (t, J = 3.0 Hz, 1H), 2.14-2.18 (m, 3H), 2.01-2.04 (m, 1H), 1.82-1.92 (m, 4H), 1.70 (d, J = 13.2 Hz, 1H), 1.26 (dq, J = 12.0, 3.0 Hz, 1H).
^13C NMR (150 MHz, _CDCl3 ) δ 144.32, 136.89, 131.37, 131.12, 127.47, 126.97, 126.89, 126.70, 126.26, 125.87, 125.60, 123.02, 120.92, 46.88, 41.11, 40.55, 38.03, 37.56, 36.79, 31.44, 29.01, 28.75, 28.28 (one sp2 carbon atom was overlapping with others).
HRMS (DART, positive) m/z calcd for _C24H23 _[ M+H] ⁺ : m/z 311.17943. Found: m/z 311.18003.

Synthesis Example 6-25: 4,4-Dimethyl-4,8,9,10,11,12,13,13a-octahydro-7b,11:9,13-dimethanocycloocta[l]cyclopenta[def]phenanthrene Synthesis method: Synthesis method B. 4-Bromo-9,9-dimethyl-9H-fluorene was used. Yield 42.1 mg, yield 43%, white solid.
^1H NMR (600 MHz, _CD2Cl2 ) δ 7.22-7.27 (m, _4H ), 7.16-7.19 (m, 2H), 3.26 (s, 1H), 2.78 (d, J = 3.0 Hz, 1H), 2.57 (dt, J = 12.0, 2.4 Hz, 1H), 2.25 (d, J = 2.4 Hz, 1H), 2.04-2.09 (m, 2H), 1.92-1.99 (m, 2H), 1.80-1.87 (m, 3H), 1.70-1.75 (m, 2H), 1.50 (s, 3H), 1.50 (s, 3H), 1.32 (d, J = 12.0 Hz, 1H).
^13C NMR (150 MHz, _CDCl3 ) δ 151.21, 150.76, 140.69, 136.88, 135.49, 133.67, 128.05, 127.87, 122.48, 120.85, 120.16, 119.90, 50.19, 48.83, 41.27, 39.51, 38.74, 38.28, 37.23, 31.58, 28.80, 28.36, 28.30, 26.73, 26.54.
HRMS (DART, positive) m/z calcd for _C25H27 [MH _] ⁺ : m/z 327.19508. Found: m/z 327.19515.

Synthesis Example 6-26: 4,4-diphenyl-4,8,9,10,11,12,13,13a-octahydro-7b,11:9,13-dimethanocycloocta[l]cyclopenta[def]phenanthrene Synthesis method: Synthesis method B. 4-Bromo-9,9-diphenyl-9H-fluorene was used. Yield 41.7 mg, yield 35%, white solid.
^1H NMR (600 MHz, _CD2Cl2 ) δ 7.19-7.28 (m, 16H), 3.31 (s, 1H), 2.80 (d, J = 3.0 Hz, _1H ), 2.58 (dt, J = 12.0, 3.0 Hz, 1H), 2.26 (t, J = 3.0 Hz, 1H), 2.07-2.10 (m, 2H), 1.93-2.01 (m, 2H), 1.77-1.86 (m, 3H), 1.71-1.76 (m, 2H), 1.34 (d, J = 11.4 Hz, 1H).
^13C NMR (150 MHz, _CDCl3 ) δ 148.59, 148.19, 146.04, 145.73, 141.18, 137.79, 136.45, 134.03, 128.50, 128.34, 128.31, 128.28, 128.15, 128.11, 126.66, 123.57, 123.30, 123.02, 121.39, 68.32, 48.70, 41.40, 39.50, 38.74, 38.24, 37.24, 31.48, 28.80, 28.38, 28.34 (five sp2 carbon atoms were overlapping with others.).
HRMS (DART, positive) m/z calcd for _C35H31 _[ M+H] ⁺ : m/z 451.24203. Found: m/z 451.23986.

Synthesis Example 6-27: 9',10',11',12',13',13a'-Hexahydro-8'H-spiro[fluorene-9,4'-[7b,11:9,13]dimethanocycloocta[l]cyclopenta[def]phenanthrene Synthesis method: Synthesis method B. 4-Bromo-9,9'-spirobifluorene was used. Yield 47.1 mg, yield 35%, white solid.
^1H NMR (600 MHz, _CDCl3 ) δ 7.84 (dt, J = 7.8, 1.2 Hz, 2H), 7.35-7.38 (m, 2H), 7.21 (t, J = 7.8 Hz, 2H), 7.06-7.13 (m, 4H), 6.80 (d, J = 7.8 Hz, 1H), 6.72 (d, J = 7.8 Hz, 1H), 6.59-6.62 (m, 2H), 3.45 (s, 1H), 2.85 (d, J = 2.4 Hz, 1H), 2.62 (dt, J = 12.0, 2.4 Hz, 1H), 2.33 (t, J = 1.8 Hz, 1H), 2.08-2.17 (m, 3H), 1.93-2.02 (m, 3H), 1.85-1.92 (m, 2H), 1.75 (d, J = 12.6 Hz, 1H), 1.46 (d, J = 12.0 Hz, 1H).
^13C NMR (150 MHz, _CDCl3 ) δ 148.28, 148.06, 146.83, 146.38, 141.91, 141.76, 140.78, 139.53, 138.21, 133.71, 128.73, 128.52, 127.81, 127.73, 124.37, 124.23, 123.31, 121.66, 121.35, 121.12, 120.07, 49.03, 41.47, 39.52, 39.02, 38.30, 37.28, 31.58, 28.83, 28.50, 28.40 (one sp3 carbon atom and three sp2 carbon atoms were overlapping with others.).
HRMS (DART, positive) m/z calcd for _C35H27 [MH _] ⁺ : m/z 447.21073. Found: m/z 447.20926.

Synthesis Example 6-28: 4-Phenyl-4,8,9,10,11,12,13,13a-octahydro-7b,11:9,13-dimethanocycloocta[5,6]benzo[1,2,3,4-def]carbazole Synthesis method: Synthesis method B. 4-Bromo-9-phenyl-9H-carbazole was used. Yield 63.2 mg, yield 55%, white solid.
^1H NMR (600 MHz, _CDCl3 ) δ 7.69 (dd, J = 8.4, 1.2 Hz, 2H), 7.57 (t, J = 7.8 Hz, 2H), 7.35-7.42 (m, 5H), 7.14 (d, J = 6.6 Hz, 1H), 7.11 (d, J = 6.6 Hz, 1H), 3.55 (d, J = 3.0 Hz, 1H), 2.92 (d, J = 3.0 Hz, 1H), 2.67 (td, J = 12.0, 3.0 Hz, 1H), 2.32 (s, 1H), 2.20 (dd, J = 12.6, 1.8 Hz, 1H), 2.10-2.13 (m, 2H), 2.01 (d, J = 12.6 Hz, 1H), 1.87-1.90 (m, 4H), 1.78 (d, J = 11.4 Hz, 1H), 1.45 (d, J = 12.6 Hz, 1H).
^13C NMR (150 MHz, _CDCl3 ) δ 140.93, 139.53, 138.33, 138.02, 134.01, 129.86, 127.32, 127.12, 126.03, 124.518, 123.02, 122.01, 115.75, 113.95, 108.07, 108.00, 50.09, 41.40, 40.06, 39.66, 38.42, 37.24, 32.34, 28.90, 28.82, 28.33 (two sp2 carbon atoms were overlapping with others.).
HRMS (DART, positive) m/z calcd for _C28H26N _[ M+H] ⁺ : m/z 376.20597. Found: m/z 376.20772.

Synthesis Example 6-29: 10,11,12,13,14,14a-hexahydro-9H-8b,12:10,14-dimethanocycloocta[e]acephenanthrene Synthesis method: Synthesis method B. 9-Bromophenanthrene was used. Yield 38.2 mg, 41%, white solid. The product was obtained as a 1:1 mixture with structural isomers.
^1H NMR (600 MHz, _CDCl3 ) δ 8.57-8.61 (m, 2x1H), 8.26-8.33 (m, 2x1H), 7.87-7.89 (m, 2x1H), 7.52-7.65 (m, 2x3H), 7.45 (d, J = 14.4 Hz, 1H), 7.38-7.40 (m, 2x1H), 7.30-7.34 (d, J = 6.6 Hz, 1H), 3.55 (s, 1H), 3.52 (s, 1H), 2.83 (d, J = 2.4 Hz, 1H), 2.79 (d, J = 2.4 Hz, 1H), 2.51-2.57 (m, 2x1H), 2.24-2.31 (m, 2×2H), 2.07-2.09 (m, 2×1H), 1.83-2.00 (m, 2×6H), 1.70 (dt, J = 13.2, 2.4 Hz, 2×1H), 1.46-1.49 (m, 1H), 1.33 (dt, J = 13.2, 2.4 Hz, 1H).
^13C NMR (150 MHz, _CDCl3 ) δ 152.44, 150.51, 144.99, 143.14, 136.11, 135.95, 134.25, 134.21, 129.38, 129.33, 128.91, 128.73, 127.82, 127.78, 126.53, 126.48, 125.29, 122.98, 119.39, 119.35, 119.23, 118.26, 117.71, 116.59, 57.46, 57.09, 50.97, 46.88, 46.47, 44.75, 44.19, 39.31, 39.15, 38.95, 37.37, 37.19, 31.84, 31.77, 29.40, 29.35, 28.87, 28.81, 28.22, 28.04.
HRMS (DART, positive) m/z calcd for _C30H25 _[ M+H] ⁺ : m/z 311.17943. Found: m/z 311.17946.

Other compounds were also identified by ¹ H NMR and other methods.

Example 1

DMPSi denotes polydimethylsilane. Sc(OTf) ₃ denotes scandium(III) trifluoromethanesulfonate.

Adamantane-fused arene compound 6 (0.1 mmol, 1 equivalent) obtained in Synthesis Example 6-1, a rhodium and platinum composite catalyst supported on polydimethylsilane and alumina (Rh/Pt(DMPSi/Al ₂ O ₃ ; 10 mol%), scandium(III) trifluoromethanesulfonate (Sc(OTf) ₃ 10 mol%) was added, followed by dehydrated heptane (1.5 mL). The test tube was placed in a stainless steel pressure vessel, and the inside of the vessel was fully replaced with hydrogen gas (10 atm (1 MPa)). The reaction solution was heated to 125°C and then stirred for 72 hours. Thereafter, the reaction solution was cooled to room temperature, filtered using Celite, and washed with ethyl acetate. The obtained organic layer was subjected to solvent distillation under reduced pressure. The crude product was purified by silica gel column chromatography (developing solvent: hexane only). Subsequently, purification was performed using gel filtration chromatography to obtain diamondoid compound 7 (2.7 mg, 12%).
^1H NMR (600 MHz, _C6D6 ) δ 1.62-2.06 (m, 18H), 1.40 (d, J = 12 Hz 1H) _, 1.08-1.34 (m, 8H), 1.01 (d, J = 10.2 Hz 1H),0.85-0.95 (m, 2H), 0.58-0.79 (m, 4H).
GC-MS(EI) 298.30 (m/z).

Examples 2 to 10
The reaction was carried out in the same manner as in Example 1, except that appropriate compounds were used as raw materials.

Example 3: (6br,8R,10S,12s)-Hexadecahydro-1H-6b,10:8,12-dimethanocycloocta[a]acenaphthylene
^1H NMR (600 MHz, _C6D6 ) δ 2.26-2.21 (m, _1H ), 1.94 (t, J = 2.7 Hz, 1H), 1.87 (d, J = 2.4 Hz, 1H), 1.82-1.39 (m, 21H), 1.35-1.31 (m, 1H), 1.21 (d, J = 11.3 Hz, 1H), 1.15-1.04 (m, 3H), 0.77-0.73 (m, 1H).
^13C NMR (600 MHz, _CDCl3 ) δ 55.2, 48.2, 41.6, 39.8, 39.4, 39.3, 38.3, 37.2, 36.2, 33.1, 31.7, 31.4, 29.5, 29.5, 28.8, 27.3, 26.1, 25.2, 25.1, 17.9.

Isomer
^1H NMR (600 MHz, _C6D6 ) δ 2.32-2.27 (m, _1H ), 2.00 (t, J = 3.1 Hz, 1H), 1.93 (d, J = 2.7 Hz, 1H), 1.88-1.37 (m, 22H), 1.27 (d, J = 12.4 Hz, 1H), 1.21-1.09 (m, 3H), 0.80 (dd, J = 12.7, 3.4 Hz, 1H).
^13C NMR (600 MHz, _CDCl3 ) δ 56.9, 49.4, 45.5, 43.4, 42.3, 40.8, 40.4, 39.8, 39.2, 38.4, 37.9, 34.0, 33.5, 31.8, 31.3, 30.1, 29.8, 29.6, 29.3, 28.7, 28.1, 27.3, 26.8, 25.9, 25.4, 22.6, 22.0, 18.5.
HRMS (ESI) m/z: [M+H]+ Calcd for _C20H30 _270.2348 ; Found 270.2339.

Example 4: (8br,10R,12S,14s)-2-Methoxyoctadecahydro-1H-8b,12:10,14-dimethanocycloocta[l]phenanthrene
^1H NMR (600 MHz, _C6D6 ) δ 3.54 (q, 1H), 3.13 (m, 3H), 2.06-1.43 (m, 22H) _, 1.42-1.35 (m, 6H), 1.31-1.24 (m, 3H), 1.06 (dd, J = 11.9, 2.6 Hz, 1H).
^13C NMR (600 MHz, _CDCl3 ) δ 131.5, 126.2, 76.8, 55.7, 52.9, 43.0, 42.4, 40.3, 38.6, 37.5, 36.8, 35.6, 32.6, 32.4, 28.9, 28.8, 27.9, 26.9, 26.7, 26.2, 24.6, 23.4.
HRMS (ESI) m/z: [M+H] ⁺ Calcd for _C22H48O _328.3705 ; Found 328.3714.

Example 5: (8br,10R,12S,14s)-N,N-dimethyloctadecahydro-1H-8b,12:10,14-dimethanocycloocta[l]phenanthren-2-amine
^1H NMR (600 MHz, _C6D6 ) δ 3.91-3.99 (1H), 3.15-3.22 (1H) _, 2.19-2.26 (2H), 1.95-2.04 (2H), 1.80-1.88 (1H), 0.98-1.81 (32H).
^13C NMR (600 MHz, _CDCl3 ) δ 64.3, 52.9, 42.7, 42.1, 39.6, 38.3, 37.2, 36.7, 35.6, 32.5, 28.8, 28.7, 28.6, 28.2, 27.7, 27.1, 26.7, 26.6, 26.0, 25.5, 24.5, 24.3, 23.7, 23.2.
HRMS (ESI) m/z: [M+H] ⁺ Calcd for _C24H38N _341.3083 ; Found 341.3081.

Example 6: (6br,8R,10S,12s)-Hexadecahydro-1H-6b,10:8,12-dimethanocycloocta[a]acenaphthylene-1-ol
^1H NMR (600 MHz, _C6D6 ) δ 1.99-1.85 (m, _7H ), 1.80-0.71 (m, 23H).
^13C NMR (600 MHz, _CDCl3 ) δ 86.2, 77.0, 76.8, 53.6, 42.4, 41.5, 38.9, 37.6, 36.6, 31.7, 31.2, 30.4, 30.3, 29.3, 29.0, 28.1, 26.8, 26.8, 22.1, 20.5.
HRMS (ESI) m/z: [M+H] ⁺ Calcd for _C20H30O _286.2296 ; Found 286.2297.

Example 7: (4br,6R,8S,10s)-Octadecahydro-1H-4b,8:6,10-dimethanocycloocta[a]cyclopenta[fg]acenaphthylene
^1H NMR (600 MHz, _C6D6 ) δ 2.53 (td, J = 11.9, 8.5 Hz, 1H), 2.42-2.36 (m, 1H) _, 2.30-2.25 (m, 1H), 2.10-1.95 (m, 3H), 1.89-1.78 (m, 5H), 1.76-1.68 (m, 3H), 1.65-1.33 (m, 14H), 1.29-1.21 (m, 2H), 1.10-1.01 (m, 2H).
^13C NMR (600 MHz, _CDCl3 ) δ 52.8, 48.4, 39.9, 39.4, 39.3, 38.7, 38.5, 38.1, 37.6, 37.3, 34.9, 34.2, 32.5, 31.5, 30.9, 29.6, 29.2, 29.0, 29.0, 27.1, 25.6, 20.5.
HRMS (ESI) m/z: [M+H]+ Calcd for _C22H32 _296.2504 ; Found 296.2510.

Example 8: (8bS,14R)-2-((8bS,10S,14R,14aR)-octadecahydro-1H-8b,12:10,14-dimethanocycloocta[l]phenanthren-7-yl)octadecahydro-1H-8b,12:10,14-dimethanocycloocta[l]phenanthrene
^1H NMR (600 MHz, _C6D6 ) δ 1.93-2.05 ( _5H ), 1.84-1.89 (1H), 1.55-1.80 (20H), 0.97-1.55 (38H).
HRMS (ESI) m/z: [M+H] ⁺ Calcd for _C44H46 _594.5164 ; Found 594.5120.

Example 9: (9s,11R,13S,14ar)-icosahydro-1H-9,13:11,14a-dimethanocycloocta[e]acephenanthrene
Isolation of 3 isomers was difficult, the ratio of isomers is 1:1.4:0.5. (from GC)
HRMS (ESI) m/z: [M+H] ⁺ Calcd for _C24H36 _324.2817 ; Found 324.2833.

Example 10: 1-((8br,10R,12S,14s)-octadecahydro-1H-8b,12:10,14-dimethanocycloocta[l]phenanthren-2-yl)ethan-1-ol
Isolation of 2 isomers was difficult, the ratio of isomers is 1:1.5 (from GC)
HRMS (ESI) m/z: [MH] ⁺ Calcd for _C24H37O _341.2844 ; Found 341.2849.

Claims

General formula (1):

[In the formula, ring A1 represents an aliphatic ring having two or more rings; R1 represents a hydrogen atom, an alkyl group, a cycloalkyl group, or an adamantyl group; and n represents an integer of 0 to 3.]
A diamondoid compound represented by the formula:
General formula (1A):

[In the formula, ring A2 and ring A3 are the same or different and represent an aliphatic ring. R1a , R1b , and R1c are the same or different and represent a hydrogen atom, an alkyl group, a cycloalkyl group, or an adamantyl group. R2a and R3a are the same or different and represent a hydrogen atom, a hydroxyl group, an alkyl group, an alkoxy group, a cycloalkyl group, an amino group, or an adamantyl group. R2a and R3a may be joined together to form an aliphatic ring.]
Or general formula (1B):

[Wherein, ring A4 and ring A5 are the same or different and represent an aliphatic ring. R1a , R1b and R1c are the same or different and represent a hydrogen atom, an alkyl group, a cycloalkyl group, or an adamantyl group. R4a and R5a are the same or different and represent a hydrogen atom, a hydroxyl group, an alkyl group, an alkoxy group, a cycloalkyl group, an amino group, or an adamantyl group. R4a and R5a may be joined together to form an aliphatic ring.]
The diamondoid compound according to claim 1, which is a compound represented by the formula:
General formula (1A1):

[In the formula, R 2a , R 2b , R 2c , R 2d , R 3a , R 3b , R 3c and R 3d are the same or different and represent a hydrogen atom, a hydroxyl group, an alkyl group, an alkoxy group, a cycloalkyl group, an amino group, or an adamantyl group. R 2a and R 2b , R 2b and R 2c , R 2c and R 2d , R 3a and R 3b , R 3b and R 3c , R 3c and R 3d , and R 2a and R 3a may be joined together to form an aliphatic ring at least at one position.]
Or general formula (1B1):

[In the formula, R 1 and n are the same as above. R 4a , R 4b , R 4c , R 5a , R 5b and R 5c are the same or different and represent a hydrogen atom, a hydroxyl group, an alkyl group, an alkoxy group, a cycloalkyl group, an amino group, or an adamantyl group. R 4a and R 4b , R 4b and R 4c , R 5a and R 5b , R 5b and R 5c , and R 4a and R 5a may be joined together to form an aliphatic ring at least at one position.]
The diamondoid compound according to claim 2, which is a compound represented by the formula:
General formula (1A'):

[In the formula, ring A2 and ring A3 are the same or different and represent an aliphatic ring. R1a , R1b , R1c , R1d , R1e , and R1f are the same or different and represent a hydrogen atom, an alkyl group, a cycloalkyl group, or an adamantyl group.]
Or general formula (1B'):

[In the formula, ring A4 and ring A5 are the same or different and represent an aliphatic ring. R1a , R1b , R1c , R1d , R1e , and R1f are the same or different and represent a hydrogen atom, an alkyl group, a cycloalkyl group, or an adamantyl group.]
The diamondoid compound according to claim 2, which is a compound represented by the formula:
General formula (1A'1):

[In the formula, R 2b , R 2c , R 2d , R 3b , R 3c and R 3d are the same or different and each represents a hydrogen atom, a hydroxyl group, an alkyl group, an alkoxy group, a cycloalkyl group, an amino group, or an adamantyl group. R 2b and R 2c , R 2c and R 2d , R 3b and R 3c , and R 3c and R 3d may be joined together at least at one position to form an aliphatic ring.]
Or general formula (1B'1):

[In the formula, R 4b , R 4c , R 5b and R 5c are the same or different and each represents a hydrogen atom, a hydroxyl group, an alkyl group, an alkoxy group, a cycloalkyl group, an amino group, or an adamantyl group. R 4b and R 4c , and R 5b and R 5c may be joined together at least at one position to form an aliphatic ring.]
The diamondoid compound according to claim 4, which is a compound represented by the formula:
A method for producing the diamondoid compound according to any one of claims 1 to 5, comprising the steps of:
(II) General formula (2):

[In the formula, R 1 and n are the same as defined above. Ring A 1 ' represents an aromatic ring corresponding to ring A 1. ]
The method includes a step of hydrogenating an adamantane-fused aromatic compound represented by the following formula (1):
The method of the present invention, wherein the catalyst comprises a catalyst containing rhodium and platinum and a Lewis acid catalyst.
The method according to claim 6, wherein the Lewis acid catalyst has an active center in an element of Group 3, Group 13, or Group 14 of the periodic table.
The method according to claim 6, wherein step (II) is carried out in the presence of an organic solvent.
The method according to claim 8, wherein the organic solvent is an alkane.
The adamantane-fused aromatic compound is
(IA) General formula (4):

[In the formula, ring A 1 ' represents an aromatic ring corresponding to ring A 1 and ring A 1 '. X 1 represents a halogen atom.]
and then reacting an aromatic compound represented by the general formula (5A) or (5B):

[In the formula, R 1 and n are the same as above.]
and reacting the compound with an adamantanone compound represented by the formula:
General formula (6):

[In the formula, A 1″ , R 1 and n are the same as defined above.]
and (IB) a step of reacting the adamantane-containing arene compound obtained in the step (IA) with a Bronsted acid and/or a Lewis acid.
The method according to claim 10, wherein the nucleophile is an organolithium compound and/or an organomagnesium compound.
The aromatic compound represented by the general formula (4) is
General formula (4A):

[In the formula, X1 is the same as defined above. Ring A2' and ring A3' may be the same or different and each represent an aromatic ring. R2a and R3a may be the same or different and each represent a hydrogen atom, a hydroxyl group, an alkyl group, an alkoxy group, a cycloalkyl group, an amino group, or an adamantyl group. R2a and R3a may be joined together to form an aromatic ring.]
Or general formula (4B):

[In the formula, ring A4 and ring A5 are the same or different and each represents an aromatic ring. X2 represents a halogen atom. R4a and R5a are the same or different and each represents a hydrogen atom, a hydroxyl group, an alkyl group, an alkoxy group, a cycloalkyl group, an amino group, or an adamantyl group. R4a and R5a may be joined together to form an aromatic ring.]
The method according to claim 10, wherein the compound is represented by the formula: