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CN103524414B - There is bridged ring derivative and the synthetic method thereof of azepine decadiene structure fragment - Google Patents

There is bridged ring derivative and the synthetic method thereof of azepine decadiene structure fragment Download PDF

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CN103524414B
CN103524414B CN201310436649.3A CN201310436649A CN103524414B CN 103524414 B CN103524414 B CN 103524414B CN 201310436649 A CN201310436649 A CN 201310436649A CN 103524414 B CN103524414 B CN 103524414B
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biphamphos
stirring
methylphenyl
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product
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CN103524414A (en
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王春江
李清华
陶海燕
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Wuhan University WHU
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D221/00—Heterocyclic compounds containing six-membered rings having one nitrogen atom as the only ring hetero atom, not provided for by groups C07D211/00 - C07D219/00
    • C07D221/02—Heterocyclic compounds containing six-membered rings having one nitrogen atom as the only ring hetero atom, not provided for by groups C07D211/00 - C07D219/00 condensed with carbocyclic rings or ring systems
    • C07D221/22—Bridged ring systems
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
    • A01N43/40—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom six-membered rings
    • A01N43/42—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom six-membered rings condensed with carbocyclic rings
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/90—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having two or more relevant hetero rings, condensed among themselves or with a common carbocyclic ring system
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
    • C07D405/02—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings
    • C07D405/04—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings directly linked by a ring-member-to-ring-member bond
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
    • C07D405/02—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings
    • C07D405/06—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings linked by a carbon chain containing only aliphatic carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
    • C07D409/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings
    • C07D409/04—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings directly linked by a ring-member-to-ring-member bond
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
    • C07D409/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings
    • C07D409/06—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings linked by a carbon chain containing only aliphatic carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D471/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00
    • C07D471/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00 in which the condensed system contains two hetero rings
    • C07D471/08—Bridged systems

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  • Organic Chemistry (AREA)
  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Dentistry (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Plant Pathology (AREA)
  • General Health & Medical Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • Pest Control & Pesticides (AREA)
  • Agronomy & Crop Science (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

The invention discloses a kind of bridged ring derivative and the synthetic method thereof with azepine decadiene structure fragment; its synthetic method is: in organic solvent; under protection of inert gas; the imines derived with 2-acyl group cycloheptatriene and amino acid methyl ester is for raw material; mantoquita/TF-BiphamPhos complex compound or silver salt/TF-BiphamPhos complex compound are catalyzer; add carbonate or organic bases; after fully reacting at-40 ~ 25 DEG C of temperature; boil off solvent, target compound of the present invention can be obtained through column chromatography.The bridged ring derivative that the present invention has azepine decadiene structure fragment has weeding activity, can be used as the effective constituent of weedicide.

Description

Bridged ring derivative with aza-decadiene structure fragment and synthetic method thereof
Technical Field
The invention belongs to the technical field of synthesis of bridged ring compounds, and particularly relates to a bridged ring derivative with an aza-decadiene structural fragment and a synthesis method thereof.
Background
In recent years, the demand for bridged ring compounds having a specific structure has increased due to the discovery of more and more biologically functional active bridged ring compounds, so that the synthesis of a variety of non-natural bridged ring compounds has been of great significance and has attracted extensive attention. (a) J.I.Halliday, M.Chebib, M.D.McLeod, Aust.J.chem.2010, 63, 808; b) J.F.Huang, C.M.Orac, S.McKay, D.B.McKay, S.C.bergmeier, bioorg.Med.chem.2008, 16, 3816; c) D.Barker, D.H. -S.Lin, J.E.Carland, C.P. -Y.Chu, M.Chebib, M.A.Brimble, G.P.Chevage, M.D.McLeod, bioorg.Med.2005, 13, 4565.).
Bridged derivatives with aza-decadiene structural fragments are an important class of compounds, which are mainly used in some pharmaceutical and bioactive compounds ((a) J.D.Winkler, M.B.Rouse, M.F.Greeney, S.J.Harrison, Y.T.Jeon, J.am.chem.Soc.2002, 124, 9726, (b) J.H.Rigby, M.Fluming, Tetrahedron Lett.2002, 43, 8643, (c) H.F.Tang, N.Yusuff, J.L.Wood, org.Lett.2001, 3, 1563.).
Disclosure of Invention
The invention aims to provide a bridged ring derivative with an aza-decadiene structural fragment and a synthesis method thereof.
The invention provides a bridged ring derivative with an aza-decadiene structural fragment, which has the following structural formula:
wherein,
R1is aryl, alkyl or hydrogen;
R2is aryl or alkyl;
R3is aryl, alkyl or hydrogen.
R is as defined above1Preferably phenyl, methylphenyl, methoxyphenyl, halophenyl, p-trifluoromethylphenyl, naphthyl, furyl, thienyl or alkyl; it is further preferably phenyl, p-methylphenyl, m-methylphenyl, o-methylphenyl, p-methoxyphenyl, p-chlorophenyl, p-trifluoromethylphenyl, 1-naphthyl, 2-furyl, 2-thienyl or methyl.
R is as defined above2Preferably halophenyl, p-nitrophenyl, phenyl, alkylphenyl, methoxyphenyl, naphthyl, furyl, thienyl, n-propyl, or phenylalkenyl; it is further preferably p-chlorophenyl, o-chlorophenyl, p-bromophenyl, p-nitrophenyl, phenyl, p-methylphenyl, o-methylphenyl, p-methoxyphenyl, m-methoxyphenyl, 1-naphthyl, 2-furyl, 2-thienyl, n-propyl or styryl.
R is as defined above3Is methyl or hydrogen.
The invention also provides a synthesis method of the compound, which comprises the following steps:
in an organic solvent, under the protection of inert gas, taking 2-acyl cycloheptatriene and imine derived from amino acid methyl ester as raw materials, taking copper salt/TF-BiphamPhos complex or silver salt/TF-BiphamPhos complex as a catalyst, adding carbonate or organic base, fully reacting at the temperature of-40-25 ℃, evaporating the solvent, and carrying out column chromatography to obtain a target compound
The following preferences may be made for the above synthetic method:
1) the molar ratio of 2-acylcycloheptatriene to amino acid methyl ester derived imine is 1: 1.2-1: 2.
2) the copper salt/TF-BiphamPhos complex and the silver salt/TF-BiphamPhos complex are prepared by the following methods:
at room temperature, respectively taking copper salt or silver salt and chiral ligand TF-BiphamPhos to dissolve in an organic solvent according to the mole number of the copper salt or the silver salt not more than the mole number of the chiral ligand TF-BiphamPhos, and reacting to obtain a copper salt/TF-BiphamPhos complex or a silver salt/TF-BiphamPhos complex.
The chiral ligand TF-BiphamPhos is chiral ligand (S) -TF-BiphamPhos or chiral ligand (R) -TF-BiphamPhos, wherein the structural formula of the chiral ligand (S) -TF-BiphamPhos is as follows:the structural formula of the chiral ligand (R) -TF-BiphamPhos is shown in the specification
3) The column chromatography uses silica gel as a filling material, uses a mixed solvent of petroleum ether and ethyl acetate as an eluent, and comprises the following steps: the volume ratio of the petroleum ether to the ethyl acetate is 5: 1.
The target compound (I) or (II) prepared by the synthesis method is subjected to [2+2] cyclization reaction with N-phenylmaleimide in an organic solvent under the irradiation of 200W-600W ultraviolet light, and the structural formula of the compound is as follows:
wherein,
R1is aryl, alkyl or hydrogen;
R2is aryl or alkyl;
R3is aryl, alkyl or hydrogen.
R is as defined above1Preferably phenyl, methylphenyl, methoxyphenyl, halophenyl, p-trifluoromethylphenyl, naphthyl, furyl, thienyl or alkyl; it is more preferably phenyl, p-methylphenyl, m-methylphenyl, o-methylphenyl, p-methoxyphenylPhenyl, p-chlorophenyl, p-trifluoromethylphenyl, 1-naphthyl, 2-furyl, 2-thienyl or methyl.
R is as defined above2Preferably halophenyl, p-nitrophenyl, phenyl, alkylphenyl, methoxyphenyl, naphthyl, furyl, thienyl, n-propyl, or phenylalkenyl; it is further preferably p-chlorophenyl, o-chlorophenyl, p-bromophenyl, p-nitrophenyl, phenyl, p-methylphenyl, o-methylphenyl, p-methoxyphenyl, m-methoxyphenyl, 1-naphthyl, 2-furyl, 2-thienyl, n-propyl or styryl.
R is as defined above3Is methyl or hydrogen.
The organic solvent for the reaction of the above-mentioned compounds (III) and (IV) is preferably tetrahydrofuran or toluene.
The target compound (I) or (II) prepared by the synthesis method is reduced and hydrogenated by sodium borohydride in an organic solvent to obtain a compound, and the structural formula of the compound is as follows:
wherein,
R1is aryl, alkyl or hydrogen;
R2is aryl or alkyl;
R3is aryl, alkyl or hydrogen.
R is as defined above1Preferably phenyl, methylphenyl, methoxyphenyl, halophenyl, p-trifluoromethylphenyl, naphthyl, furyl, thienyl or alkyl; it is further preferably phenyl, p-methylphenyl, m-methylphenyl, o-methylphenyl, p-methoxyphenyl, p-chlorophenyl, p-trifluoromethylphenyl, 1-naphthyl, 2-furyl, 2-thienyl or methyl.
R is as defined above2Preferably a halophenyl groupP-nitrophenyl, phenyl, alkylphenyl, methoxyphenyl, naphthyl, furyl, thienyl, n-propyl, or phenylalkenyl; it is further preferably p-chlorophenyl, o-chlorophenyl, p-bromophenyl, p-nitrophenyl, phenyl, p-methylphenyl, o-methylphenyl, p-methoxyphenyl, m-methoxyphenyl, 1-naphthyl, 2-furyl, 2-thienyl, n-propyl or styryl.
R is as defined above3Is methyl or hydrogen.
The organic solvent for the reaction of the above-mentioned compounds (V) and (VI) is preferably tetrahydrofuran or diethyl ether.
The series of compounds (I), (II), (III), (IV), (V) and (VI) prepared by the invention are tested for bactericidal activity, and the series of compounds (I), (II), (III), (IV), (V) and (VI) are all found to have bactericidal activity and can be used as the active ingredient of the bactericide.
Compared with the prior art, the invention has the following characteristics:
1) the invention synthesizes a series of novel bridged derivatives with aza-decadiene structural fragments, and the bridged derivatives have herbicidal activity and can be used as active ingredients of herbicides.
2) The method has the advantages of simple synthesis, low cost, high yield, good corresponding selectivity of the obtained target compound, 75-88% of yield and more than or equal to 91% of corresponding selectivity excess;
3) the copper salt/TF-BiphamPhos complex and the silver salt/TF-BiphamPhos complex which are used as catalysts in the method have the advantages of high catalytic reaction speed and low catalyst consumption in the reaction.
Detailed Description
In order that the invention may be better understood, reference will now be made to the following examples.
The chiral ligand (S) -TF-BiphamPhos used in the following examples have the structural formulaThe structural formula of the chiral ligand (R) -TF-BiphamPhos is shown in the specification
Example 1
Preparation of
A25 mL reaction tube was charged with 0.01mmol of Cu (CH)3CN)4BF4And 0.011mmol (S) -TF-BiphamPhos, adding 1mL dichloromethane under nitrogen protection, stirring at room temperature for 1 hour, then adding 0.24mmol2- (p-chlorobenzylideneamino) methyl acetate, 0.20mmol 2-phenylacetylcycloheptatriene, and 0.03mmol triethylamine in sequence at-40 ℃, stirring for 24 hours, evaporating the solvent, and subjecting the product to silica gel column chromatography (petroleum ether/ethyl acetate 5/1) to obtain a white solid with a yield of 86%, an enantioselectivity of the product of 98%, HPLC (Chiralpak IB-H, i-propanol/hexane =10/90, flow rate1.0mL/min, lambda =254nm; t%r=13.54and17.38min.)[α]25 D=-461.2(c0.74，CHCl3);1HNMR(CDCl3，TMS，300MHz)7.67(d，J=7.2Hz，2H)，7.52-7.41(m，3H)，7.32(d，J=8.1Hz，2H)，7.25(d，J=8.1Hz，2H)，6.79(d，J=7.8Hz，1H)，6.11(dd，J1=8.4Hz，J2=11.7Hz，1H)，5.70(dd，J1=7.8Hz，J2=11.4Hz，1H)，4.24(m，1H)，4.16(m，1H)，4.04(m，1H)，3.45(s，3H)，3.11(m，1H)，2.50-2.45(m，1H)，1.80-1.66(m，2H);13C NMR(CDCl3，TMS，75MHz)198.3，172.3，140.7，139.8，139.7，139.3，138.4，132.5，131.3，129.4，128.2，127.9，127.2，125.8，65.0，64.1，51.7，40.7，34.0，27.7;IR(KBr)ν2926，2846，2360，2340，1736，1654，1638，1588，1491，1273，1179，1122，1089，800，773，669cm-1HRMS calculated value for C24H23ClNO3408.1374, measurement 408.1361.
Example 2
Preparation of
A25 mL reaction tube was charged with 0.01mmol of Cu (CH)3CN)4BF4And 0.011mmol (S) -TF-BiphamPhos, adding 1mL dichloromethane under the protection of nitrogen, stirring at room temperature for 1 hour, then adding 0.24mmol2- (o-chlorobenzylideneamino) methyl acetate, 0.20mmol 2-phenylacetylcycloheptatriene and 0.03mmol triethylamine at-40 ℃, stirring for 24 hours, evaporating the solvent, and subjecting the product to silica gel column chromatography (petroleum ether/ethyl acetate 5/1) to obtain a white solid with a yield of 82%, an enantioselectivity of 95% and HPLC (Chiralpak IB-H, i-propanol/hexane =10/90, flow rate1.0mL/min, lambda =254nm; t%r=7.71and9.95min.)[α]25 D=-299.0(c1.32，CHCl3);1HNMR(CDCl3，TMS，300MHz)7.69(d，J=6.9Hz，2H)，7.52-7.37(m，4H)，7.27-7.14(m，3H)，6.82(d，J=8.1Hz，1H)，6.15(dd，J1=8.1Hz，J2=11.7Hz，1H)，5.62(dd，J1=7.5Hz，J2=11.7Hz，1H)，4.59(m，1H)，4.18(m，1H)，4.10(m，1H)，3.45(s，3H)，3.31(m，1H)，2.54-2.50(m，1H)，1.80-1.67(m，2H);13C NMR(CDCl3，TMS，75MHz)198.3，172.2，140.9，140.1，139.3，138.5，132.0，131.3，129.4，129.1，128.7，128.0，127.9，127.5，126.5，126.0，65.4，61.9，51.7，38.0，34.2，27.8;IR(KBr)ν2944，2923，2849，2340，1736，1641，1588，1571，1437，1271，1237，1179，1121，754，724cm-1HRMS calculated value for C24H23ClNO3408.1371, measurement 408.1361.
Example 3
Preparation of
A25 mL reaction tube was charged with 0.01mmol of Cu (CH)3CN)4BF4And 0.011mmol (S) -TF-BiphamPhos, adding 1mL dichloromethane under nitrogen protection, stirring at room temperature for 1 hour, then adding 0.24mmol2- (p-bromophenylideneamino) methyl acetate, 0.20mmol 2-phenylacetylcycloheptatriene, and 0.03mmol triethylamine in sequence at-40 ℃, stirring for 24 hours, evaporating the solvent, and subjecting the product to silica gel column chromatography (petroleum ether/ethyl acetate 5/1) to obtain a white solid with 82% yield, 95% enantioselectivity of the product, HPLC (ChiralpaAD k-H, i-propanol/hexane =10/90, flow rate1.0mL/min, lambda =254nm; t%r=21.49and29.10min.)[α]25 D=-475.1(c1.50，CHCl3);1HNMR(CDCl3，TMS，300MHz)7.67(d，J=7.2Hz，2H)，7.50-7.40(m，5H)，7.19(d，J=8.1Hz，2H)，6.79(d，J=8.1Hz，1H)，6.09(dd，J1=8.4Hz，J2=11.7Hz，1H)，5.68(dd，J1=7.2Hz，J2=11.4Hz，1H)，4.21(m，1H)，4.15(m，1H)，4.02(m，1H)，3.44(s，3H)，3.10(m，1H)，2.48-2.44(m，1H)，1.78-1.74(m，2H);13C NMR(CDCl3，TMS，75MHz)198.3，172.2，143.2，140.7，140.3，139.8，139.2，138.4，131.2，129.4，127.9，127.7，125.9，120.6，65.1，64.2，51.7，40.7，34.0，27.8;IR(KBr)ν2949，2926，2850，2369，1736，1662，1641，1588，1489，1400，1272，1236，1122，1064，1009，896，799，722，664cm-1HRMS calculated value for C24H23BrNO3452.0868, measurement 452.0856.
Example 4
Preparation of
A25 mL reaction tube was charged with 0.01mmol of Cu (CH)3CN)4BF4And 0.011mmol (S) -TF-BiphamPhos, adding 1mL dichloromethane under nitrogen protection, stirring at room temperature for 1 hour, then adding 0.24mmol2- (p-nitrobenzylideneamino) methyl acetate, 0.20mmol 2-phenylacetylcycloheptatriene and 0.03mmol triethylamine in sequence at-40 ℃, stirring for 24 hours, evaporating the solvent, and subjecting the product to silica gel column chromatography (petroleum ether/ethyl acetate 5/1) to obtain a white solid with yield of 87%, enantioselectivity of the product is 98%, HPLC (Chiralpak IB-H, i-propanol/hexane =30/70, flow rate1.0mL/min, lambda =254nm; t%r=12.57and30.60min.)[α]25 D=-447.9(c1.22，CHCl3);1HNMR(CDCl3，TMS，300MHz)8.22(d，J=8.7Hz，2H)，7.68(d，J=6.9Hz，2H)，7.53-7.45(m，5H)，6.81(d，J=7.8Hz，1H)，6.13(dd，J1=8.1Hz，J2=11.4Hz，1H)，5.62(dd，J1=7.2Hz，J2=11.4Hz，1H)，4.39(d，J=2.7Hz，1H)，4.19(m，1H)，4.05(d，J=3.6Hz，1H)，3.46(s，3H)，3.21-3.20(m，1H)，2.55-2.51(m，1H)，1.85-1.80(m，2H);13C NMR(CDCl3，TMS，75MHz)198.3，172.1，148.7，146.8，141.0，139.0，138.7，138.3，131.5，129.4，128.0，126.9，126.5，123.5，65.0，64.4，51.8，40.6，34.0，27.8;IR(KBr)ν2945，2923，2851，2364，2337，1736，1640，1597，1518，1437，1347，1256，1122，1063，879，852，753cm-1HRMS calculated value for C24H23N2O5419.1612, measurement 419.1602.
Example 5
Preparation of
A25 mL reaction tube was charged with 0.01mmol of Cu (CH)3CN)4BF4And 0.011mmol (S) -TF-BiphamPhos, adding 1mL dichloromethane under nitrogen protection, stirring at room temperature for 1 hour, then adding 0.24mmol2- (benzylideneamino) methyl acetate, 0.20mmol 2-phenylacetylcycloheptatriene and 0.03mmol triethylamine in sequence at-40 ℃, stirring for 24 hours, evaporating the solvent, and subjecting the product to silica gel column chromatography (petroleum ether/ethyl acetate 5/1) to obtain a white solid with a yield of 83%, the enantioselectivity of the product is 97%, HPLC (Chiralpak IB-H, i-propanol/hexane =10/90, flow rate1.0mL/min, lambda =254nm; t%r=12.90and20.30min.)[α]25 D=-623.5(c0.74，CHCl3);1H NMR(CDCl3，TMS，300MHz)7.68(d，J=6.9Hz，2H)，7.53-7.43(m，3H)，7.40-7.24(m，5H)，6.80(d，J=8.1Hz，1H)，6.09(dd，J1=8.1Hz，J2=11.7Hz，1H)，5.72(dd，J1=7.5Hz，J2=11.4Hz，1H)，4.26(m，1H)，4.16(m，1H)，4.04(d，J=3.3Hz，1H)，3.45(s，3H)，3.14(m，1H)，2.50-2.45(m，1H)，1.78-1.74(m，2H);13C NMR(CDCl3，TMS，75MHz)198.4，172.4，141.2，140.7，140.5，139.5，138.6，131.2，129.4，128.2，127.9，126.8，125.9，125.6，65.3，64.8，51.7，41.0，34.1，28.0;IR(KBr)ν2949，2924，2851，2335，1736，1652，1646，1617，1587，1457，1436，1274，1237，1123，1062，1027，895，877，720cm-1HRMS calculated value for C24H24NO3374.1755, measurement 374.1751.
Example 6
Preparation of
A25 mL reaction tube was charged with 0.01mmol of Cu (CH)3CN)4BF4And 0.011mmol (S) -TF-BiphamPhos, adding 1mL dichloromethane under nitrogen protection, stirring at room temperature for 1 hour, then adding 0.24mmol2- (p-methylbenzylideneamino) methyl acetate, 0.20mmol 2-phenylacetylcycloheptatriene and 0.03mmol triethylamine in sequence at-40 ℃, stirring for 24 hours, evaporating the solvent, and subjecting the product to silica gel column chromatography (petroleum ether/ethyl acetate 5/1) to obtain a white solid with a yield of 82%, an enantioselectivity excess of 97% and HPLC (Chiralpak IB-H, i-propanol/hexane =10/90, flow rate1.0mL/min, lambda =254nm; t%r=12.48and18.72min.)[α]25 D=-409.8(c0.72，CHCl3);1HNMR(CDCl3，TMS，300MHz)7.67(d，J=7.5Hz，2H)，7.50-7.40(m，3H)，7.20-7.12(m，4H)，6.79(d，J=7.8Hz，1H)，6.18(dd，J1=8.7Hz，J2=11.7Hz，1H)，5.75(dd，J1=7.2Hz，J2=11.4Hz，1H)，4.23(m，1H)，4.15(m，1H)，4.04(d，J=3.9Hz，1H)，3.44(s，3H)，3.12(m，1H)，2.48-2.44(m，1H)，2.33(s，3H)，1.77-1.72(m，2H);13C NMR(CDCl3，TMS，75MHz)198.5，172.5，140.7，140.4，139.6，138.6，138.2，136.3，131.2，129.4，128.8，127.9，125.8，125.5，65.3，64.6，51.7，41.0，34.1，27.9，21.0;IR(KBr)ν2955，2922，2852，2344，1736，1638，1586，1528，1437，1378，1273，1123，1062，895，753cm-1HRMS calculated value for C25H26NO3388.1914, measurement 388.1907.
Example 7
Preparation of
A25 mL reaction tube was charged with 0.01mmol of Cu (CH)3CN)4BF4And 0.011mmol (S) -TF-BiphamPhos, in nitrogenAdding 1mL of dichloromethane under the protection of gas, stirring at room temperature for 1 hour, then adding 0.24mmol2- (o-methylbenzylideneamino) methyl acetate, 0.20mmol 2-phenylacetylcycloheptatriene and 0.03mmol triethylamine in sequence at-40 ℃, stirring for 24 hours, evaporating the solvent, and subjecting the product to silica gel column chromatography (petroleum ether/ethyl acetate 5/1) to obtain a white solid with a yield of 84% and an enantioselectivity of 93% for the product, (Chiralpak IB-H, i-propanol/hexane =10/90, flow rate1.0mL/min, lambda =254nm; t-propanol/hexane =10/90, andr=11.41and14.80min.)[α]25 D=-337.0(c0.30，CHCl3);1H NMR(CDCl3，TMS，300MHz)7.70(d，J=7.5Hz，2H)，7.52-7.42(m，3H)，7.16-7.06(m，4H)，6.83(d，J=8.1Hz，1H)，6.17(dd，J1=8.4Hz，J2=11.7Hz，1H)，5.68(dd，J1=7.5Hz，J2=11.4Hz，1H)，4.37(d，J=3.0Hz，1H)，4.17(m，1H)，4.09(d，J=3.9Hz，1H)，3.44(s，3H)，3.01(m，1H)，2.50-2.39(m，4H)，1.80-1.76(m，2H);13C NMR(CDCl3，TMS，75MHz)198.4，172.2，140.6，139.4，139.2，138.5，133.8，131.2，130.2，129.4，127.9，127.1，126.6，126.3，125.8，125.6，65.6，61.7，51.6，38.7，34.2，28.1，19.1;IR(KBr)ν2945，2924，2853，2364，2337，1738，1642，1587，1501，1435，1378，1272，1121，1063，878，811，749cm-1HRMS calculated value for C25H26NO3388.1917, measurement 388.1907.
Example 8
Preparation of
A25 mL reaction tube was charged with 0.01mmol of Cu (CH)3CN)4BF4Adding 1mL of dichloromethane into 0.011mmol (S) -TF-BiphamPhos under the protection of nitrogen, stirring for 1 hour at room temperature, and then sequentially adding 0.24mmol2- (m-methoxybenzylidene) at-40 DEG CAmino) methyl acetate, 0.20mmol 2-phenylacetylcycloheptatriene, and 0.03mmol triethylamine, stirred for 24H, the solvent was evaporated off and the product was chromatographed over silica gel (petrol ether/ethyl acetate 5/1) to give a white solid in 77% yield with 95% enantioselectivity of the product (Chiralpak IB-H, i-propanol/hexane =20/80, flow rate1.0ml/min, λ =254nm; t;, tr=12.11and12.99min.)[α]25 D=-377.6(c1.12，CHCl3);1H NMR(CDCl3，TMS，300MHz)7.67(d，J=6.9Hz，2H)，7.53-7.41(m，3H)，7.29-7.24(m，1H)，6.90-6.79(m，4H)，6.11(dd，J1=8.1Hz，J2=11.4Hz，1H)，5.76(dd，J1=7.5Hz，J2=11.4Hz，1H)，4.24(d，J=3.3Hz，1H)，4.15(m，1H)，4.04(d，J=4.2Hz，1H)，3.82(s，3H)，3.45(s，3H)，3.13(m，1H)，2.50-2.45(m，1H)，1.75(m，2H);13C NMR(CDCl3，TMS，75MHz)198.5，172.4，159.5，142.9，140.6，140.5，139.6，138.6，131.3，129.4，129.2，127.9，125.6，118.3，112.0，111.8，65.3，64.7，55.2，51.7，40.9，34.1，27.9;IR(KBr)ν3022，2952，2925，2848，2345，1736，1638，1618，1585，1491，1457，1437，1260，1237，1178，1122，1047，895，773cm-1HRMS calculated value for25H26NO4404.1865, measurement 404.1856.
Example 9
Preparation of
A25 mL reaction tube was charged with 0.01mmol of Cu (CH)3CN)4BF4Adding 1mL of dichloromethane into 0.011mmol (S) -TF-BiphamPhos under the protection of nitrogen, stirring at room temperature for 1 hour, then adding 0.24mmol2- (p-methoxybenzylideneamino) methyl acetate, 0.20mmol 2-phenylacetylcycloheptatriene and 0.03mmol triethylamine at-40 ℃, stirring for 24 hours, and evaporating the solventThe product was chromatographed on a silica gel column (petrol ether/ethyl acetate 5/1) to give a white solid in 83% yield with 98% enantioselectivity of the product (Chiralpak AD-H, i-propanol/hexane =15/85, flow rate1.0mL/min, lambda =220nm; tr=27.14and30.92min.)[α]25 D=-647.4(c0.84，CHCl3);1H NMR(CDCl3，TMS，300MHz)7.67(d，J=7.2Hz，2H)，7.50-7.40(m，3H)，7.21(d，J=8.4Hz，2H)，6.87(d，J=8.4Hz，2H)，6.80(d，J=8.1Hz，1H)，6.10(dd，J1=8.1Hz，J2=11.7Hz，1H)，5.76(dd，J1=7.5Hz，J2=11.4Hz，1H)，4.20(d，J=3.3Hz，1H)，4.14(m，1H)，4.03(d，J=4.2Hz，1H)，3.79(s，3H)，3.44(s，3H)，3.10(m，1H)，2.48-2.43(m，1H)，1.77-1.72(m，2H);13C NMR(CDCl3，TMS，75MHz)198.4，172.4，158.4，140.8，140.6，139.5，133.4，131.2，129.4，127.9，126.9，125.5，113.5，65.3，64.3，55.1，51.7，41.0，34.1，27.9;IR(KBr)ν2945，2925，2852，2362，1737，1642，1577，1501，1437，1383，1248，1122，1063，1032，895，832，778cm-1HRMS calculated value for C25H26NO4404.1857, measurement 404.1856.
Example 10
Preparation of
A25 mL reaction tube was charged with 0.01mmol of Cu (CH)3CN)4BF4And 0.011mmol (S) -TF-BiphamPhos, adding 1mL dichloromethane under the protection of nitrogen, stirring at room temperature for 1 hour, then sequentially adding 0.24mmol2- (1-naphthalene benzylidene amino) methyl acetate, 0.20mmol 2-phenylacetylcycloheptatriene and 0.03mmol triethylamine at-40 ℃, stirring for 24 hours, evaporating the solvent, and subjecting the product to silica gel column chromatography (petroleum ether/ethyl acetate 5/1) to obtain a white solid with the yield of 81 percent and the enantioselectivity of the product96% sexual excess (Chiralpak AD-H, i-propenol/hexane =30/70, flow rate1.0mL/min, lambda =254nm; tr=8.21and23.20min.)[α]25 D=-350.9(c0.82，CHCl3);1H NMR(CDCl3，TMS，300MHz)8.07(d，J=8.1Hz，1H)，7.90(d，J=7.5Hz，1H)，7.79-7.71(m，3H)，7.60-7.43(m，6H)，7.28-7.26(m，1H)，6.83(d，J=8.1Hz，1H)，6.10(dd，J1=8.1Hz，J2=11.7Hz，1H)，5.47(dd，J1=7.5Hz，J2=11.4Hz，1H)，4.99(d，J=3.0Hz，1H)，4.25-4.20(m，2H)，3.47(s，3H)，3.32(m，1H)，2.67-2.62(m，1H)，1.86-1.82(m，2H);13C NMR(CDCl3，TMS，75MHz)198.5，172.4，140.8，140.4，139.5，138.5，137.1，136.9，133.6，131.3，129.9，129.5，129.1，128.0，127.4，126.0，125.4，125.1，123.1，122.4，65.8，61.1，51.7，40.0，34.5，28.1;IR(KBr)ν2945，2925，2852，2362，2347，1736，1638，1591，1517，1429，1352，1260，1123，1063，879，856，751cm-1HRMS calculated value for C28H26NO3424.1915, measurement 424.1907.
Example 11
Preparation of
A25 mL reaction tube was charged with 0.01mmol of Cu (CH)3CN)4BF4And 0.011mmol (S) -TF-BiphamPhos, adding 1mL dichloromethane under nitrogen protection, stirring at room temperature for 1 hour, then adding 0.24mmol2- (2-furylbenzylidene amino) methyl acetate, 0.20mmol 2-phenylacetylcycloheptatriene and 0.03mmol triethylamine at-40 ℃, stirring for 24 hours, evaporating the solvent, and subjecting the product to silica gel column chromatography (petroleum ether/ethyl acetate 5/1) to obtain a white solid with a yield of 81% and an enantioselectivity of 98%, (Chiralpak IB-H, i-propenol/hexane =10/90, flow rate1.0mL/min, lambda =254nm; t%r=9.78and19.96min.)[α]25 D=-331.3(c0.68，CHCl3);1H NMR(CDCl3，TMS，300MHz)7.65(d，J=6.9Hz，2H)，7.53-7.38(m，4H)，6.81(d，J=7.8Hz，1H)，6.34-6.33(m，1H)，6.18-6.09(m，2H)，5.91(dd，J1=7.2Hz，J2=11.7Hz，1H)，4.31(m，1H)，4.14(m，1H)，4.04(m，1H)，3.45(s，3H)，3.30-3.29(m，1H)，2.45-2.37(m，1H)，1.74-1.62(m，2H);13C NMR(CDCl3，TMS，75MHz)198.3，172.2，154.6，141.3，140.6，140.4，139.6，138.6，131.2，129.4，127.9，125.8，110.1，105.3，64.5，60.0，51.8，38.5，34.0，26.8;IR(KBr)ν2945，2923，2853，2371，2342，1736，1641，1588，1512，1437，1363，1274，1124，1064，879，796，753cm-1HRMS calculated value for C22H21NO4362.1395, measurement 362.1387.
Example 12
Preparation of
A25 mL reaction tube was charged with 0.01mmol of Cu (CH)3CN)4BF4And 0.011mmol (S) -TF-BiphamPhos, adding 1mL dichloromethane under the protection of nitrogen, stirring at room temperature for 1 hour, then adding 0.24mmol2- (2-thiophenylmethyleneamino) methyl acetate, 0.20mmol 2-phenylacetylcycloheptatriene and 0.03mmol triethylamine in sequence at-40 ℃, stirring for 24 hours, evaporating the solvent, and subjecting the product to silica gel column chromatography (petroleum ether/ethyl acetate 5/1) to obtain a white solid with yield of 83%, and enantioselectivity of the product of 94%, (Chiralpak IB-H, i-propenol/hexane =10/90, flow rate1.0mL/min, lambda =254nm; t%r=12.85and18.63min.)[α]25 D=-285.6(c0.70，CHCl3);1H NMR(CDCl3，TMS，300MHz)7.66(d，J=7.2Hz，2H)，7.51-7.40(m，3H)，7.26-7.21(m，1H)，6.99-6.98(m，2H)，6.81(d，J=7.5Hz，1H)，6.18-6.03(m，2H)，4.48(m，1H)，4.14(m，1H)，4.07(m，1H)，3.45(s，3H)，3.23(m，1H)，2.47-2.42(m，1H)，1.78-1.68(m，2H);13C NMR(CDCl3，TMS，75MHz)198.3，172.1，158.5，145.3，140.0，139.4，138.5，131.3，129.4，127.9，126.6，126.0，123.7，122.8，65.0，61.9，51.7，40.6，34.0，27.3;IR(KBr)ν2921，2850，2347，1736，1638，1588，1561，1440，1257，1178，1121，1062，891，718，694cm-1HRMS calculated value for C22H21NO3380.1325, measurement 380.1315.
Example 13
Preparation of
A25 mL reaction tube was charged with 0.01mmol of Cu (CH)3CN)4BF4And 0.011mmol (S) -TF-BiphamPhos, adding 1mL dichloromethane under the protection of nitrogen, stirring at room temperature for 1 hour, then adding 0.24mmol2- (propylmethyleneamino) methyl acetate, 0.20mmol 2-phenylacetylcycloheptatriene and 0.03mmol triethylamine in sequence at-40 ℃, stirring for 24 hours, evaporating the solvent, and subjecting the product to silica gel column chromatography (petroleum ether/ethyl acetate 5/1) to obtain a white solid with a yield of 75% and an enantioselectivity of 91%, (Chiralpak AD-H, i-propanol/hexane =5/95, flow rate1.0mL/min, lambda =254nm; t%r=21.12and23.92min.)[α]25 D=-226.2(c0.66，CHCl3);1H NMR(CDCl3，TMS，300MHz)7.63(d，J=8.1Hz，2H)，7.49-7.41(m，3H)，6.79(d，J=6.6Hz，1H)，6.21-6.19(m，2H)，4.08(m，1H)，3.88(m，1H)，3.42(s，3H)，2.98(m，1H)，2.74(m，1H)，2.24-2.19(m，1H)，1.62-1.40(m，6H)，0.97-0.92(m，3H);13C NMR(CDCl3，TMS，75MHz)198.5，172.8，140.9，140.4，139.5，138.7，131.1，129.4，127.9，125.5，64.4，62.0，51.6，38.2，36.8，34.5，27.2，19.4，14.1;IR(KBr)ν2954，2924，2854，2345，1736，1640，1585，1491，1458，1438，1271，722，700，669，631cm-1HRMS calculated value for C21H26NO3340.1916, measurement 340.1907.
Example 14
Preparation of
A25 mL reaction tube was charged with 0.01mmol of Cu (CH)3CN)4BF4And 0.011mmol (S) -TF-BiphamPhos, adding 1mL dichloromethane under the protection of nitrogen, stirring at room temperature for 1 hour, then adding 0.24mmol2- (styrylmethyleneamino) methyl acetate, 0.20mmol 2-phenylacetylcycloheptatriene and 0.03mmol triethylamine in sequence at-40 ℃, stirring for 24 hours, evaporating the solvent, and subjecting the product to silica gel column chromatography (petroleum ether/ethyl acetate 5/1) to obtain a white solid with a yield of 81% and an enantioselectivity of 97%, (Chiralpak IB-H, i-propanol/hexane =10/90, flow rate1.0mL/min, lambda =254nm; t = 10/90)r=17.08and27.68min.)[α]25 D=-136.2(c0.98，CHCl3);1H NMR(CDCl3，TMS，300MHz)7.67-7.65(m，2H)，7.45-7.23(m，8H)，6.81-6.79(m，1H)，6.61-6.56(m，1H)，6.25-6.20(m，3H)，4.12(m，1H)，3.98(m，1H)，3.86(m，1H)，3.45(s，3H)，2.96(m，1H)，2.37-2.34(m，1H)，1.71-1.67(m，2H);13C NMR(CDCl3，TMS，75MHz)198.4，172.5，140.9，140.7，139.5，138.6，136.7，131.3，129.9，129.8，129.5，128.5，128.0，127.4，126.3，125.7，64.4，63.5，51.8，40.3，34.1，27.3;IR(KBr)ν2949，2926，2851，2369，1739，1642，1595，1525，1435，1360，1245，1121，1064，879，866，749cm-1HRMS calculated value for C26H26NO3400.1920, measurement value 400.1907。
Example 15
Preparation of
A25 mL reaction tube was charged with 0.01mmol of Cu (CH)3CN)4BF4And 0.011mmol (S) -TF-BiphamPhos, adding 1mL dichloromethane under the protection of nitrogen, stirring at room temperature for 1 hour, then adding 0.24mmol2- (phenylmethyleneamino) methyl propionate, 0.20mmol 2-phenylacetylcycloheptatriene and 0.03mmol triethylamine in sequence at-40 ℃, stirring for 24 hours, evaporating the solvent, and subjecting the product to silica gel column chromatography (petroleum ether/ethyl acetate 5/1) to obtain a white solid with a yield of 84% and an enantioselectivity of 94%, (Chiralpak IB-H, i-propanol/hexane =5/95, flow rate1.0mL/min, lambda =254nm; tr=13.42and14.83min.)[α]25 D=-354.0(c0.16，CHCl3);1H NMR(CDCl3，TMS，300MHz)7.74(d，J=7.2Hz，2H)，7.55-7.42(m，3H)，7.38-7.30(m，5H)，6.73(d，J=7.8Hz，1H)，6.10(dd，J1=8.1Hz，J2=11.7Hz，1H)，5.66(dd，J1=7.2Hz，J2=11.4Hz，1H)，4.44(m，1H)，3.93(m，1H)，3.36(s，3H)，3.11(m，1H)，2.67-2.62(m，1H)，1.98(brs，1H)，1.73-1.69(m，4H)，1.55-1.50(m，1H);13C NMR(CDCl3，TMS，100MHz)197.9，175.1，142.2，141.2，140.2，138.2，138.1，131.8，130.0，128.3，128.1，126.9，126.1，125.4，64.9，58.1，52.0，40.8，37.8，24.1，22.6;IR(KBr)ν2957，2921，2851，2349，1765，1707，1629，1618，1570，1507，1458，1267，1230，1133，1113，888，833，752cm-1HRMS calculated value for C25H26NO3388.1908, measurement 388.1907.
Example 16
Preparation of
A25 mL reaction tube was charged with 0.01mmol of Cu (CH)3CN)4BF4And 0.011mmol (S) -TF-BiphamPhos, adding 1mL dichloromethane under the protection of nitrogen, stirring at room temperature for 1 hour, then adding 0.24mmol2- (p-chlorophenyl methyleneamino) methyl propionate, 0.20mmol 2-phenylacetylcycloheptatriene and 0.03mmol triethylamine at-40 ℃, stirring for 24 hours, evaporating the solvent, and subjecting the product to silica gel column chromatography (petroleum ether/ethyl acetate 5/1) to obtain a white solid with yield of 87% and enantioselectivity of 98%, (Chiralpak IB-H, i-propenol/hexane =10/90, flow rate1.0mL/min, lambda =254nm; t%r=8.71and9.68min.)[α]25 D=-292.0(c0.30，CHCl3);1H NMR(CDCl3，TMS，300MHz)7.73(d，J=7.2Hz，2H)，7.53-7.42(m，3H)，7.32(d，J=8.4Hz，2H)，7.26(d，J=8.4Hz，2H)，6.72(d，J=8.1Hz，1H)，6.10(dd，J1=8.1Hz，J2=11.7Hz，1H)，5.63(dd，J1=7.2Hz，J2=11.1Hz，1H)，4.41(m，1H)，3.93(d，J=4.2Hz，1H)，3.35(s，3H)，3.09(m，1H)，2.65-2.61(m，1H)，1.89(brs，1H)，1.71(s，3H)，1.55-1.51(m，1H);13C NMR(CDCl3，TMS，75MHz)197.8，175.2，149.1，142.3，140.0，139.6，137.9，132.5，131.8，129.9，128.3，128.1，127.5，125.6，64.7，57.5，52.0，40.6，37.7，24.0，22.7;IR(KBr)ν2945，2924，2853，2333，1734，1643，1588，1491，1444，1376，1267，1134，1112，1089，888，817，768cm-1HRMS calculated value for25H25NO3422.1523, measurement 422.1518.
Example 17
Preparation of
A25 mL reaction tube was charged with 0.01mmol of Cu (CH)3CN)4BF4And 0.011mmol (S) -TF-BiphamPhos, adding 1mL dichloromethane under the protection of nitrogen, stirring at room temperature for 1 hour, then adding 0.24mmol2- (p-chlorophenyl methylene amino) methyl acetate, 0.20mmol 2-p-methylphenyl acetyl cycloheptatriene and 0.03mmol triethylamine at-40 ℃, stirring for 24 hours, evaporating the solvent, and subjecting the product to silica gel column chromatography (petroleum ether/ethyl acetate 5/1) to obtain a white solid with a yield of 81% and an enantioselectivity of 96%, (Chiralpak IB-H, i-propenol/hexane =10/90, flow rate1.0mL/min, lambda =254nm; t%r=12.56and14.73min.)[α]25 D=-396.3(c1.04，CHCl3);1HNMR(CDCl3，TMS，300MHz)7.60(d，J=8.1Hz，2H)，7.33-7.23(m，6H)，6.77(d，J=7.8Hz，1H)，6.10(dd，J1=8.4Hz，J2=11.4Hz，1H)，5.67(dd，J1=7.5Hz，J2=11.4Hz，1H)，4.22(m，1H)，4.15(m，1H)，4.02(m，1H)，3.41(s，3H)，3.09(m，1H)，2.49-2.41(m，4H)，1.79-1.75(m，2H);13C NMR(CDCl3，TMS，75MHz)198.1，172.3，142.1，140.9，139.8，139.4，138.5，135.5，132.6，129.8，128.7，128.3，127.3，125.9，65.1，64.2，51.7，40.8，34.3，27.9，21.5;IR(KBr)ν2949，2923，2851，2369，2334，1736，1637，1595，1520，1437，1373，1256，1122，1063，878，840，745cm-1HRMS calculated value for C25H25NO3422.1527, measurement 422.1518.
Example 18
Preparation of
0.0 portion was added to a 25mL reaction tube1mmol Cu(CH3CN)4BF4And 0.011mmol (S) -TF-BiphamPhos, adding 1mL dichloromethane under the protection of nitrogen, stirring at room temperature for 1 hour, then adding 0.24mmol2- (p-chlorophenyl methylene amino) methyl acetate, 0.20mmol 2-o-methylphenylacetylcycloheptatriene and 0.03mmol triethylamine at-40 ℃, stirring for 24 hours, evaporating the solvent, and subjecting the product to silica gel column chromatography (petroleum ether/ethyl acetate 5/1) to obtain a white solid with the yield of 84% and the enantioselectivity of 97%, (Chiralpak IB-H, i-propenol/hexane =10/90, flow rate1.0mL/min, lambda =254nm; t%r=8.92and10.14min.)[α]25 D=-467.8(c0.70，CHCl3);1HNMR(CDCl3，TMS，300MHz)7.31-7.19(m，8H)，6.81(d，J=8.1Hz，1H)，6.07(dd，J1=8.1Hz，J2=11.7Hz，1H)，5.72(dd，J1=7.2Hz，J2=11.1Hz，1H)，4.28(m，1H)，4.08(m，2H)，3.65(s，3H)，3.13(m，1H)，2.49-2.45(m，1H)，2.27(s，3H)，1.79-1.75(m，1H);13C NMR(CDCl3，TMS，75MHz)200.0，172.5，142.1，141.2，141.0，139.6，139.4，135.8，132.6，130.4，129.2，128.3，127.9，127.2，126.0，125.0，65.6，64.3，51.9，40.7，32.5，27.9，19.3;IR(KBr)ν2949，2925，2852，2347，1737，1647，1643，1585，1491，1437，1291，1236，1131，1061，896，741cm-1HRMS calculated value for C25H25NO3422.1524, measurement 422.1518.
Example 19
Preparation of
A25 mL reaction tube was charged with 0.01mmol of Cu (CH)3CN)4BF4Adding 1mL of dichloromethane into 0.011mmol (S) -TF-BiphamPhos under the protection of nitrogen, stirring for 1 hour at room temperature, and then sequentially adding 0.24mmol2 at-40 DEG CMethyl (p-chlorophenylmethyleneamino) acetate, 0.20mmol 2-m-methylphenylacetylcycloheptatriene and 0.03mmol triethylamine, after stirring for 24H, the solvent was evaporated and the product was chromatographed on a silica gel column (petroleum ether/ethyl acetate 5/1) to give a white solid with a yield of 86% and an enantioselectivity of 98% for the product (Chiralpak IB-H, i-propanol/hexane =10/90, flow rate1.0mL/min, lambda =254nm; t; (Chiralpak IB-H, i-propanol/hexane = 10/90; flow rate1.0 mL/min; lambda =254nm; t;) was addedr=8.91and9.98min.)[α]25 D=-430.0(c0.70，CHCl3);1HNMR(CDCl3，TMS，300MHz)7.47-7.44(m，2H)，7.33-7.23(m，6H)，6.80(d，J=7.8Hz，1H)，6.11(dd，J1=8.1Hz，J2=11.7Hz，1H)，5.70(dd，J1=7.5Hz，J2=11.4Hz，1H)，4.23(d，J=3.3Hz，1H)，4.15(m，1H)，4.03(d，J=4.2Hz，1H)，3.46(s，3H)，3.11(m，1H)，2.45-2.42(m，4H)，1.79-1.66(m，2H);13C NMR(CDCl3，TMS，75MHz)198.5，172.2，140.8，139.7，139.3，138.4，137.8，132.5，132.0，129.6，128.7，128.2，127.7，127.2，126.6，125.9，65.1，64.1，51.7，40.7，33.9，27.8，21.2;IR(KBr)ν2952，2925，2851，2371，2340，1736，1647，1585，1491，1436，1380，1254，1199，1178，1090，1014，896，795，741cm-1HRMS calculated value for C25H25NO3422.1523, measurement 422.1518.
Example 20
Preparation of
A25 mL reaction tube was charged with 0.01mmol of Cu (CH)3CN)4BF4Adding 1mL of dichloromethane into 0.011mmol (S) -TF-BiphamPhos under the protection of nitrogen, stirring at room temperature for 1 hour, then adding 0.24mmol2- (p-chlorophenyl methylene amino) methyl acetate, 0.20mmol 2-p-methoxybenzeneacetyl cycloheptatriene and 0.03mmol triethylamine at-40 ℃, stirring for 24 hours, and evaporatingSolvent, and the product was chromatographed on a silica gel column (petrol ether/ethyl acetate 5/1) to give a white solid in 86% yield with 98% enantioselectivity of the product (Chiralpak IB-H, i-propanol/hexane =15/85, flow rate1.0mL/min, lambda =254nm; tr=15.28and16.53min.)[α]25 D=-441.5(c1.00，CHCl3);1HNMR(CDCl3，TMS，300MHz)7.73(d，J=8.4Hz，2H)，7.32(d，J=8.4Hz，2H)，7.26(d，J=8.4Hz，2H)，6.94(d，J=8.4Hz，2H)，6.72(d，J=8.4Hz，1H)，6.10(dd，J1=8.1Hz，J2=11.7Hz，1H)，5.66(dd，J1=7.2Hz，J2=11.1Hz，1H)，4.21(m，1H)，4.13(m，1H)，4.00(m，1H)，3.87(s，3H)，3.37(s，3H)，3.08(m，1H)，2.49-2.45(m，1H)，1.81-1.69(m，2H);13C NMR(CDCl3，TMS，75MHz)197.1，172.2，162.5，141.0，139.9，138.9，137.2，132.5，132.0，130.4，128.2，127.3，125.9，113.2，65.0，64.1，55.3，51.6，40.7，34.8，27.9;IR(KBr)ν2949，2927，2849，2344，1736，1655，1618，1599，1273，1238，1171，1122，1028，843，754cm-1HRMS calculated value for25H25NO4438.1476, measurement 438.1467.
Example 21
Preparation of
A25 mL reaction tube was charged with 0.01mmol of Cu (CH)3CN)4BF4Adding 1mL of dichloromethane into 0.011mmol (S) -TF-BiphamPhos under the protection of nitrogen, stirring at room temperature for 1 hour, then sequentially adding 0.24mmol2- (p-chlorophenyl methyleneamino) methyl acetate, 0.20mmol 2-p-chlorophenyl acetyl cycloheptatriene and 0.03mmol triethylamine at-40 ℃, stirring for 24 hours, evaporating the solvent, and performing silica gel column chromatography (petroleum ether/ethyl acetate 5/1) on the product to obtain a white solid with the yield of 81 percent and the enantioselectivity of the product being excessive97%，(Chiralpak IB-H，i-propanol/hexane=10/90，flow rate1.0mL/min，λ=254nm;tr=11.57and14.55min.)[α]25 D=-362.0(c0.36，CHCl3);1HNMR(CDCl3，TMS，300MHz)7.63(d，J=8.4Hz，2H)，7.41(d，J=8.4Hz，2H)，7.33(d，J=8.4Hz，2H)，7.24(d，J=8.4Hz，2H)，6.75(d，J=8.1Hz，1H)，6.11(dd，J1=8.1Hz，J2=11.7Hz，1H)，5.72(dd，J1=7.2Hz，J2=11.1Hz，1H)，4.24(d，J=3.3Hz，1H)，4.13(m，1H)，4.02(d，J=4.2Hz，1H)，3.44(s，3H)，3.11(m，1H)，2.49-2.45(m，1H)，1.78-1.68(m，2H);13C NMR(CDCl3，TMS，75MHz)197.2，172.4，140.6，140.3，139.7，139.3，137.7，136.8，132.7，131.0，128.4，128.3，127.3，125.8，65.1，64.3，51.8，40.8，34.2，27.8;IR(KBr)ν2950，2922，2851，2347，1737，1654，1587，1491，1457，1375，1256，1122，1064，896，832，750cm-1HRMS calculated value for C24H22NO3Cl2442.0987, measurement 442.0971.
Example 22
Preparation of
A25 mL reaction tube was charged with 0.01mmol of Cu (CH)3CN)4BF4And 0.011mmol (S) -TF-BiphamPhos, adding 1mL dichloromethane under the protection of nitrogen, stirring at room temperature for 1 hour, then adding 0.24mmol2- (p-chlorophenyl methylene amino) methyl acetate, 0.20mmol 2-p-trifluoromethylphenylacetylcycloheptatriene and 0.03mmol triethylamine at-40 ℃, stirring for 24 hours, evaporating the solvent, and subjecting the product to silica gel column chromatography (petroleum ether/ethyl acetate 5/1) to obtain a white solid with yield of 83%, enantioselectivity of 96%, (Chiralpak AD-H, i-propanol/hexane =10/90, flow rate1.0mL/min, lambda =254nm; t%r=23.74and32.27min.)[α]25 D=-297.0(c0.26，CHCl3);1H NMR(CDCl3，TMS，300MHz)7.74-7.71(m，3H)，7.31-7.24(m，5H)，6.76(m，1H)，6.11(m，1H)，5.76(m，1H)，4.25(m，1H)，4.14(m，1H)，4.04(m，1H)，3.49(s，3H)，3.13(m，1H)，2.46(m，1H)，1.78-1.67(m，2H);13C NMR(CDCl3，TMS，100MHz)197.4，172.4，146.3，141.1，140.8，140.5，132.8，129.6，128.5，128.0(q，J=280.4Hz)，127.3，125.8，125.4，125.1(q，J=3.8Hz)，65.2，64.4，52.0，40.8，33.7，27.8;IR(KBr)ν2945，2926，2852，2369，2335，1737，1630，1595，1511，1449，1344，1272，1123，1064，879，853，753cm-1HRMS calculated value for C25H22NO3F3476.1239, measurement 476.1235.
Example 23
Preparation of
A25 mL reaction tube was charged with 0.01mmol of Cu (CH)3CN)4BF4And 0.011mmol (S) -TF-BiphamPhos, adding 1mL dichloromethane under the protection of nitrogen, stirring at room temperature for 1 hour, then adding 0.24mmol2- (p-chlorophenyl methyleneamino) methyl acetate, 0.20mmol2- (1-naphthylacetyl) cycloheptatriene and 0.03mmol triethylamine at-40 ℃, stirring for 24 hours, evaporating the solvent, and subjecting the product to silica gel column chromatography (petroleum ether/ethyl acetate 5/1) to obtain a white solid with 88% yield and 98% enantioselectivity, (Chiralpak OD-H, i-proenol/hexane =10/90, flow rate1.0mL/min, lambda =254nm; t%r=18.54min and21.95min.)[α]25 D=-321.4(c1.10，CHCl3);1H NMR(CDCl3，TMS，300MHz)7.93-7.86(m，3H)，7.56-7.47(m，4H)，7.30(d，J=8.4Hz，2H)，7.21(d，J=8.4Hz，2H)，6.90(d，J=8.1Hz，1H)，6.01(dd，J1=8.1Hz，J2=11.7Hz，1H)，5.72(dd，J1=7.2Hz，J2=11.4Hz，1H)，4.30-4.25(m，2H)，4.13(m，1H)，3.66(s，3H)，3.15(m，1H)，2.54-2.49(m，1H)，1.85-1.80(m，1H)，1.65(brs，1H);13C NMR(CDCl3，TMS，75MHz)199.6，172.8，142.6，141.9，141.2，139.6，137.4，133.5，132.6，130.9，129.9，128.4，128.2，127.2，126.9，126.4，126.2，126.0，125.3，124.4，65.6，64.4，52.0，40.8，32.8，27.9;IR(KBr)ν2949，2925，2344，1736，1638，1584，1491，1436，1280，1250，1193，1137，779，735cm-1HRMS calculated value for28H25NO3458.1519, measurement 458.1518.
Example 24
Preparation of
A25 mL reaction tube was charged with 0.01mmol of Cu (CH)3CN)4BF4And 0.011mmol (S) -TF-BiphamPhos, adding 1mL dichloromethane under the protection of nitrogen, stirring at room temperature for 1 hour, then adding 0.24mmol2- (p-chlorophenyl methyleneamino) methyl acetate, 0.20mmol2- (2-furan) cycloheptatriene and 0.03mmol triethylamine at-40 ℃, stirring for 24 hours, evaporating the solvent, and subjecting the product to silica gel column chromatography (petroleum ether/ethyl acetate 5/1) to obtain a white solid with a yield of 75% and an enantioselectivity of 97%, (Chiralpak IB-H, i-propanol/hexane =15/85, flow rate1.0mL/min, lambda =254nm; t%r=19.90min and22.71min.)[α]25 D=-457.7(c0.84，CHCl3);1H NMR(CDCl3，TMS，300MHz)7.66(m，1H)，7.32(d，J=8.4Hz，2H)，7.24(d，J=8.4Hz，2H)，7.12-7.11(m，1H)，7.03(d，J=8.1Hz，1H)，6.55(m，1H)，6.17(dd，J1=8.1Hz，J2=12.0Hz，1H)，5.69(dd，J1=6.9Hz，J2=11.7Hz，1H)，4.19(m，1H)，4.03-3.98(m，2H)，3.36(s，3H)，3.10(m，1H)，2.48-2.44(m，1H)，1.82-1.63(m，2H);13C NMR(CDCl3，TMS，75MHz)184.5，171.8，151.5，146.8，140.5，139.8，139.2，135.6，132.5，128.3，127.3，125.9，120.1，111.7，65.0，64.1，51.5，40.7，35.1，27.9;IR(KBr)ν2923，2852，2345，1736，1654，1637，1629，1560，1465，1291，1126，1014，792，758，747cm-1HRMS calculated value for C20H23NO4498.1159, measurement 398.1154.
Example 25
Preparation of
A25 mL reaction tube was charged with 0.01mmol of Cu (CH)3CN)4BF4And 0.011mmol (S) -TF-BiphamPhos, adding 1mL dichloromethane under the protection of nitrogen, stirring at room temperature for 1 hour, then adding 0.24mmol2- (p-chlorophenyl methyleneamino) methyl acetate, 0.20mmol2- (2-thiophene) cycloheptatriene and 0.03mmol triethylamine at-40 ℃, stirring for 24 hours, evaporating the solvent, and subjecting the product to silica gel column chromatography (petroleum ether/ethyl acetate 5/1) to obtain a white solid with a yield of 81%, an enantioselectivity of the product of 97%, (Chiralpak IB-H, i-propanol/hexane =15/85, flow rate1.0mL/min, lambda =254nm; t%r=13.93min and15.25min.)[α]25 D=-411.2(c0.56，CHCl3);1H NMR(CDCl3，TMS，300MHz)7.65-7.60(m，2H)，7.32(d，J=8.1Hz，2H)，7.26(d，J=8.1Hz，2H)，7.14-7.11(m，1H)，6.94(d，J=7.8Hz，1H)，6.15(dd，J1=8.4Hz，J2=12.0Hz，1H)，5.67(dd，J1=7.2Hz，J2=11.7Hz，1H)，4.20(m，1H)，4.04(m，1H)，3.98(d，J=4.2Hz，1H)，3.30(s，3H)，3.09(m，1H)，2.49-2.44(m，1H)，1.83-1.74(m，2H);13C NMR(CDCl3，TMS，75MHz)189.8，171.8，143.3，141.0，139.8，138.9，135.5，134.3，133.4，132.5，128.2，127.5，127.3，125.8，64.9，64.0，51.4，40.7，35.5，27.9;IR(KBr)ν2925，2880，2377，2340，1736，1655，1337，1624，1561，1492，1412，1236，1089，1035，838，735，568cm-1HRMS calculated value for C20H23NO3SCl 414.0928, measurement 414.0925.
Example 26
Preparation of
A25 mL reaction tube was charged with 0.01mmol of Cu (CH)3CN)4BF4And 0.011mmol (S) -TF-BiphamPhos, adding 1mL dichloromethane under the protection of nitrogen, stirring at room temperature for 1 hour, then adding 0.24mmol2- (p-chlorophenyl methylene amino) methyl acetate, 0.20mmol 2-acetyl cycloheptatriene and 0.03mmol triethylamine at-40 ℃, stirring for 24 hours, evaporating the solvent, and subjecting the product to silica gel column chromatography (petroleum ether/ethyl acetate 5/1) to obtain a white solid with yield of 78% and enantioselectivity of 96%, (Chiralpak IB-H, i-propanol/hexane =10/90flow rate1.0mL/min, lambda =254nm; t =10/90r=13.77min and17.63min.)[α]25 D=-556.0(c0.26，CHCl3);1H NMR(CDCl3，TMS，300MHz)7.29(d，J=8.4Hz，2H)，7.19-7.15(m，3H)，6.18(dd，J1=8.1Hz，J2=11.7Hz，1H)，5.71(dd，J1=7.2Hz，J2=11.4Hz，1H)，4.22(d，J=3.6Hz，1H)，3.95(d，J=3.9Hz，1H)，3.90(m，1H)，3.63(s，3H)，3.07(m，1H)，2.37(m，4H)，1.69-1.65(m，2H);13C NMR(CDCl3，TMS，75MHz)199.1，172.3，141.0，140.2，139.6，136.4，132.4，128.2，127.1，125.8，65.7，64.4，51.6，40.4，32.8，27.6，25.6;IR(KBr)ν2967，2924，2853，2364，1736，1662，1590，1492，1436，1361，1255，1125，1064，881，834，775cm-1HRMS calculated value for C19H21NO3346.1211, measurement 346.1205.
Example 27
Preparation of
A25 mL reaction tube was charged with 0.01mmol of Cu (CH)3CN)4BF4And 0.011mmol (S) -TF-BiphamPhos, adding 1mL dichloromethane under nitrogen protection, stirring at room temperature for 1 hour, then adding 0.24mmol2- (p-chlorobenzylideneamino) methyl acetate, 0.20mmol 2-phenylacetylcycloheptatriene, and 0.03mmol triethylamine in this order at-40 deg.C, stirring for 24 hours, evaporating off the solvent, subjecting the product to silica gel column chromatography (petroleum ether/ethyl acetate 5/1) to obtain a white solid, adding 2mL tetrahydrofuran, 50mg N-phenylmaleimide under 500W ultraviolet light for refluxing for 7 hours, after sufficient reaction, evaporating off the solvent, subjecting the product to silica gel column chromatography (petroleum ether/ethyl acetate 3/1) to obtain a white solid with a yield of 75%, an enantioselectivity of 99% of the product, HPLC (Chiralpak IB-H, i-panprool/hexane =50/50flow 1.0mL/min, λ =254nm, tr=21.64min and30.65min.)[α]25 D=-53.7(c0.82CHCl3);1H NMR(CDCl3，TMS，300MHz)7.73(d，J=7.8Hz，2H)，7.58-7.55(m，1H)，7.49-7.31(m，9H)，6.91(d，J=7.8Hz，2H)，6.36(d，J=3.6Hz，1H)，4.13(m，1H)，4.03(m，1H)，3.83(d，J=3.0Hz，1H)，3.75-3.72(m，1H)，3.29-3.23(m，4H)，2.93-2.92(m，1H)，2.62-2.57(m，2H)，2.39-2.34(m，2H)，2.14(m，1H);13C NMR(CDCl3，TMS，75MHz)198.1，177.5，176.7，171.7，144.4，140.3，140.1，136.9，133.1，132.5，131.6，131.4，129.9，129.2，128.8，128.3，127.2，126.1，64.0，63.3，51.6，43.7，43.4，41.4，40.3，40.1，34.3，32.3;IR(KBr)ν2952，2929，2853，2344，1736，1711，1685，1598，1497，1381，1257，1182，1091，810，753，694cm-1HRMS calculated value for C34H30ClN2O5581.1838, measurement 581.1838.
Example 28
Preparation of
A25 mL reaction tube was charged with 0.01mmol of Cu (CH)3CN)4BF4And 0.011mmol (S) -TF-BiphamPhos, adding 1mL of dichloromethane under the protection of nitrogen, stirring at room temperature for 1 hour, then adding 0.24mmol of 2- (p-chlorobenzylideneamino) methyl acetate, 0.20mmol of 2-phenylacetylcycloheptatriene at-40 ℃, and 0.03mmol triethylamine, stirring for 24H, evaporating the solvent, subjecting the product to silica gel column chromatography (petroleum ether/ethyl acetate 5/1) to obtain a white solid, adding 2ml tetrahydrofuran and 7.6mg NaBH4, stirring at room temperature for 10H, after full reaction, evaporating the solvent, subjecting the product to silica gel column chromatography (petroleum ether/ethyl acetate 1/1) to obtain a white solid with a yield of 85% and an enantioselectivity of 98% for the product, HPLC (Chiralpak AD-H, i-propanol/hexane =20/80flow rate1.0mL/min,. lambda =254nm; t.r=10.27min and15.96min.)[α]25 D=-247.5(c0.86，CHCl3);1H NMR(CDCl3，TMS，300MHz)7.32-7.29(m，7H)，7.12(d，J=8.4Hz，2H)，6.54(d，J=7.8Hz，1H)，6.11(dd，J1=8.1Hz，J2=11.4Hz，1H)，5.21(dd，J1=6.9Hz，J2=10.8Hz，1H)，5.11(s，1H)，3.98(m，1H)，3.81-3.77(m，1H)，3.66-3.63(m，1H)，3.15(m，1H)，2.91(m，1H)，2.41-2.31(m，3H)，2.09-2.04(m，1H)，1.53-1.49(m，1H);13C NMR(CDCl3，TMS，75MHz)145.2，142.2，140.4，132.3，130.4，128.4，128.1，127.8，127.5，126.9，124.8，120.8，65.7，65.0，64.1，62.1，41.1，37.6，29.5，28.3;IR(KBr)ν2922，2851，2344，1650，1561，1491，1445，1422，1121，1091，1057，1014，832，759，701cm-1HRMS calculated value for C23H24ClNO2382.1574, measurement 382.1559.
Example 29
Preparation of
A25 mL reaction tube was charged with 0.01mmol of Cu (CH)3CN)4BF4And 0.011mmol (R) -TF-BiphamPhos, adding 1mL dichloromethane under nitrogen protection, stirring at room temperature for 1 hour, then adding 0.24mmol2- (p-chlorobenzylideneamino) methyl acetate, 0.20mmol 2-phenylacetylcycloheptatriene and 0.03mmol triethylamine in sequence at-40 ℃, stirring for 24 hours, evaporating the solvent, and subjecting the product to silica gel column chromatography (petroleum ether/ethyl acetate 5/1) to obtain a white solid with a yield of 84%, an enantioselectivity of 98% of the product, HPLC (Chiralpak IB-H, i-propanol/hexane =10/90, flow rate1.0mL/min, lambda =254nm; t%r=13.54and17.38min.)[α]25 D=+461.2(c0.74，CHCl3)。
Example 30
Preparation of
A25 mL reaction tube was charged with 0.01mmol of Cu (CH)3CN)4BF4Adding 1mL of dichloromethane into 0.011mmol (R) -TF-BiphamPhos under the protection of nitrogen, stirring for 1 hour at room temperature, then adding 0.24mmol2- (o-chlorobenzylideneamino) methyl acetate, 0.20mmol 2-phenylacetylcycloheptatriene and 0.03mmol triethylamine into the mixture at-40 ℃, stirring for 24 hours, evaporating the solvent,the product was chromatographed on a silica gel column (petrol ether/ethyl acetate 5/1) to give a white solid in 85% yield with 95% enantioselectivity of the product, HPLC (Chiralpak IB-H, i-propanol/hexane =10/90, flow rate1.0mL/min, lambda =254nm; tr=7.71and9.95min.)[α]25 D=+299.0(c1.32，CHCl3)。
Example 31
Preparation of
A25 mL reaction tube was charged with 0.01mmol of Cu (CH)3CN)4BF4And 0.011mmol (R) -TF-BiphamPhos, adding 1mL dichloromethane under nitrogen protection, stirring at room temperature for 1 hour, then adding 0.24mmol2- (p-bromophenylideneamino) methyl acetate, 0.20mmol 2-phenylacetylcycloheptatriene, and 0.03mmol triethylamine in sequence at-40 ℃, stirring for 24 hours, evaporating the solvent, and subjecting the product to silica gel column chromatography (petroleum ether/ethyl acetate 5/1) to obtain a white solid with a yield of 80%, an enantioselectivity of 95% and HPLC (Chiralpak AD-H, i-propanol/hexane =10/90, flow rate1.0mL/min, lambda =254nm; t%r=21.49and29.10min.)[α]25 D=-475.1(c1.50，CHCl3)。
Example 32
Preparation of
A25 mL reaction tube was charged with 0.01mmol of Cu (CH)3CN)4BF4Adding 1mL of dichloromethane into 0.011mmol (R) -TF-BiphamPhos under the protection of nitrogen, stirring for 1 hour at room temperature, and then sequentially adding 0.24mmol2- (p-nitrobenzeneamino) methyl acetate and 0.40 ℃ below zero20mmol 2-phenylacetylcycloheptatriene, and 0.03mmol triethylamine, after stirring for 24H, the solvent was evaporated off and the product was chromatographed on a silica gel column (petrol ether/ethyl acetate 5/1) to give a white solid in 88% yield with an enantioselectivity of 98% and HPLC (Chiralpak IB-H, i-propanol/hexane =30/70, flow rate1.0mL/min, lambda =254nm; tr=12.57and30.60min.)[α]25 D=+447.9(c1.22，CHCl3)。
Example 33
Preparation of
A25 mL reaction tube was charged with 0.01mmol of Cu (CH)3CN)4BF4And 0.011mmol (R) -TF-BiphamPhos, adding 1mL dichloromethane under nitrogen protection, stirring at room temperature for 1 hour, then adding 0.24mmol2- (benzylideneamino) methyl acetate, 0.20mmol 2-phenylacetylcycloheptatriene and 0.03mmol triethylamine in sequence at-40 ℃, stirring for 24 hours, evaporating the solvent, and subjecting the product to silica gel column chromatography (petroleum ether/ethyl acetate 5/1) to obtain a white solid with a yield of 80%, an enantioselectivity of the product of 97%, HPLC (Chiralpak IB-H, i-propanol/hexane =10/90, flow rate1.0mL/min, lambda =254nm; t%r=12.90and20.30min.)[α]25 D=+623.5(c0.74，CHCl3)。
Example 34
Preparation of
A25 mL reaction tube was charged with 0.01mmol of Cu (CH)3CN)4BF4And 0.011mmol (R) -TF-BiphamPhos, adding 1mL dichloromethane under the protection of nitrogen, stirring for 1 hour at room temperature, and reacting0.24mmol2- (p-methylbenzylideneamino) methyl acetate, 0.20mmol 2-phenylacetylcycloheptatriene and 0.03mmol triethylamine were added successively at-40 ℃ and, after stirring for 24H, the solvent was evaporated off and the product was chromatographed over silica gel (petroleum ether/ethyl acetate 5/1) to give a white solid in 83% yield with an enantioselectivity of 97% and HPLC (Chiralpak IB-H, i-propanol/hexane =10/90, flow rate1.0mL/min, lambda =254nm; t;, tr=12.48and18.72min.)[α]25 D=+409.8(c0.72，CHCl3)。
Example 35
Preparation of
A25 mL reaction tube was charged with 0.01mmol of Cu (CH)3CN)4BF4And 0.011mmol (R) -TF-BiphamPhos, adding 1mL dichloromethane under the protection of nitrogen, stirring at room temperature for 1 hour, then adding 0.24mmol2- (o-tolyleneamino) methyl acetate, 0.20mmol 2-phenylacetylcycloheptatriene and 0.03mmol triethylamine at-40 ℃, stirring for 24 hours, evaporating the solvent, and subjecting the product to silica gel column chromatography (petroleum ether/ethyl acetate 5/1) to obtain a white solid with a yield of 84%, and an enantioselectivity excess of 93% of the product, (Chiralpak IB-H, i-propenol/hexane =10/90, flow rate1.0mL/min, lambda =254nm; t%r=11.41and14.80min.)[α]25 D=+337.0(c0.30，CHCl3)。
Example 36
Preparation of
A25 mL reaction tube was charged with 0.01mmol of Cu (CH)3CN)4BF4And 0.011mmol (R) -TF-BiphamPhos, added with 1mL of dichloromethane under nitrogen protection and stirred at room temperature for 1 hour, then added with 0.24mmol of 2- (m-methoxyphenylmethyleneamino) methyl acetate, 0.20mmol of 2-phenylacetylcycloheptatriene, and 0.03mmol of triethylamine in sequence at-40 ℃, stirred for 24 hours, evaporated to remove the solvent, and the product chromatographed on silica gel column (petroleum ether/ethyl acetate 5/1) to give a white solid with a yield of 80%, with an enantioselectivity of 95%, (Chiralpak IB-H, i-propanol/hexane =20/80, flow rate1.0mL/min, lambda =254nm; t%r=12.11and12.99min.)[α]25 D=+377.6(c1.12，CHCl3)。
Example 37
Preparation of
A25 mL reaction tube was charged with 0.01mmol of Cu (CH)3CN)4BF4And 0.011mmol (R) -TF-BiphamPhos, adding 1mL dichloromethane under the protection of nitrogen, stirring at room temperature for 1 hour, then adding 0.24mmol2- (p-methoxybenzylideneamino) methyl acetate, 0.20mmol 2-phenylacetylcycloheptatriene and 0.03mmol triethylamine at-40 ℃, stirring for 24 hours, evaporating the solvent, and subjecting the product to silica gel column chromatography (petroleum ether/ethyl acetate 5/1) to obtain a white solid with a yield of 81% and an enantioselectivity of 98%, (Chiralpak AD-H, i-propanol/hexane =15/85, flow rate1.0mL/min, lambda =220nm; t%r=27.14and30.92min.)[α]25 D=+647.4(c0.84，CHCl3)。
Example 38
Preparation of
At 25mL0.01mmol of Cu (CH) was added to the reaction tube3CN)4BF4And 0.011mmol (R) -TF-BiphamPhos, adding 1mL dichloromethane under the protection of nitrogen, stirring at room temperature for 1 hour, then adding 0.24mmol2- (1-naphthylbenzylideneamino) methyl acetate, 0.20mmol 2-phenylacetylcycloheptatriene and 0.03mmol triethylamine at-40 ℃, stirring for 24 hours, evaporating the solvent, and subjecting the product to silica gel column chromatography (petroleum ether/ethyl acetate 5/1) to obtain a white solid with the yield of 85% and the enantioselectivity of 96%, (ChiralpaAD-H, i-propenol/hexane =30/70, flow rate1.0mL/min, lambda =254nm; t%r=8.21and23.20min.)[α]25 D=+350.9(c0.82，CHCl3)。
Example 39
Preparation of
A25 mL reaction tube was charged with 0.01mmol of Cu (CH)3CN)4BF4And 0.011mmol (R) -TF-BiphamPhos, adding 1mL dichloromethane under the protection of nitrogen, stirring at room temperature for 1 hour, then adding 0.24mmol2- (2-furylbenzylidene amino) methyl acetate, 0.20mmol 2-phenylacetylcycloheptatriene and 0.03mmol triethylamine at-40 ℃, stirring for 24 hours, evaporating the solvent, and subjecting the product to silica gel column chromatography (petroleum ether/ethyl acetate 5/1) to obtain a white solid with yield of 82% and enantioselectivity of 98%, (Chiralpak IB-H, i-prodiol/hexane =10/90, flow rate1.0mL/min, lambda =254nm; t%r=9.78and19.96min.)[α]25 D=+331.3(c0.68，CHCl3)。
Example 40
Preparation of
A25 mL reaction tube was charged with 0.01mmol of Cu (CH)3CN)4BF4And 0.011mmol (R) -TF-BiphamPhos, adding 1mL dichloromethane under the protection of nitrogen, stirring at room temperature for 1 hour, then adding 0.24mmol2- (2-thiophenylmethyleneamino) methyl acetate, 0.20mmol 2-phenylacetylcycloheptatriene and 0.03mmol triethylamine in sequence at-40 ℃, stirring for 24 hours, evaporating the solvent, and subjecting the product to silica gel column chromatography (petroleum ether/ethyl acetate 5/1) to obtain a white solid with the yield of 85% and the enantioselectivity of 94%, (Chiralpak IB-H, i-propenol/hexane =10/90, flow rate1.0mL/min, lambda =254nm; t%r=12.85and18.63min.)[α]25 D=+285.6(c0.70，CHCl3)。
EXAMPLE 41
Preparation of
A25 mL reaction tube was charged with 0.01mmol of Cu (CH)3CN)4BF4And 0.011mmol (R) -TF-BiphamPhos, adding 1mL dichloromethane under the protection of nitrogen, stirring at room temperature for 1 hour, then adding 0.24mmol2- (propylmethyleneamino) methyl acetate, 0.20mmol 2-phenylacetylcycloheptatriene and 0.03mmol triethylamine in sequence at-40 ℃, stirring for 24 hours, evaporating the solvent, and subjecting the product to silica gel column chromatography (petroleum ether/ethyl acetate 5/1) to obtain a white solid with a yield of 77% and an enantioselectivity of 91%, (Chiralpak AD-H, i-propanol/hexane =5/95, flow rate1.0mL/min, lambda =254nm; t%r=21.12and23.92min.)[α]25 D=-226.2(c0.66，CHCl3)。
Example 42
Preparation of
A25 mL reaction tube was charged with 0.01mmol of Cu (CH)3CN)4BF4And 0.011mmol (R) -TF-BiphamPhos, adding 1mL dichloromethane under the protection of nitrogen, stirring at room temperature for 1 hour, then adding 0.24mmol2- (styrylmethyleneamino) methyl acetate, 0.20mmol 2-phenylacetylcycloheptatriene and 0.03mmol triethylamine in sequence at-40 ℃, stirring for 24 hours, evaporating the solvent, and subjecting the product to silica gel column chromatography (petroleum ether/ethyl acetate 5/1) to obtain a white solid with a yield of 80% and an enantioselectivity of 97%, (Chiralpak IB-H, i-propanol/hexane =10/90, flow rate1.0mL/min, lambda =254nm; t = 10/90)r=17.08and27.68min.)[α]25 D=+136.2(c0.98，CHCl3)。
Example 43
Preparation of
A25 mL reaction tube was charged with 0.01mmol of Cu (CH)3CN)4BF4And 0.011mmol (R) -TF-BiphamPhos, adding 1mL dichloromethane under the protection of nitrogen, stirring at room temperature for 1 hour, then adding 0.24mmol2- (phenylmethyleneamino) methyl propionate, 0.20mmol 2-phenylacetylcycloheptatriene and 0.03mmol triethylamine at-40 ℃, stirring for 24 hours, evaporating the solvent, and subjecting the product to silica gel column chromatography (petroleum ether/ethyl acetate 5/1) to obtain a white solid with a yield of 84% and an enantioselectivity of 94%, (Chiralpak IB-H, i-propanol/hexane =5/95, flow rate1.0mL/min, lambda =254nm; t%r=13.42and14.83min.)[α]25 D=+354.0(c0.16，CHCl3)。
Example 44
Preparation of
A25 mL reaction tube was charged with 0.01mmol of Cu (CH)3CN)4BF4And 0.011mmol (R) -TF-BiphamPhos, adding 1mL dichloromethane under the protection of nitrogen, stirring at room temperature for 1 hour, then adding 0.24mmol2- (p-chlorophenyl methyleneamino) methyl propionate, 0.20mmol 2-phenylacetylcycloheptatriene and 0.03mmol triethylamine at-40 ℃, stirring for 24 hours, evaporating the solvent, and subjecting the product to silica gel column chromatography (petroleum ether/ethyl acetate 5/1) to obtain a white solid with a yield of 86% and an enantioselectivity of 98%, (Chiralpak IB-H, i-propenol/hexane =10/90, flow rate1.0mL/min, lambda =254nm; t%r=8.71and9.68min.)[α]25 D=+292.0(c0.30，CHCl3)。
Example 45
Preparation of
A25 mL reaction tube was charged with 0.01mmol of Cu (CH)3CN)4BF4And 0.011mmol (R) -TF-BiphamPhos, adding 1mL dichloromethane under the protection of nitrogen, stirring at room temperature for 1 hour, then adding 0.24mmol2- (p-chlorophenyl methylene amino) methyl acetate, 0.20mmol 2-p-methylphenyl acetyl cycloheptatriene and 0.03mmol triethylamine at-40 ℃, stirring for 24 hours, evaporating the solvent, and subjecting the product to silica gel column chromatography (petroleum ether/ethyl acetate 5/1) to obtain a white solid with the yield of 80 percent and the enantioselectivity of 96 percent, (Chiralpak IB-H, i-propanol/hexane =10/90, flow rate1.0mL/min, lambda =254nm; t = 10/90)r=12.56and14.73min.)[α]25 D=+396.3(c1.04，CHCl3)。
Example 46
Preparation of
A25 mL reaction tube was charged with 0.01mmol of Cu (CH)3CN)4BF4And 0.011mmol (R) -TF-BiphamPhos, adding 1mL dichloromethane under the protection of nitrogen, stirring at room temperature for 1 hour, then adding 0.24mmol2- (p-chlorophenyl methylene amino) methyl acetate, 0.20mmol 2-o-methylphenylacetylcycloheptatriene and 0.03mmol triethylamine at-40 ℃, stirring for 24 hours, evaporating the solvent, and subjecting the product to silica gel column chromatography (petroleum ether/ethyl acetate 5/1) to obtain a white solid with the yield of 84%, the enantioselectivity of the product is 97%, (Chiralpak IB-H, i-propenol/hexane =10/90, flow rate1.0mL/min, lambda =254nm; t%r=8.92and10.14min.)[α]25 D=+467.8(c0.70，CHCl3)。
Example 47
Preparation of
A25 mL reaction tube was charged with 0.01mmol of Cu (CH)3CN)4BF4And 0.011mmol (R) -TF-BiphamPhos, adding 1mL dichloromethane under the protection of nitrogen, stirring at room temperature for 1 hour, then adding 0.24mmol2- (p-chlorophenyl methylene amino) methyl acetate, 0.20mmol 2-m-methylphenylacetylcycloheptatriene and 0.03mmol triethylamine at-40 ℃, stirring for 24 hours, evaporating the solvent, and subjecting the product to silica gel column chromatography (petroleum ether/ethyl acetate 5/1) to obtain a white solid with the yield of 85% and the enantioselectivity of 98%, (Chiralpak IB-H, i-propenol/hexane =10/90, flow rate1.0mL/min, lambda =254nm; t%r=8.91and9.98min.)[α]25 D=+430.0(c0.70，CHCl3)。
Example 48
Preparation of
A25 mL reaction tube was charged with 0.01mmol of Cu (CH)3CN)4BF4And 0.011mmol (R) -TF-BiphamPhos, adding 1mL dichloromethane under the protection of nitrogen, stirring at room temperature for 1 hour, then adding 0.24mmol2- (p-chlorophenyl methyleneamino) methyl acetate, 0.20mmol 2-p-methoxybenzoacetyl cycloheptatriene and 0.03mmol triethylamine at-40 ℃, stirring for 24 hours, evaporating the solvent, and subjecting the product to silica gel column chromatography (petroleum ether/ethyl acetate 5/1) to obtain a white solid with yield of 87% and enantioselectivity of 98%, (Chiralpak IB-H, i-propenol/hexane =15/85, flow rate1.0mL/min, lambda =254nm; t%r=15.28and16.53min.)[α]25 D=+441.5(c1.00，CHCl3)。
Example 49
Preparation of
A25 mL reaction tube was charged with 0.01mmol of Cu (CH)3CN)4BF4And 0.011mmol (R) -TF-BiphamPhos, adding 1mL dichloromethane under the protection of nitrogen, stirring at room temperature for 1 hour, then adding 0.24mmol2- (p-chlorophenyl methylene amino) methyl acetate, 0.20mmol 2-p-chlorophenyl acetyl cycloheptatriene and 0.03mmol triethylamine at-40 ℃, stirring for 24 hours, evaporating the solvent, and subjecting the product to silica gel column chromatography (petroleum ether/ethyl acetate 5/1) to obtain a white solid with yield of 83%, enantioselectivity of the product of 97%, (Chiralpak IB-H, i-propenol/hexane =10/90, flow rate1.0mL/min，λ=254nm;tr=11.57and14.55min.)[α]25 D=+362.0(c0.36，CHCl3)。
Example 50
Preparation of
A25 mL reaction tube was charged with 0.01mmol of Cu (CH)3CN)4BF4And 0.011mmol (R) -TF-BiphamPhos, adding 1mL dichloromethane under the protection of nitrogen, stirring at room temperature for 1 hour, then adding 0.24mmol2- (p-chlorophenyl methylene amino) methyl acetate, 0.20mmol 2-p-trifluoromethylphenylacetylcycloheptatriene and 0.03mmol triethylamine at-40 ℃, stirring for 24 hours, evaporating the solvent, and subjecting the product to silica gel column chromatography (petroleum ether/ethyl acetate 5/1) to obtain a white solid with a yield of 81% and an enantioselectivity of 96%, (Chiralpak AD-H, i-propanol/hexane =10/90, flow rate1.0mL/min, lambda =254nm; t%r=23.74and32.27min.)[α]25 D=+297.0(c0.26，CHCl3)。
Example 51
Preparation of
A25 mL reaction tube was charged with 0.01mmol of Cu (CH)3CN)4BF4Adding 1mL of dichloromethane into 0.011mmol (R) -TF-BiphamPhos under the protection of nitrogen, stirring at room temperature for 1 hour, then sequentially adding 0.24mmol2- (p-chlorophenyl methylene amino) methyl acetate, 0.20mmol2- (1-naphthylacetyl) cycloheptatriene and 0.03mmol triethylamine at-40 ℃, stirring for 24 hours, evaporating the solvent, and performing silica gel column chromatography (petroleum ether/ethyl acetate 5/1) on the product to obtain a white solid, wherein the yield is 85 percentThe enantioselectivity of the product was 98%, (Chiralpak OD-H, i-propanol/hexane =10/90, flow rate1.0mL/min, lambda =254nm; tr=18.54min and21.95min.)[α]25 D=+321.4(c1.10，CHCl3)。
Example 52
Preparation of
A25 mL reaction tube was charged with 0.01mmol of Cu (CH)3CN)4BF4And 0.011mmol (R) -TF-BiphamPhos, adding 1mL dichloromethane under the protection of nitrogen, stirring at room temperature for 1 hour, then adding 0.24mmol2- (p-chlorophenyl methyleneamino) methyl acetate, 0.20mmol2- (2-furan) cycloheptatriene and 0.03mmol triethylamine at-40 ℃, stirring for 24 hours, evaporating the solvent, and subjecting the product to silica gel column chromatography (petroleum ether/ethyl acetate 5/1) to obtain a white solid with 73% yield and 97% enantioselectivity of the product, (Chiralpak IB-H, i-propanol/hexane =15/85, flow rate1.0mL/min, lambda =254nm; t = 15/85)r=19.90min and22.71min.)[α]25 D=+457.7(c0.84，CHCl3)。
Example 53
Preparation of
A25 mL reaction tube was charged with 0.01mmol of Cu (CH)3CN)4BF4Adding 1mL of dichloromethane into 0.011mmol (R) -TF-BiphamPhos under the protection of nitrogen, stirring for 1 hour at room temperature, then adding 0.24mmol2- (p-chlorophenyl methylene amino) methyl acetate, 0.20mmol2- (2-thiophene) cycloheptatriene and 0.03mmol triethylamine into the mixture at-40 ℃, stirring for 24 hours, evaporating the solvent, and reacting the productColumn chromatography on silica gel (petrol ether/ethyl acetate 5/1) gave a white solid with a yield of 81% and an enantioselectivity of the product of 97%, (Chiralpak IB-H, i-propanol/hexane =15/85, flow rate1.0mL/min, lambda =254nm; tr=13.93min and15.25min.)[α]25 D=+411.2(c0.56，CHCl3)。
Example 54
Preparation of
A25 mL reaction tube was charged with 0.01mmol of Cu (CH)3CN)4BF4And 0.011mmol (R) -TF-BiphamPhos, adding 1mL dichloromethane under the protection of nitrogen, stirring at room temperature for 1 hour, then adding 0.24mmol2- (p-chlorophenyl methylene amino) methyl acetate, 0.20mmol 2-acetyl cycloheptatriene and 0.03mmol triethylamine at-40 ℃, stirring for 24 hours, evaporating the solvent, and subjecting the product to silica gel column chromatography (petroleum ether/ethyl acetate 5/1) to obtain a white solid with the yield of 76% and the enantioselectivity of the product of 96%, (Chiralpak IB-H, i-propanol/hexane =10/90flow rate1.0mL/min, lambda =254nm; tr=13.77min and17.63min.)[α]25 D=+556.0(c0.26，CHCl3)。
Example 55
Preparation of
A25 mL reaction tube was charged with 0.01mmol of Cu (CH)3CN)4BF4Adding 1mL of dichloromethane into 0.011mmol (R) -TF-BiphamPhos under the protection of nitrogen, stirring at room temperature for 1 hour, and then sequentially adding 0.24mmol2- (p-chlorobenzylideneamino) methyl acetate and 0.20mmol 2-phenethyl at-40 DEG CAcylcycloheptatriene and 0.03mmol triethylamine were stirred for 24H, the solvent was evaporated off, the product was chromatographed over silica gel (petrol ether/ethyl acetate 5/1) to give a white solid, 2ml tetrahydrofuran and 50mg N-phenylmaleimide were added under 500W UV irradiation at reflux for 7H, after thorough reaction, the solvent was evaporated off, the product was chromatographed over silica gel (petrol ether/ethyl acetate 3/1) to give a white solid in 73% yield and an enantioselectivity of 99% for the product, HPLC (Chiralpak IB-H, i-propanol/hexane =50/50flow rate1.0mL/min, lambda =254nm; t%r=21.64min and30.65min.)[α]25 D=+53.7(c0.82CHCl3)。
Example 56
Preparation of
To a 25mL reaction tube was added 0.01mmol Cu (CH)3CN)4BF4Adding 1mL of dichloromethane into 0.011mmol (R) -TF-BiphamPhos under the protection of nitrogen, stirring at room temperature for 1 hour, then adding 0.24mmol2- (p-chlorobenzylideneamino) methyl acetate, 0.20mmol 2-phenylacetylcycloheptatriene and 0.03mmol triethylamine at-40 ℃, stirring for 24 hours, evaporating the solvent, and performing silica gel column chromatography (petroleum ether/ethyl acetate 5/1) on the product to obtain a white solid, adding 2mL of tetrahydrofuran and 7.6mg NaBH 5/14After stirring at room temperature for 10H, the reaction was complete, the solvent was evaporated and the product was chromatographed on silica gel (petrol ether/ethyl acetate 1/1) to give a white solid in 81% yield with an enantioselectivity of 98% and HPLC (Chiralpak AD-H, i-propanol/hexane =20/80flow rate1.0mL/min, λ =254nm; t)r=10.27min and15.96min.) [α]25 D=+247.5(c0.86，CHCl3)。
In the synthesis of the compounds (III) and (IV), the ultraviolet irradiation power can be controlled within 200W-600W. Generally, the ultraviolet light irradiation power is high, and the irradiation time is correspondingly shortened; on the contrary, the irradiation time is correspondingly prolonged.
In the above examples 1 to 56, Cu (CH)3CN)4BF4Can be prepared from Cu (OTf)2、CuOTf、CuI、CuBr、CuCl、Cu(ClO)4CuOAc, Cu (OAc), etc., AgOAc may be selected from AgOTf, AgPF6Equal substitution, K2CO3Can be prepared from Na2CO3、Cs2CO3Or triethylamine, or the like, wherein the solvent dichloromethane is selected from diethyl ether, ethyl acetate, tetrahydrofuran, methanol, and chloroform, and N is2May be replaced by other inert gases.
In examples 27 and 55 above, tetrahydrofuran as a solvent was replaced by toluene, and in examples 28 and 56, tetrahydrofuran as a solvent was replaced by diethyl ether.
The yields and corresponding selective excesses of the compounds obtained in examples 1 to 56 are shown in Table 1.
Table 1 yield and enantiomeric excess of the compound obtained in the example
Example 57
Detection of bactericidal activity
The concentration of the liquid medicine is 50ppm, the prepared agar sheets are taken by a 5mm emptier, the agar sheets are respectively picked into each culture dish, a blank control is arranged, the agar sheets are cultured in a constant temperature incubator at 27 ℃ for 48 to 72 hours, the diameter of the bacterial plaque is checked, and the inhibition rate = (the diameter of the control bacterial plaque-the diameter of the sample bacterial plaque)/the diameter of the control bacterial plaque multiplied by 100 percent is repeated at the same time. The results are shown in Table 2.
Cosolvent: dimethyl phthalide amine; emulsifier: tween-80; preparing a solution: sterile water. Wherein, dimethyl phthalide amine/H2O = 1/1000; emulsifier/H2O =5/1000 (weight percentage).
TABLE 2 bacteriostatic ratio of the compounds of the invention

Claims (5)

1. Bridged ring derivatives having an azadecadiene structural fragment, characterized by the structural formula:
wherein,
R1is phenyl, p-methylphenyl, m-methylphenyl, o-methylphenyl, p-methoxyphenyl, p-chlorophenyl, p-trifluoromethylphenyl, 1-naphthyl, 2-furyl, 2-thienyl or methyl;
R2is o-chlorophenyl, p-bromophenyl, p-nitrophenyl, phenyl, p-methylphenyl, o-methylphenyl, p-methoxyphenyl, m-methoxyphenyl, 1-naphthyl, 2-furyl, 2-thienyl, n-propyl or styryl;
R3is methyl or hydrogen.
2. The method for synthesizing bridged derivatives having an azadecadiene structural segment as claimed in claim 1, wherein:
in an organic solvent, under the protection of inert gas, taking 2-acyl cycloheptatriene and imine derived from amino acid methyl ester as raw materials, taking copper salt/TF-BiphamPhos complex or silver salt/TF-BiphamPhos complex as a catalyst, adding carbonate or organic base, fully reacting at the temperature of-40-25 ℃, evaporating the solvent, and carrying out column chromatography to obtain a target compound
The structural formula of the imine derived from the amino acid methyl ester is shown in the specification
The TF-BiphamPhos is (S) -TF-BiphamPhos or (R) -TF-BiphamPhos, and the structural formula of the (S) -TF-BiphamPhos is shown in the specificationThe structural formula of (R) -TF-BiphamPhos is as follows:
wherein R is1Is phenyl, p-methylphenyl, m-methylphenyl, o-methylphenyl, p-methoxyphenyl, p-chlorophenyl, p-trifluoromethylphenyl, 1-naphthyl, 2-furyl, 2-thienyl or methyl;
R2is o-chlorophenyl, p-bromophenyl, p-nitrophenyl, phenyl, p-methylbenzenePhenyl, o-methylphenyl, p-methoxyphenyl, m-methoxyphenyl, 1-naphthyl, 2-furyl, 2-thienyl, n-propyl or styryl;
R3is methyl or hydrogen.
3. The method of synthesis of claim 2, wherein:
the molar ratio of the 2-acylcycloheptatriene to the amino acid methyl ester-derived imine is 1: 1.2-1: 2.
4. the method of synthesis of claim 2, wherein:
the copper salt/TF-BiphamPhos complex and the silver salt/TF-BiphamPhos complex are prepared by the following method:
at room temperature, respectively taking copper salt or silver salt and chiral ligand TF-BiphamPhos to dissolve in an organic solvent according to the mole number of the copper salt or the silver salt not more than the mole number of the chiral ligand TF-BiphamPhos, and reacting to obtain a copper salt/TF-BiphamPhos complex or a silver salt/TF-BiphamPhos complex.
5. Use of the compound of claim 1 as an active ingredient in the preparation of a bactericide.
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