TW201004965A - New borane-amine complexes and their application in Suzuki-type cross-coupling reactions - Google Patents

Abstract

The invention relates to new amine complexes of B-organyl-9-borabicyclo[3.3.l]no-nanes and to solutions of said complexes. Furthermore, the invention relates to a method of using trialkylborane-amine complexes in Suzuki-type cross-coupling reactions and to a process to form new carbon-carbon bonds in a Suzuki-type cross-coupling reaction with a triorganoborane, which is carried out in the presence of an amine.

Description

201004965 VI. INSTRUCTIONS OF THE INVENTION: TECHNICAL FIELD OF THE INVENTION The present invention relates to novel B-organo-9-borobicyclo[3·3·1]indole-alkylamine complexes and solutions of such complexes. Further, the present invention relates to a method of using a tris-borane borane amine complex in a eucalyptus-type cross-coupling reaction, and forming a new carbon-carbon bond in a cross-coupling reaction with a 'triorganoborane' eucalyptus type The process is carried out in the presence of an amine. [Prior Art] 0 The cross-coupling reaction between organic electrophiles and organoboron derivatives via transition metal catalysis to form new carbon-carbon bonds is called Suzuki-type cross-coupling reaction (Miyaura, N.; Suzuki, A·, Chem Rev. 95, pp. 2457-2483 (1995)). For example, in this eucalyptus-type cross-coupling reaction, tri-organoborane can be used as a source of nucleophilic organic moieties that are coupled to organic electrophiles. The readily available B-organo-9-borobicyclo[3.3.1]nonane (B-organo-9-BBN) is a particularly useful reactant in such cross-coupling reactions because of the exocyclic alkyl groups. In the bicyclic 9-borobicyclo[3.3.1]nonane skeleton preferential coupling (Miyaura, N.; Suzuki, A. et al., j. Am. Chem. Soc. 111, 314-321 (1989); Netherton , MR et al., j. Am. Chem. Soc. 123, pp. 10099 to 101 00 (2001)). Hydrogenation of τ thin or block hydrocarbons with 9-borobicyclo[3·3.1]pyrene (9-ΒΒΝ) is easy to obtain a variety of Β-organo-9-borobicyclo[3.3.丨]decane β in favorable conditions The hydrazine-hydrogenation reaction via a suitable olefin and subsequent Suzuki-type cross-coupling reaction with an organic electrophile can form a ruthenium-organic group 9βββ in a two-step process in the same reaction vessel by one-pot synthesis ( For example 139668.doc 201004965

Rodriguez A. et al., Org. Biomol. Chem. 1, 973-977 (2003)). 9-BBN forms a pyrophoric solid with only a low solubility in a typical organic solvent due to its dimeric structure (Soderquist, JA; Brown, HC, J. Org. Chem. 46, pp. 4599-4600 (1981)) . These characteristics may hinder the large-scale application of 9-BBN, so alternatives are needed. It is known that 9-BBN dimerization vessels can be cleaved by the addition of certain Lewis bases and in some cases form stable 9-BBN-Lewis base complexes (Brown, HC et al., J. Am. Chem. Soc. 104, pp. 7148 to 7155 (1982); Gazzetta Chimica Italiana 117, pp. 517-523 (1987)). However, 9-BBN-pyridine complex (Brown, H_C., J. Org. Chem. 45, pp. 846-849 (1980)) shows only a relatively low ability to act as a shed hydrogenator (Brown, HC). Et al., Inorg. Chem. 16, pp. 3090 to 3094 (1977)). Recently, novel dialkylboraneamine complexes have been developed which are more suitable for the hydroboration reaction and thus obtain the corresponding trialkylboraneamine complex or mixture (WO 2008/055859). SUMMARY OF THE INVENTION One object of the present invention is to develop novel trialkylborane amine complexes and solutions thereof. Another object of the present invention is to provide a novel process for the use of a trialkylborane amine complex in a eucalyptus type cross-coupling reaction. A further object of the present invention is to develop a process for forming a new carbon-carbon bond in a Suzuki-type cross-coupling reaction which is carried out in the presence of an amine. Accordingly, a novel B-organo-9-borobicyclo[3.3.1]nonaneamine complex of formula (1) has been found: 201004965

(1), wherein: R is an organic group containing at least one direct # knot to a carbon atom of a ruthenium atom; and the amine is a substituted pyridine of the formula (2):

(2) 'R is <^-(:1()alkyl, Cl-C8 alkoxy*Ci_C8 alkoxyalkyl; and R3 is hydrogen or Cl-ClG alkyl, Ci-Cs alkoxy or CVC8-alkoxy-Cl-Cl oxime;

Or an alkylamine of the formula (3): r4r5nh, (3), wherein: R is hydrogen or C!-C1G alkyl; Another embodiment of the present invention is a solution comprising at least one novel B-organo 9-cyclopenta[3.3.1] guanidinamide complex and at least one solvent of the formula ( ???) 0 139668.doc 201004965 One example is a new method for forming a new carbon-carbon bond using a B-organo-9-BBN-amine complex of formula (1) in a Suzuki-type cross-coupling reaction. Further, a method of forming a new carbon-carbon bond has been found which comprises a cross-coupling reaction with a triorganic suzuki type which is carried out in the presence of an amine. [Embodiment] The novel B-organo-9-borobicyclo[3.3.1]nonaneamine complex of the present invention has the chemical structure of the formula (1):

Wherein: R1 is an organic group containing at least one carbon atom directly bonded to a boron atom; and the amine is a substituted pyridine of the formula (2): R2

(2), where: R2 is Ci-c,. An alkyl group, a Cl-C oxy group or a Cl_c8-alkoxy-Ci_Ci fluorenyl group; and R is hydrogen or a decyl group, a C1-C8 oxy group or a Ci-C8-alkoxy-CV Cl fluorene group; 139668.doc (3), 201004965 or alkylamine r4r5nh of formula (3) wherein: R is hydrogen or c^-Cio, and R is Ci-Ci. The novel organic compound-9-BBN-amine wherein the amine is substituted by the formula (2) In a preferred embodiment of the invention, the complex has the chemical structure of the formula (1), 0 bite.

As used in connection with the present invention, the term "organic group" means an organic group containing at least one carbon atom which may contain a hetero atom such as hydrogen, oxygen, nitrogen, sulfur, phosphorus, H, gas, bromine, iodine, boron. , bismuth, selenium, tin, or transition t is a genus such as iron, recorded sputum and so on. The organic group may have any straight or cyclic, branched or unbranched, monocyclic or polycyclic, carbocyclic or heterocyclic, saturated or unsaturated molecular structure, and may contain protected or unprotected functional groups. Further, the organic group may be bonded to a polymer or a polymer having a molecular weight of up to 1 to 10,000 Daltons, or a part thereof. Preferred organic groups are C^C:24 alkyl, Cs-Cm cycloalkyl, substituted alkyl, C2-C22 dilute, (5-fluorene-15 ring and C2-C22 fast group. For the purposes of the invention, the term "R Ci_C24 alkyl" means a branched or unbranched saturated hydrocarbon group comprising between 1 and 24 carbon atoms; examples are methyl, ethyl, propyl, isopropyl, butyl, Isobutyl, t-butyl, tert-butyl, pentyl, isopentyl, second pentyl, 1,2-dimethylpropyl, 1,1 dimethylpropyl, hexyl, 4· Mercaptopentyl, benzylidene, 2-methylpentyl, 3-methylpentyl, 1,1-dimethylbutyl, 2,2-dimethylbutyl I39668.doc 201004965 base, 3,3 - monomethylbutyl, 1,2-decylbutyl, iota, 3-didecylbutyl, 1,2,2-trimethylpropyl, 1,1,2-trimethylpropyl , heptyl, methylhexyl, 1-decylhexyl, 2,2-dimercaptopentyl, 3,3-didecylpentyl, 4 4 · dimethylpentyl, 1,2-dimethyl Pentyl, 1,3-dioxylpentyl, 14-didecylpentyl, 1,2,3-trimethylbutyl, 1,1,2-trimethylbutyl, trimethylbutyl , octyl, 6-methylglycol , κ methylheptyl, m3 tetradecyl butyl, fluorenyl ' 1-methyloctyl, 2-decyloctyl, 3-methyloctyl, 4-methyloctyl, 5-methyl octyl , 6-methyloctyl or 7-fluorenyloctyl, bethylheptyl, 2-ethylheptyl, 3-ethylheptyl, 4-ethylheptyl or 5-ethylheptyl, 1- Propylhexyl, 2-propylhexyl or 3-propylhexyl, decyl, 1-methylindolyl, 2-mercaptopurinyl, 3-mercaptopurinyl, 4-methylindolyl, 5-methyl Base group, 6-fluorenyl fluorenyl, 7-methyl fluorenyl and 8-methylindolyl, ethyl octyl, 2-ethyloctyl, 3-ethyloctyl, 4-ethyl octyl , 5-ethyloctyl or 6-ethyloctyl, 1-propylheptyl, 2-propylheptyl, 3-propylheptyl or 4-propylheptyl, undecyl, methyl Mercapto, 2-methylindolyl, 3·methylindolyl, 4-mercaptodecyl, 5-methylindenyl, 6-methylindenyl, 7-methylindenyl, 8-methylindole Or 9-methylindenyl, i-ethylindenyl, 2·ethylindolyl, 3-ethylindenyl, 4-ethylindenyl, 5-ethylindenyl, 6-ethylindenyl Or 7-ethylindenyl, 丨-propyloctyl, 2-propyloctyl, 3-propyloctyl, 4-propyloctyl or 5-propyl octyl , hexylheptyl, 2 butylheptyl or 3-butylheptyl, 1-pentylhexyl, dodecyl, methylundecyl, 2-methylundecyl, 3-methylundecyl, 4 _methylundecyl, 5-methylundecyl, 6-methylundecyl, 7-methylundecyl, 8-methylundecyl, 9-f-endecyl or 10-methyl Eleven, ethyl hydrazino, 2-ethyl fluorenyl, 139668.doc 201004965 3-ethyl fluorenyl, 4-ethyl fluorenyl, 5-ethyl fluorenyl, 6-ethyl fluorenyl, 7-B Alkyl or 8-ethylindenyl, 1-propylindenyl, 2-propylindenyl, 3-propylindenyl, 4-propylindenyl, 5-propylindenyl or 6-propyl Mercapto, 1-butyloctyl, 2-butyloctyl, 3-butyloctyl or 4-butyloctyl, iota-2-pentylheptyl and iso-s-s-s. Preferred are ethyl, propyl, isopropyl, butyl, isobutyl, second butyl, tert-butyl, pentyl, isopentyl, second amyl ' 1,2-dimethylpropane An alkyl group of a group, ι, ι·dimercaptopropyl, hexyl and octyl. The term "C3_C" 6 cycloalkyl" means a saturated hydrocarbon group containing between 3 and 16 carbon atoms and including a monocyclic or polycyclic moiety. Examples are cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclodecyl or cyclodecyl. Preferred are cycloalkyl, cyclopentyl and cyclohexylcycloalkyl groups. The term "substituted alkyl" means that at least one hydrogen atom is passed through a halogen atom (such as gas, gas, han or moth), an alkoxy group, an ester group, a tricarboyl group, a C6_CM aryl group or a C3-CM heteroaryl group. Substituted alkyl. The sf "C^-Cm alkoxy group" means a group derived from an aliphatic monool having a carbon atom of between 1 and 2 Å. The term "Ce-Cw aryl" means an unsaturated oxy group comprising between 6 and 14 carbon atoms and comprising at least one aromatic ring system such as phenyl or naphthyl or any other aromatic ring system. The term "C3-Cl4 heteroaryl" denotes a monocyclic or polycyclic aromatic ring system containing between 3 and 14 ring atoms in which at least one ring carbon atom is replaced by a hetero atom such as nitrogen, oxygen or sulfur. . Examples are: pyridyl, piperidylthiopyranyl, quinolyl, isoquinolyl, acridinyl, pyridazinyl, pyrimidinyloxazinyl, cyanoazinyl, triazinyl, pyrrolyl, furyl, Thienyl hydrazine 139668.doc -9- 201004965 base, isodecyl, pyrazolyl, imidazolyl, oxazolyl, isoxazolyl, oxazolyl, isothiazolyl and triazolyl. The term "C2-C22 alkenyl" means a straight or branched chain unsaturated hydrocarbon group containing between 2 and 22 carbon atoms and including at least one carbon-carbon double bond. Examples are vinyl, propyl, 1-methylethenyl, butylidene, isobutyl, 3-methyl-2-butenyl, 1-pentenyl, decyl-hexenyl, 3 _Hexenyl, 2,5-dimethylhex-4-en-3-yl, 1-heptenyl, 3-heptenyl, 1-octenyl, 1-decenyl, 2-decene , 3-decenyl, 1-decenyl, 3-decenyl, 1,3-butadienyl, iota, 4-pentadienyl, U·hexadienyl and M•hexadiene base. Preferred are alkenyl groups of vinyl, allyl, butenyl, isobutenyl, 1,3-butadienyl and 2,5-dimethylhex-4-en-3-yl. The term "Cs-Ch cycloalkenyl" means an unsaturated hydrocarbon group containing between 5 and 15 carbon atoms and including at least one carbon-carbon double bond and a monocyclic or polycyclic moiety. Examples are cyclopentenyl, methylcyclopentenylcyclohexenyl, cyclooctenyl, 1,3·cyclopentadienyl, 13·cyclohexadienyl, 14 cyclohexenyl, 1 , 3_cycloheptadienyl, 13,5-cycloheptatrienyl and 13 cyclooctyltetraenyl. The "CrC22 alkynyl group" means a straight or branched chain unsaturated hydrocarbon group containing between 2 and 22 carbon atoms and including at least one carbon-carbon reference bond. Examples of alkynyl groups include ethynyl, 2, propyl fast and 2 butyl or 3 ^ blocks. According to the invention, the substituted pyridine of formula (2) can be, for example, 2-methyl „bite, 2, 3-dimethyl ton bite, 2 4 dimethyl guanidine bit, 2 5 曱 2 ton bite, 5 ethyl 2-methyl pyridine, 4 ethyl 2 · methyl pyridine, 3 ethyl methyl 139668. Doc 201004965 pyridine, 2,5-diethylpyridine, 5-propyl-2-methylpyridine, 4-propyl-2-methyl ° bite, 5-isopropyl-2-methyl " Change, 5-tributyl-2-indenyl group than bite, 5-n-hexyl-2-methylpyridine, 4-isobutyl-2-methylpyridine or 2,4-dipropyl The preferred formula (2) "bite is 2-mercapto" than bite, 2,3-dimethylu ratio bite, 2,4-dimercaptopyridine, 2,5-lutidine and 5-ethyl-2-mercaptopyridine. In a preferred embodiment of the invention, the novel B-organo- 9-8]51-amine* complex has the chemical structure of formula (1) wherein Ri is Directly bonded to the organic group of the boron atom via two methylene groups and (1) shows the part of the formula > bch2ch2-, that is, R1 is -CH2CH3 or -CH2CH2-organic. These are preferably (1) Derivatives can For example) by the hydrogenation of a terminal olefin with a 9-BBN or 9-BBN amine complex, which is attributed to the well-known anti-Marknikov location selectivity of these hydrogenation reactions (anti_Mark〇vnik) 〇v regioselectivty). Examples of such preferred B-organo-9-BBN-amine complexes (1) have the chemical structure of the formula ,), wherein Ri is ethyl, propyl, butyl, pentyl , hexyl and octyl. _ In the case where the organic group R1 is substituted on the -BCH2CH2. moiety, the R1 group becomes more bulky and the mismatch between the amine and the triorganoborane may be hindered. In some cases Underneath, it was found that the novel B-organo-9-BBN-amine complex is not wrong. The mixture of B-organo-9-BBN has no mismatch in other cases. However, it contains any amine and B-organic. The composition of the -9-BBN derivative can be used very often for other reactions independent of the formation of the complex (see below). In another preferred embodiment of this month, the novel lysine B is conjugated with an organic amine. The chemical structure of the formula (1) wherein the amine is a compound of the formula (2) 139668.doc •11 · 201004965 wherein R3 is hydrogen or In a preferred embodiment of the invention, the novel oxime-organo-9-nonylamine complex has the chemical structure of formula (1) wherein Ri is _CH2CH3 or • CHzCH2-organic and the amine is 2-picoline, 2,3-dimethylpyridine, 2'-heart dimethylpyridinium, 2,5-lutidine or 5-ethyl-2-methylpyridine. The "B NMR spectrum of the novel B-organo-9-BBN-amine complex of formula (1) typically exhibits a broad single peak with a chemical shift δ between +10 ppm and +35 ppm, which indicates Strong coordination between the amine and the trialkylborane moiety. For example, the <octyl-9-boradicyclo[3.3.1]nonane-2-methylpyridine complex shows "b NMR resonance at δ = 26.6 ppm (see Example 1). The novel B-organo-9-BBN-amine complex (1) can be, for example, via an unsaturated compound such as an olefin or an alkyne with a 9-BBN or 9-BBN-Lewis base complex (eg, 9-BBN) Boron hydrogenation of -THF or 9-BBN-dimethylsulfide, followed by addition of the respective amines of formula (2) or (3) to the resulting organic -9-bbn derivative. Alternatively, the olefin or alkyne can be directly hydrobored with a complex of 9-BBN with an amine of formula (2) or an amine of formula (3). Accordingly, another embodiment of the present invention is a process for the synthesis of a novel B-organo-9-BBN-amine complex comprising the steps of: an olefin or an alkyne with 9-BBN and an amine of formula (2) or Boron hydrogenation of the amine of formula (3), or hydroboration of a dilute or alkyne with a 9-BBN or 9-BBN-Lewis base followed by the addition of an amine of formula (2) or an amine of formula (3). If necessary, the hydroboration reaction of an olefin or an alkyne with a 9-BBN or 9-BBN complex can be carried out in solution in the presence of at least one solvent. Preferably, the complex of 9-BBN with an amine of formula (2) or an amine of formula (3) is reacted with an olefin or an alkyne in an organic solvent 139668.doc -12- 201004965. Since the solubility of these 9·ΒΒΝ-amine complexes in organic solvents is generally higher compared to 9-BBN, it allows operation at higher concentrations, thereby allowing higher reactor loading and avoidance and handling as : 9-ΒΒΝ related difficulties of fire solids. Thus the initial product of this synthetic route is a solution of the novel oxime-organo-9-oxime-amine complex (1). These solutions may be used directly for further reaction, or the neodymium-organo-9-anthracene-amine complex (1) may be isolated in pure form by evaporation of the solvent. A preferred method of removing the solvent is to evaporate under reduced pressure to lower the boiling point of the solvent.謇 Accordingly, another embodiment of the present invention is a solution comprising at least one novel fluorene-organo-9-oxime-amine complex of formula (1) and at least one solvent. A suitable solvent for the solution of the present invention is a solvent in which the Β_organo- 9- decylamine complex has high solubility. Examples are ethers (such as diethyl ether, tetrahydrofuran or 2-hydrazinotetrahydrofuran), thioethers (such as disulfide or hydrazine, 6-thiazolidine) and hydrocarbons (such as pentane, hexane, heptane, cyclohexane, toluene or Xylene). Preferred solvents for the solution comprising at least one of the formula (1) fluorenyl-organyl-9 hydrazine complex are tetrahydrofuran, 2, methyltetrahydrofuran, dimethyl sulfide, hydrazine thioxane, toluene, hexane, Heptane or cyclohexane, preferably tetrahydrofuran, 2-methyltetrahydrofuran, toluene, hexane, heptane or cyclohexane. • The solution of the invention typically contains a concentration between 〇〇5 m〇1/1#5 丨/丨, preferably between 0.1 111 〇1/1 and 5 mol/丨, more preferably 〇5 and 3 Novel Β·organoyl- 9BBN•amine complex of formula (1) between mol/1. Another embodiment of the present invention is a method of synthesizing a solution comprising at least one novel B-organo-9-BBN-amine complex of formula (1) and at least one solvent, which comprises the steps of: at least one solvent Boron hydrogenation of an olefin or an alkyne I39668.doc •13· 201004965 with a 9-BBN complex with an amine of formula (2) or an amine of formula (3) or an alkene or alkyne with 9-BBN or 9_BBN-Loan Base argon argon argon followed by addition of an amine of formula (2) or an amine of formula (3). A further embodiment of the invention is a method of synthesizing a novel B organic group _9_ BBN-amine complex of formula (1), It comprises the steps of hydroborating an olefin or an alkyne with a complex of 9-BBN with an amine of formula (2) or an amine of formula (3) in at least one solvent, or olefin or alkyne with 9_BBN or 9_BBN_ The Lewis base complex is hydrobored followed by the addition of the amine of formula (2) or the amine of formula (3), and the complex is isolated from the formed solution. The separation is preferably carried out by evaporation of the solvent. Novel method for forming novel carbon-carbon bonds using the novel B-organic 9-BBN-amine complex of formula (1) in a eucalyptus-type cross-coupling reaction The novel B-organo-9-BBN-amine complex of the formula 〇) is used directly in the eucalyptus cross-coupling reaction without the need to separate the amine from the trialkylborane to develop a cost-effective method. In addition, it has been found that the presence of an amine does not interfere with the catalytic cycle in the Suzuki-type cross-coupling reaction with a tri-carbo-boride as a nucleophile. The facts indicate whether a miscibility is formed between the tri-alkyl sane and the amine. It does not matter whether there is a dynamic equilibrium between the tri- or pyro-paraffin and the amine substance separated by the hydrazine. This is of great value because the trialkylborane is easily via an anthracene and an alkyne and a dialkyl group. Prepared by a hydroboration reaction of a borane amine complex which is easier to handle and has a higher solubility than the corresponding dialkylborane without any amine. Therefore, dioxane The crude reaction product between a borane amine complex and an olefin or an alkyne can be directly used in a Suzuki-type cross-coupling reaction. 139668.doc -14- 201004965 Therefore, another aspect of the present invention is the formation of a new carbon-carbon Key method comprising diorganoborane Wood type cross-coupling reaction, which is carried out in the presence of an amine. Another embodiment of the present invention is a method of forming a new carbon-carbon bond comprising the steps of: olefin or alkyne and diorganoborane amine Boron hydroboration, and the resulting mixture of triorganoborane and amine in a eucalyptus type cross-coupling reaction. In one embodiment of the invention 'the three organoboranes in the process are Β_organyl-9- An anthracene derivative, such as fluorenyl-octyl-9-oxime. In another embodiment of the invention, the amine in the methods is substituted with formula (2) as defined above. Bipyridine or formula (3) Alkylamines. EXAMPLES The following examples illustrate the invention without limiting it. All reactions were carried out under dry and anaerobic conditions. Example 1: Hydroboration of 1-octene with 9-non-2-mercaptopyridine complex 29.5 g of 9-fluoren-2-mercaptopyridine The 43.1% by weight solution of the compound in raF (60 mmol) was diluted with 65 mi of anhydrous THF and cooled to hydrazine (>c. Slowly added 6.73 g of 1-octene (6 〇mm〇i) and at room temperature After the mixture was stirred for three hours, the reaction mixture was analyzed by nB NMR spectroscopy to reveal that there was no 9-BBN-2-mercaptopyridine complex ο"6 ppm) remaining and it was found to be B_xin at 26.6 ppm. The main peak of the base_9·ββν_2_mercaptopyridine complex. Using this fluorenyl-octyl-9-indole-2-mercaptopyridine complex in THF A 1.02 hydrazine stock solution was prepared for the following Suzuki experiment. 139668.doc •15· 201004965 Example 2: Hydroboration of 10-undecenoate and 9-BBN-2-mercaptopyridine complexes 2.5 g of 9-BBN-2- diluted with 10 ml of anhydrous THF A 43.1 wt% solution of the methylpyridine complex in THF (5 mmol). Then 1.12 ml of methyl 10-undecenoate (5 mmol) was added dropwise and the mixture was stirred at room temperature for three hours. The reaction mixture was then analyzed by "B NMR spectroscopy, revealing that no 9-BBN-2-mercaptopyridine complex (δ = -1·6 ppm) remained and that it was found to be B- at 6 = 29.6 ppm. The main peak of ll-undecenoate)-9-BBN-2-methylpyridine complex. φ Example 3: Hydroboration of isoprene with 9-BBN-2-methylpyridine complex

A solution of 2.69 g of 9-BBN-2-methylpyridine complex in 40% by weight in THF (5 mmol) was diluted with 10 ml of dry THF. Then 0.5 ml of isoprene (5 mmol) was added and the mixture was stirred at room temperature for 24 hours. The reaction mixture was then analyzed by nB NMR spectroscopy to reveal the residue without 9-BBN-2-methylpyridine (δ = -1·6 ppm). Two resonances belonging to the mismatched and uncoordinated products were observed at δ=76·1 ppm and 18.1 ppm (1:0.71 = triorgano boron G alkane-2-methylpyridine: triorganosorane) . The proton spectrum shows the two isomers formed by addition of either double bond of isoprene. Example 4: Eucalyptus coupling of iodobenzene with B-octyl-9-BBN-2-methylpyridine complex (sp2-sp3) 139668.doc -16- 201004965

PdCI2(dppf).DCM NaOH 汆 THF reflux, 22h

123 mg (0.15 mmol) PdCl2(dppf).DCM complex ([1, Γ-bis(diphenylphosphino)-ferrocene]palladium dichloride-(11)- complex and dichloro Methane), 12 ml of steamed THF and 1.02 g (5 mmol) of ethene were mixed. Subsequently, 7.53 g of B-octyl-9-BBN-2-mercaptopyridine complex was added to a 16 wt% solution in THF, followed by the addition of 5 ml of 3 Μ sodium hydroxide (NaOH).

W solution gave a dark brown reaction mixture. The mixture was heated to reflux for 22 hours. then cooled to room temperature, hexane (20 mL) was added and the mixture was then quenched with hydrogen peroxide (H 2 〇 2, 30 w%, 2 ml). Stirring was continued for 10 minutes until the gas evolution stopped. The aqueous layer was separated from EtOAc (EtOAc) (EtOAc m. The crude product (1 - 83 g) was purified by silica gel column chromatography (yield hexane) to afford 558 mg (59%) of pure 1-octylbenzene as colorless oil. • Example 5: Suzuki coupling of 1-iodo-4-nitrobenzene with B-octyl-9-BBN-2-mercaptopyridine complex (sp2-sp3)

PdC!2(dppf).DCM 3M K3P04.H20, THF rt, 22h

02N

Ch3 200 mg (0.25 mmol) of PdCl2(dppf).DCM complex, 14.6 139668.doc -17- 201004965 ml of distilled THF and 1.245 g of 5 iodine-4-nitrobenzene. Then add 5.39 ml A 1.02 hydrazine solution of B-octyl-9-BBN-2-methylpyridine complex, followed by the addition of 3.33 ml of an aqueous solution of potassium phthalate (Κ3Ρ04) to give a black reaction mixture. The mixture was stirred for 21 h, then added Hexane (20 ml) followed by water (5 ml) and hydrogen peroxide (H 2 〇 2, 30 w%, 2 ml). Stirring was continued for 10 minutes until gas evolution ceased. The black mixture was filtered through a pad of celite. The aqueous layer was separated from the organic layer and extracted with diethyl ether (2×15 ml). The combined organic layer was dried over sodium sulfate The product was formed to give 0.70 φ g (60%) of 1-nitro-4-octylbenzene as a colorless oil. Example 6: Methyl 4-bromobenzoate and B-octyl-9-BBN-2-methyl Suzuki coupling of pyridine complex (sp2-sp3)

204 mg (0.25 mmol) of PdCl2(dppf).DCM complex, 14.6 ml of distilled THF and 1.08 g (5 mmol) of 4-indolyl methacrylate were mixed. Subsequently, 5.39 ml of a 1.02 Torr solution of B-octyl-9-BBN-2-mercaptopyridine complex was added, followed by the addition of 3.33 ml of an aqueous solution of potassium phthalate (Κ3Ρ04) to give a black reaction mixture. The mixture was stirred for 23 h then hexane (20 mL) was added followed by water (5 ml) and hydrogen peroxide (H202, 30 w%, 2 ml). Stirring was continued for 10 minutes until the gas evolution stopped. Separate the aqueous layer from the organic layer 139668.doc •18. 201004965 and extract with diethyl ether (2χ 15 mL). The combined organic layers were dried over sodium sulfate (Na.sub.2SO.sub.), filtered and evaporated to dry. The crude product was purified by EtOAc EtOAc (EtOAc:EtOAc:EtOAc . Example 7: Suzuki coupling of ethyl 4-bromobutyrate with B-octyl-9-BBN-2-mercaptopyridine complex (sp3-sp3)

Br-s^\/C〇2Et

Pd(OAc)2l P(Cy)3 k3po4.h2o, thf rt, 22 h h3c CO,Et 1.38 g (6 mmol) of solid potassium phosphate (K3P04.H20), 50 mg (0.2 mmol) of acetic acid lE-(II (Pd(OAc)2) and 112 mg (0.4 mmol) of tricyclohexylhydrazine (P(Cy)3) were mixed. The mixture was purged with nitrogen for 15 minutes, and then 5.88 ml of a solution of B-octyl-9-BBN-2-methylpyridine complex (6 mmol) in THF 1.02 EtOAc was added to the solid. The mixture was diluted with 5.9 mL anhydrous THF and was taken ethyl 4-bromobutyrate (975 mg, 5.0 mmol). The black suspension was stirred at room temperature for 22 h, then hydrogen peroxide (H202, 30 w%, 2 ml) was added and stirring was continued for another 10 minutes. After that time, diethyl ether (20 ml) was added followed by water (5 ml). The aqueous layer was separated from the organic layer and extracted twice with diethyl ether (2×15 mL). The combined organic layers were dried over sodium sulfate (Na2SO4) filtered and evaporated to dry. The crude product was purified by EtOAc EtOAc (EtOAc) elute For all useful purposes, all of the above references are incorporated herein by reference in their entirety by reference to 139 668. doc. While the invention has been shown and described with respect to the specific embodiments of the present invention, it will be apparent to those skilled in the art The modifications and adaptations are not limited to the specific forms shown and described herein. 139668.doc -20·

Claims (1)

201004965 VII. Scope of application for patents·· Organic group·9_Bronobicyclo[3.3.1J 1. A chemical compound with the general formula (!) Of which: (1), A direct bond to the butterfly R is an at least one organic group; and the amine having a carbon atom is a substituted pyridine of the formula (2): R1 Wherein: R2 is CVCw alkyl, CVCs alkoxy or CVC8-alkoxy·Cl-ClG alkyl; and R3 is hydrogen or CVCw alkyl, CVCs alkoxy SCVCV alkoxy-(VC1Q, or formula) (3) an alkylamine R4R5NH (3), wherein: R4 is hydrogen or (Vc1()alkyl; and R is 匸1 <10 alkyl. 139668.doc 4 201004965 2. The organic group of claim 1 9_shed double ring [3·3·1] 壬院amine complex' wherein the amine is substituted pyridine of formula (2). 3_ such as the oxime-organo-9-borobicyclo ring of claim 1 [3.3. 1] a decylamine complex wherein the amine is 2-methylpyridine, 2,3-dimethylpyridine, 2,4-dimethylpyridyl, 2,5-lutidine or 5-B Benzyl-2-methylpyridine. 4_ The oxime-organo-9-borobicyclo[3.3.1]nonaneamine complex of claim 1, wherein R, -CH2CH3 or -CH2CH2-organic. For example, the B-organo-9-borobicyclo[3.3.1]nonaneamine complex of claim 1 wherein alkyl, C3-C16 cycloalkyl, substituted alkyl, 2 22 syl, C5 -Ci5 cycloaliphatic or C2_C22 fast radical. 6. The B-organo-9-borobicyclo[3.3.1]nonaneamine complex of claim 1, wherein R1 is -CHAH3 or -C^CH2.organic Base, and The amine is 2-methyl 0-bite, 2,3-dimercaptopyridine, 2,4-dimercaptopyridine, 2,5-lutidine or 5-ethyl-2-methylpyridine. A solution comprising at least one oxime organic group _94 methamine complex of formula (1) and at least one solvent. 8. The solution of claim 7, wherein the solvent is selected from the group consisting of the following : tetrahydrofuran '2-methyltetrahydrofuran, dimethyl sulfide, 16 thiazepine, toluene, hexane, heptane and cyclohexane. 9. A synthesis comprising at least one B-organic group of formula (1) _9_BBN_ A method of a solution of an amine complex and at least one solvent, comprising the steps of: olefin or alkyne boron in a complex of 9-BBN with an amine of formula (2) or an amine of formula (3) in at least one solvent Hydrogenation, or hydroboration of an alkene or an alkyne with 9-BBN or 9_BBN Lewis complex, followed by addition of an amine of formula (2) or an amine of formula I39668.doc 201004965 r. l. A synthetic B-organic group of formula (1) A method of -9-BBN-amine complex comprising the steps of: hydroboring an olefin or an alkyne with a complex of 9-BBN with an amine of formula (2) or an amine of formula (3) or 9-BBN Or 9-BBN-Louis The complex is hydrogenated to a dilute hydrocarbon or alkyne shed. Then an amine of formula (2) or an amine of formula (3) is added. 11. A synthetic B-organo-9-BBN-amine complex of formula (1) A method comprising the steps of: hydroborating an alkene or an alkyne with a complex of 9·ΒΒΝ with an amine of the formula (2) or an amine of the formula (3) in at least one solvent, or 9 BBNs 9-BBN - A Lewis complex is used to hydrogenate a dilute hydrocarbon or a block hydrocarbon, followed by the addition of an amine of formula (2) or an amine of formula (3), and separation of the complex from the resulting solution. 12. A method of using a 3-organo- 9_ BBN-amine complex of formula (1) to form a new carbon-carbon bond in a Suzuki-type cross-coupling reaction. 13. A method of forming a new carbon-carbon bond comprising a eucalyptus-type cross-coupling reaction with triorganoborane, the reaction being carried out in the presence of an amine. 14. The method of claim 13, wherein the triorganoborane is a B-organic-9 ΒBN derivative. 15. The method of claim 13, wherein the amine is substituted by formula (2). Than bite or formula, (3) alkylamine. 16. A method of forming a new carbon-carbon bond comprising the steps of: hydroborating an alkene or an alkyne with a diorganoborolanamine complex, and using a triorganoborane in a Suzuki-type cross-coupling reaction. The resulting mixture of amines. 17. The method of claim 16, wherein the triorganoborane is a β-organoindole derivative. The method of claim 16, wherein the amine is a substituted pyridine of the formula (2) or an alkylamine of the formula (3). 139668.doc -4- 201004965 IV. Designated representative map: (1) The representative representative of the case is: (none) (2) The symbol of the symbol of the representative figure is simple: 5. If there is a chemical formula in this case, please reveal the best display. Chemical formula of the inventive feature: 139668.doc