CN106279292B

CN106279292B - Metal iridium complex, monocrystalline, benzindole class compound and synthetic method and application

Info

Publication number: CN106279292B
Application number: CN201510305993.8A
Authority: CN
Inventors: 游书力; 叶克印; 吴可嘉
Original assignee: Shanghai Institute of Organic Chemistry of CAS
Current assignee: Shanghai Institute of Organic Chemistry of CAS
Priority date: 2015-06-04
Filing date: 2015-06-04
Publication date: 2018-12-18
Anticipated expiration: 2035-06-04
Also published as: CN106279292A

Abstract

本发明公开了一种金属铱络合物、单晶、苯并吲哚类化合物及合成方法和应用。该方法，包含下列步骤：有机溶剂中，在碱的存在下，将手性三唑卡宾盐分别与[Ir(cod)X¹]₂、[Ir(cod)X^1a]₂、[Ir(cod)X^1b]₂、[Ir(cod)X^1c]₂、[Ir(cod)X^1d]₂或[Ir(cod)X^1e]₂进行络合反应，即可。本发明还公开了金属铱络合物作为催化剂在不对称烯丙基取代反应中的应用。本发明的金属铱络合物以三唑卡宾作为配体，合成方法和后处理简单，且在金属铱催化的不对称烯丙基取代反应中具有非常好的效果。 The invention discloses a metal iridium complex, a single crystal, a benzindole compound, a synthesis method and an application. The method comprises the following steps: in an organic solvent, in the presence of a base, the chiral triazole carbene salt is respectively mixed with [Ir(cod)X ¹ ] ₂ , [Ir(cod)X ^1a ] ₂ , [Ir(cod)X 1a ] 2 , [Ir(cod)X 1a ] 2 , [Ir(cod)X 1a ] 2 )X ^1b ] ₂ , [Ir(cod)X ^1c ] ₂ , [Ir(cod)X ^1d ] ₂ or [Ir(cod)X ^1e ] ₂ for complexation reaction. The invention also discloses the application of the metal iridium complex as a catalyst in the asymmetric allyl substitution reaction. The metal iridium complex of the invention uses triazolecarbene as a ligand, has simple synthesis method and post-treatment, and has very good effect in metal iridium-catalyzed asymmetric allyl substitution reaction.

Description

Metal iridium complex, single crystal, benzindole compound, synthesis method and application

技术领域technical field

本发明涉及一种金属铱络合物、单晶、苯并吲哚类化合物及合成方法和应用。The invention relates to a metal iridium complex, a single crystal, a benzindole compound, a synthesis method and an application.

背景技术Background technique

金属铱催化的不对称烯丙基取代反应可以高对映选择性、区域选择性的构建碳碳键和碳杂键，在合成中得到了广泛的应用。目前此类反应使用的催化剂主要是[Ir(cod)Cl]₂和手性膦氮配体[(a)Miyabe,H.；Takemoto,Y.Synlett2005,1641.(b)Takeuchi,R.；Kezuka,S.Synthesis2006,3349.(c)Helmchen,G.；Dahnz,A.；Dübon,P.；Schelwies,M.；Weihofen,R.Chem.Commun.2007,675.(d)Helmchen,G.；In Iridium Complexes inOrganic Synthesis；Oro,L.A.；Claver,C.Eds.；Wiley-VCH:Weinheim,Germany,2009；p211.(e)Hartwig,J.F.；Stanley,L.M.Acc.Chem.Res.2010,43,1461.(f)Hartwig,J.F.；Pouy,M.J.Top.Organomet.Chem.2011,34,169.(g)Liu,W.-B.；Xia,J.-B.；You,S.-L.Top.Organomet.Chem.2012,38,155.(h)Tosatti,P.；Nelson,A.；Marsden,S.P.Org.Biomol.Chem.2012,10,3147.]。氮杂环卡宾由于其自身的强σ给电子能力和独特的空间构造，与膦配体一样，可作为一种很好的金属配体在催化反应中得到应用。相比于常见的咪唑类卡宾、咪唑啉类卡宾、噻唑类卡宾，三唑卡宾由于其较弱的给电子能力，在金属催化中的应用较少。特别是，使用手性三唑卡宾作为配体在烯丙基取代反应中的应用到目前为止还没有文献报道。Metal iridium-catalyzed asymmetric allyl substitution reactions can construct carbon-carbon bonds and carbon-heterobonds with high enantioselectivity and regioselectivity, and have been widely used in synthesis. The catalysts currently used in this type of reaction are mainly [Ir(cod)Cl] ₂ and chiral phosphine nitrogen ligands [(a) Miyabe, H.; Takemoto, Y.Synlett 2005, 1641. (b) Takeuchi, R.; Kezuka , S.Synthesis2006, 3349. (c) Helmchen, G.; Dahnz, A.; Dübon, P.; Schelwies, M.; In Iridium Complexes in Organic Synthesis; Oro, LA; Claver, C. Eds.; Wiley-VCH: Weinheim, Germany, 2009; p211.(e) Hartwig, JF; (f) Hartwig, JF; Pouy, MJ Top. Organomet. Chem. 2011, 34, 169. (g) Liu, W.-B.; Xia, J.-B.; .2012, 38, 155. (h) Tosatti, P.; Nelson, A.; Marsden, SP Org. Biomol. Chem. 2012, 10, 3147.]. Nitrocyclic carbene, like phosphine ligands, can be used as a good metal ligand for catalytic reactions due to its strong σ electron-donating ability and unique steric structure. Compared with common imidazole carbenes, imidazoline carbenes, and thiazole carbenes, triazole carbenes are less used in metal catalysis due to their weaker electron donating ability. In particular, the use of chiral triazolecarbenes as ligands in allylic substitution reactions has not been reported so far.

发明内容Contents of the invention

本发明所要解决的技术问题是为了提供一种与现有技术完全不同的金属铱络合物、单晶、苯并吲哚类化合物及合成方法和应用。本发明的金属铱络合物以三唑卡宾作为配体，合成方法和后处理简单，且在金属铱催化的烯丙基取代反应中具有非常好的效果。因此，该金属铱络合物对于金属铱催化的烯丙基取代反应催化剂类型的拓展以及反应类型的丰富都具有非常重要的意义，并且在金属铱催化的烯丙基取代反应中制得一类苯并吲哚类化合物。The technical problem to be solved by the present invention is to provide a metal iridium complex, single crystal, benzindole compound, synthesis method and application completely different from the prior art. The metal iridium complex of the invention uses triazolecarbene as a ligand, has simple synthesis method and post-treatment, and has very good effect in metal iridium-catalyzed allyl substitution reaction. Therefore, the metal iridium complex is of great significance for the expansion of metal iridium-catalyzed allyl substitution reaction catalyst types and the enrichment of reaction types, and a class of Benzindole compounds.

本发明提供了一种通式I、通式II、通式III、通式IV、通式V或通式VI所示的金属铱络合物，其中用*标注的碳为手性碳或非手性碳，当为手性碳时，所述的手性碳为S构型或R构型；The present invention provides a metal iridium complex represented by general formula I, general formula II, general formula III, general formula IV, general formula V or general formula VI, wherein the carbon marked with * is a chiral carbon or a non-chiral carbon Chiral carbon, when chiral carbon, said chiral carbon is S configuration or R configuration;

通式I～VI中，R¹、R^1a、R^1b、R^1c、R^1d和R^1e独立地为C₁-C₈的烷基、C₃-C₆的环烷基、C₁-C₈的全氟烷基、取代或未取代的C₆-C₂₀的芳基，或者取代或未取代的C₂-C₂₀的杂芳基；In general formulas I～VI, R ¹ , R ^1a , R ^1b , R ^1c , R ^1d and R ^1e are independently C ₁ -C ₈ alkyl, C ₃ -C ₆ cycloalkyl, C ₁ -C ₈ perfluoroalkyl, substituted or unsubstituted C ₆ -C ₂₀ aryl, or substituted or unsubstituted C ₂ -C ₂₀ heteroaryl;

R²、R^2’、R^2a、R^2a’、R^2b、R^2b’、R^2c和R^2c’独立地为氢、C₁-C₈的烷基、C₃-C₆的环烷基、C₁-C₈的全氟烷基、取代或未取代的C₆-C₂₀的芳基，或者取代或未取代的C₂-C₂₀的杂芳基；或者R²和R^2’及其相连的碳原子共同构成C₅-C₈的环烷基；R ² , R ^2' , R ^2a , R ^2a' , R ^2b , R ^2b' , R ^2c and R ^2c' are independently hydrogen, C ₁ -C ₈ alkyl, C ₃ -C ₆ cycloalkyl , C ₁ -C ₈ perfluoroalkyl, substituted or unsubstituted C ₆ -C ₂₀ aryl, or substituted or unsubstituted C ₂ -C ₂₀ heteroaryl; or R ² and R ^2' and The carbon atoms connected together form a C ₅ -C ₈ cycloalkyl group;

R³为其中，R_a为C₁-C₈的烷基、C₁-C₈的全氟烷基、取代或未取代的C₆-C₂₀的芳基，或者取代或未取代的C₂-C₂₀的杂芳基；R_b为C₁-C₈的烷基、C₁-C₈的烷氧基、C₁-C₈的全氟烷基、取代或未取代的C₆-C₂₀的芳基、或者取代或未取代的C₂-C₂₀的杂芳基； ^R3 is Wherein, R _a is C ₁ -C ₈ alkyl, C ₁ -C ₈ perfluoroalkyl, substituted or unsubstituted C ₆ -C ₂₀ aryl, or substituted or unsubstituted C ₂ -C ₂₀ Heteroaryl; R _b is C ₁ -C ₈ alkyl, C ₁ -C ₈ alkoxy, C ₁ -C ₈ perfluoroalkyl, substituted or unsubstituted C ₆ -C ₂₀ aryl group, or a substituted or unsubstituted C ₂ -C ₂₀ heteroaryl group;

R⁴、R^4a和R^4b独立地为氢、C₁-C₈的烷基或其中，R_c、R_c’和R_c”独立地为C₁-C₈的烷基；R ⁴ , R ^4a and R ^4b are independently hydrogen, C ₁ -C ₈ alkyl or Wherein, R _c , R _c ' and R _c " are independently C ₁ -C ₈ alkyl groups;

R⁵为氢、卤素、C₁-C₈的烷基、C₃-C₆的环烷基、C₁-C₈的全氟烷基、取代或未取代的C₆-C₂₀的芳基，或者取代或未取代的C₆-C₂₀的杂芳基；R ⁵ is hydrogen, halogen, C ₁ -C ₈ alkyl, C ₃ -C ₆ cycloalkyl, C ₁ -C ₈ perfluoroalkyl, substituted or unsubstituted C ₆ -C ₂₀ aryl , or a substituted or unsubstituted C ₆ -C ₂₀ heteroaryl;

X¹、X^1a、X^1b、X^1c、X^1d和X^1e独立地为卤素或C₁-C₈的烷氧基；X ¹ , X ^1a , X ^1b , X ^1c , X ^1d and X ^1e are independently halogen or C ₁ -C ₈ alkoxy;

其中，所述的取代的C₆-C₂₀的芳基或所述的取代的C₂-C₂₀的杂芳基中的所述的取代是指被下列一个或多个取代基取代：卤素(所述的卤素较佳地为F、Cl、Br或I)、C₁-C₁₆的烃氧基(所述的C₁-C₁₆的烃氧基较佳地为C₁-C₈的烃氧基；所述的C₁-C₈的烃氧基较佳地为C₁-C₄的烃氧基；所述的C₁-C₄的烃氧基较佳地为甲氧基、乙氧基、正丙氧基、异丙氧基、正丁氧基、异丁氧基或叔丁氧基)、C₁-C₁₆的烷基(所述的C₁-C₁₆的烷基较佳地为C₁-C₈的烷基；所述的C₁-C₈的烷基较佳地为C₁-C₄的烷基；所述的C₁-C₄的烷基较佳地为甲基、乙基、正丙基、异丙基、正丁基、异丁基或叔丁基)、C₁-C₁₆的氟代烷基(所述的C₁-C₁₆的氟代烷基是指被一个或多个氟原子取代的C₁-C₁₆的烷基；所述的C₁-C₁₆的氟代烷基较佳地为C₁-C₈的氟代烷基；所述的C₁-C₈的氟代烷基较佳地为C₁-C₄的氟代烷基；所述的C₁-C₄的氟代烷基较佳地为三氟甲基)、硝基或氨基，当取代基为多个时，所述的取代基相同或不同。Wherein, the substitution in the substituted C ₆ -C ₂₀ aryl or the substituted C ₂ -C ₂₀ heteroaryl refers to being substituted by one or more of the following substituents: halogen ( The halogen is preferably F, Cl, Br or I), a C ₁ -C ₁₆ alkoxy group (the C ₁ -C ₁₆ alkoxy group is preferably a C ₁ -C ₈ hydrocarbon Oxygen; the C ₁ -C ₈ alkoxy is preferably a C ₁ -C ₄ alkoxy; the C ₁ -C ₄ alkoxy is preferably a methoxy, ethyl oxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy or tert-butoxy), C ₁ -C ₁₆ alkyl (the C ₁ -C ₁₆ alkyl is more Preferably C ₁ -C ₈ alkyl; said C ₁ -C ₈ alkyl is preferably C ₁ -C ₄ alkyl; said C ₁ -C ₄ alkyl is preferably is methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl or tert-butyl), C ₁ -C ₁₆ fluoroalkyl (the C ₁ -C ₁₆ fluoroalkyl Alkyl refers to a C ₁ -C ₁₆ alkyl group substituted by one or more fluorine atoms; the C ₁ -C ₁₆ fluoroalkyl group is preferably a C ₁ -C ₈ fluoroalkyl group; The C ₁ -C ₈ fluoroalkyl group is preferably a C ₁ -C ₄ fluoroalkyl group; the C ₁ -C ₄ fluoroalkyl group is preferably trifluoromethyl) , nitro or amino, when there are multiple substituents, the substituents are the same or different.

R¹、R^1a、R^1b、R^1c、R^1d、R^1e、R²、R²’、R^2a、R^2a’、R^2b、R^2b’、R^2c、R^2c’、R_a、R_b、R⁴、R^4a、R^4b、R_c、R_c’、R_c”和R⁵中，所述的C₁-C₈的烷基较佳地为C₁-C₄的烷基，所述的C₁-C₄的烷基较佳地为甲基、乙基、正丙基、异丙基、正丁基、异丁基或叔丁基。R ¹ , R ^1a , R ^1b , R ^1c , R ^1d , R ^1e , R ² , R ² ', R ^2a , R ^2a' , R ^2b , R ^2b' , R ^2c , R ^2c' , R _a , R In _b , R ⁴ , R ^4a , R ^4b , R _c , R _c ′, R _c ” and R ⁵ , the C ₁ -C ₈ alkyl group is preferably a C ₁ -C ₄ alkyl group, The C ₁ -C ₄ alkyl group is preferably methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl or tert-butyl.

R¹、R^1a、R^1b、R^1c、R^1d、R^1e、R²、R²’、R^2a、R^2a’、R^2b、R^2b’、R^2c、R^2c’和R⁵中，所述的C₃-C₆的环烷基较佳地为环丙基、环丁基、环戊基或环己基。R ¹ , R ^1a , R ^1b , R ^1c , R ^1d , R ^1e , R ² , R ² ', R ^2a , R ^2a' , R ^2b , R ^2b' , R ^2c , R ^2c' and R ⁵ , The C ₃ -C ₆ cycloalkyl group is preferably cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl.

R¹、、R^1a、R^1b、R^1c、R^1d、R^1e、R²、R²’、R^2a、R^2a’、R^2b、R^2b’、R^2c、R^2c’、R_a、R_b、和R⁵中，所述的C₁-C₈的全氟烷基较佳地为其中，包括各自的同分异构体形式。R ¹ , R ^1a , R ^1b , R ^1c , R ^1d , R ^1e , R ² , R ² ', R ^2a , R ^2a' , R ^2b , R ^2b' , R ^2c , R ^2c' , R _a , In R _b and R ⁵ , the C ₁ -C ₈ perfluoroalkyl group is preferably in, Each isomeric form is included.

R¹、R^1a、R^1b、R^1c、R^1d、R^1e、R²、R²’、R^2a、R^2a’、R^2b、R^2b’、R^2c、R^2c’、R_a、R_b、和R⁵中，所述的取代或未取代的C₆-C₂₀的芳基较佳地为取代或未取代的C₆-C₁₄的芳基。所述的取代或未取代的C₆-C₁₄的芳基较佳地为取代或未取代的苯基、取代或未取代的萘基、取代或未取代的9-蒽基或取代或未取代的9-菲基所述的取代的苯基较佳地为 R ¹ , R ^1a , R ^1b , R ^1c , R ^1d , R ^1e , R ² , R ² ', R ^2a , R ^2a' , R ^2b , R ^2b' , R ^2c , R ^2c' , R _a , R In _b , and R ⁵ , the substituted or unsubstituted C ₆ -C ₂₀ aryl group is preferably a substituted or unsubstituted C ₆ -C ₁₄ aryl group. The substituted or unsubstituted C ₆ -C ₁₄ aryl is preferably substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted 9-anthracenyl or substituted or unsubstituted 9-phenanthyl The substituted phenyl group is preferably

R¹、R^1a、R^1b、R^1c、R^1d、R^1e、R²、R²’、R^2a、R^2a’、R^2b、R^2b’、R^2c、R^2c’、R_a、R_b、和R⁵中，所述的取代或未取代的C₂-C₂₀的杂芳基较佳地是指杂原子为O、N或S，杂原子数为1-4个的取代或未取代的C₂-C₂₀的杂芳基。所述的杂原子为O、N或S，杂原子数为1-4个的取代或未取代的C₂-C₂₀的杂芳基较佳地为取代或未取代的C₂-C₁₀的杂芳基。所述的取代或未取代的C₂-C₁₀的杂芳基较佳地为取代或未取代的呋喃基、取代或未取代的吡啶基，或取代或未取代的噻吩基。R ¹ , R ^1a , R ^1b , R ^1c , R ^1d , R ^1e , R ² , R ² ', R ^2a , R ^2a' , R ^2b , R ^2b' , R ^2c , R ^2c' , R _a , R _b , and R ⁵ , the substituted or unsubstituted C ₂ -C ₂₀ heteroaryl preferably refers to the heteroatom is O, N or S, the number of heteroatoms is 1-4 substituted or unsubstituted Substituted C ₂ -C ₂₀ heteroaryl. The heteroatom is O, N or S, and the substituted or unsubstituted C ₂ -C ₂₀ heteroaryl with 1-4 heteroatoms is preferably a substituted or unsubstituted C ₂ -C ₁₀ heteroaryl. The substituted or unsubstituted C ₂ -C ₁₀ heteroaryl is preferably substituted or unsubstituted furyl, substituted or unsubstituted pyridyl, or substituted or unsubstituted thienyl.

R_b、X¹、X^1a、X^1b、X^1c、X^1d和X^1e中，所述的C₁-C₈的烷氧基较佳地为C₁-C₄的烷氧基。所述的C₁-C₄的烷氧基较佳地为甲氧基、乙氧基、正丙氧基、异丙氧基、正丁氧基、异丁氧基或叔丁氧基。In R _b , X ¹ , X ^1a , X ^1b , X ^1c , X ^1d and X ^1e , the C ₁ -C ₈ alkoxy group is preferably a C ₁ -C ₄ alkoxy group. The C ₁ -C ₄ alkoxy group is preferably methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy or tert-butoxy.

X¹、X^1a、X^1b、X^1c、X^1d和X^1e中，所述的卤素较佳地为氟、氯、溴或碘。In X ¹ , X ^1a , X ^1b , X ^1c , X ^1d and X ^1e , the halogen is preferably fluorine, chlorine, bromine or iodine.

当R²和R^2’及其相连的碳原子共同构成C₅-C₈的环烷基时，所述的C₅-C₈的环烷基较佳地为环戊基或环己基。When R ² and R ^2′ and their connected carbon atoms together form a C ₅ -C ₈ cycloalkyl group, the C ₅ -C ₈ cycloalkyl group is preferably cyclopentyl or cyclohexyl.

R³中，所述的较佳地为 R ³ , the preferably

R⁴、R^4a或R^4b中，所述的较佳地为 Among R ⁴ , R ^4a or R ^4b , the preferably

较佳地，Preferably,

通式I中，R¹为C₃-C₆的环烷基或者取代或未取代的C₆-C₂₀的芳基；X¹为卤素或C₁-C₈的烷氧基。通式I中的结构中也可以含有手性中心，例如 In the general formula I, R ¹ is a C ₃ -C ₆ cycloalkyl group or a substituted or unsubstituted C ₆ -C ₂₀ aryl group; X ¹ is a halogen or a C ₁ -C ₈ alkoxy group. In general formula I Structures can also contain chiral centers, e.g.

通式II中，R^1a为C₃-C₆的环烷基或者取代或未取代的C₆-C₂₀的芳基；R²和R^2’独立地为取代或未取代的C₆-C₂₀的芳基，或者取代或未取代的C₂-C₂₀的杂芳基；或者R²和R^2’及其相连的碳原子共同构成C₅-C₈的环烷基；R³为其中，R_a为C₁-C₈的烷基、C₁-C₈的全氟烷基、取代或未取代的C₆-C₂₀的芳基，或取代或未取代的C₂-C₂₀的杂芳基；R_b为C₁-C₈的烷基、C₁-C₈的烷氧基、C₁-C₈的全氟烷基、取代或未取代的C₆-C₂₀的芳基、或者取代或未取代的C₂-C₂₀的杂芳基；X^1a为卤素或C₁-C₈的烷氧基；In general formula II, R ^1a is C ₃ -C ₆ cycloalkyl or substituted or unsubstituted C ₆ -C ₂₀ aryl; R ² and R ^2' are independently substituted or unsubstituted C ₆ -C ₂₀ aryl, or substituted or unsubstituted C ₂ -C ₂₀ heteroaryl; or R ² and R ^2' and their connected carbon atoms together form a C ₅ -C ₈ cycloalkyl; R ³ is Wherein, R _a is C ₁ -C ₈ alkyl, C ₁ -C ₈ perfluoroalkyl, substituted or unsubstituted C ₆ -C ₂₀ aryl, or substituted or unsubstituted C ₂ -C ₂₀ Heteroaryl; R _b is C ₁ -C ₈ alkyl, C ₁ -C ₈ alkoxy, C ₁ -C ₈ perfluoroalkyl, substituted or unsubstituted C ₆ -C ₂₀ aryl or substituted or unsubstituted C ₂ -C ₂₀ heteroaryl; X ^1a is halogen or C ₁ -C ₈ alkoxy;

通式III中，R^1b为取代或未取代的C₆-C₂₀的芳基；R^2a、R^2a’和R⁴独立地为C₁-C₈的烷基；X^1b为卤素；In general formula III, R ^1b is a substituted or unsubstituted C ₆ -C ₂₀ aryl group; R ^2a , R ^2a' and R ⁴ are independently C ₁ -C ₈ alkyl groups; X ^1b is halogen;

通式IV中，R^1c为取代或未取代的C₆-C₂₀的芳基；R^2b和R^2b’独立地为C₁-C₈的烷基、C₁-C₈的全氟烷基、取代或未取代的C₆-C₂₀的芳基，或者取代或未取代的C₂-C₂₀的杂芳基；R^4a独立地为氢、C₁-C₈的烷基或其中，R_c、R_c’或R_c”独立地为C₁-C₈的烷基；R⁵为氢或卤素；X^1c为卤素或C₁-C₈的烷氧基；In general formula IV, R ^1c is a substituted or unsubstituted C ₆ -C ₂₀ aryl group; R ^2b and R ^2b' are independently C ₁ -C ₈ alkyl, C ₁ -C ₈ perfluoroalkyl , substituted or unsubstituted C ₆ -C ₂₀ aryl, or substituted or unsubstituted C ₂ -C ₂₀ heteroaryl; R ^4a is independently hydrogen, C ₁ -C ₈ alkyl or Wherein, R _c , R _c 'or R _c ” are independently C ₁ -C ₈ alkyl; R ⁵ is hydrogen or halogen; X ^1c is halogen or C ₁ -C ₈ alkoxy;

通式V中，R^1d为取代或未取代的C₆-C₂₀的芳基；R^2c、R^2c’和R^4b独立地为氢、C₁-C₈的烷基、C₁-C₈的全氟烷基、取代或未取代的C₆-C₂₀的芳基，或者取代或未取代的C₂-C₂₀的杂芳基；X^1c为卤素或C₁-C₈的烷氧基；In general formula V, R ^1d is a substituted or unsubstituted C ₆ -C ₂₀ aryl group; R ^2c , R ^2c' and R ^4b are independently hydrogen, C ₁ -C ₈ alkyl, C ₁ -C ₈ Perfluoroalkyl, substituted or unsubstituted C ₆ -C ₂₀ aryl, or substituted or unsubstituted C ₂ -C ₂₀ heteroaryl; X ^1c is halogen or C ₁ -C ₈ alkoxy ;

通式VI中，R^1e为取代或未取代的C₆-C₂₀的芳基；X^1e为卤素或C₁-C₈的烷氧基。In the general formula VI, R ^1e is a substituted or unsubstituted C ₆ -C ₂₀ aryl group; X ^1e is a halogen or a C ₁ -C ₈ alkoxy group.

通式I所示的化合物，较佳地为如下任一化合物：The compound shown in general formula I is preferably any one of the following compounds:

通式II所示的化合物，较佳地为如下任一化合物：The compound shown in general formula II is preferably any one of the following compounds:

通式III所示的化合物，较佳地为如下任一化合物：The compound shown in general formula III is preferably any one of the following compounds:

通式IV所示的化合物，较佳地为如下任一化合物：The compound shown in general formula IV is preferably any one of the following compounds:

通式V所示的化合物，较佳地为如下任一化合物：The compound represented by general formula V is preferably any one of the following compounds:

通式VI所示的化合物，较佳地为如下任一化合物：The compound shown in general formula VI is preferably any one of the following compounds:

本发明还提供了一种金属铱络合物IIIa的单晶，在使用辐射源为Cu-Kα的单晶X射线衍射光谱中，晶体属单斜系，空间群为P21，其晶胞参数： α＝90°，β＝92.5300(10)°，γ＝90°，晶胞体积晶胞内不对称单位数Z＝2；The present invention also provides a single crystal of metal iridium complex IIIa. In the single crystal X-ray diffraction spectrum using a radiation source of Cu-Kα, the crystal belongs to the monoclinic system, the space group is P21, and its unit cell parameters are: α=90°, β=92.5300(10)°, γ=90°, unit cell volume The number of asymmetric units in the unit cell Z=2;

本发明还提供了一种金属依络合物IIIa的单晶的制备方法，其包括下列步骤：将金属铱络合物IIIa与良性溶剂混合后，滴加不良性溶剂，直至恰好出现浑浊，再滴加良性溶剂，静置，即可。The present invention also provides a method for preparing a single crystal of the metal complex IIIa, which comprises the following steps: after mixing the metal iridium complex IIIa with a benign solvent, adding a poor solvent dropwise until just turbidity occurs, and then Add a benign solvent dropwise and let it stand.

所述的良性溶剂较佳地是指对金属依络合物IIIa溶解性好的溶剂(可为室温、1个标准大气压下，溶解度大于0.1mg/10mL)的溶剂，优选卤代烃类溶剂。所述的卤代烃类溶剂较佳地为二氯甲烷(DCM)。所述的良性溶剂的用量不作具体限定，只要能够溶解金属依络合物IIIa，得到澄清透明的溶液即可。一般地，所述的良性溶剂与金属依络合物IIIa的体积质量比较佳地为1mL/20mg-1mL/40mg。The benign solvent preferably refers to a solvent with good solubility to the metal complex IIIa (it can be a solvent with a solubility greater than 0.1 mg/10 mL at room temperature and 1 standard atmospheric pressure), preferably a halogenated hydrocarbon solvent. The halogenated hydrocarbon solvent is preferably dichloromethane (DCM). The amount of the benign solvent used is not specifically limited, as long as it can dissolve the metal complex IIIa and obtain a clear and transparent solution. Generally, the volume-mass ratio of the benign solvent to the metal complex IIIa is preferably 1mL/20mg-1mL/40mg.

所述的不良性溶剂较佳地是指对金属依络合物IIIa的溶解性差(可以为室温、1个标准大气压下，溶解度小于0.1mg/100mL)的溶剂，较佳地为烷烃类溶剂。所述的烷烃类溶剂较佳地为正己烷。所述的不良性溶剂的用量不作具体限定，其用量一般是将其滴加到金属铱络合物IIIa与良性溶剂形成的溶液中，恰好出现浑浊为止。所述的不良性溶剂与金属铱络合物IIIa的体积质量比较佳地为1mL/5mg-1mL/1mg。The poor solvent preferably refers to a solvent with poor solubility to the metal complex IIIa (it can be room temperature, under 1 standard atmospheric pressure, the solubility is less than 0.1mg/100mL), preferably an alkane solvent. The alkane solvent is preferably n-hexane. The amount of the poor solvent is not specifically limited, and its amount is generally added dropwise to the solution formed by the metal iridium complex IIIa and the benign solvent, until it becomes turbid. The volume mass ratio of the poor solvent and metal iridium complex IIIa is preferably 1mL/5mg-1mL/1mg.

所述的混合的温度可为本领域常规的温度，较佳地为10～30℃。所述的静置的温度可为本领域常规的温度，较佳地为-30℃--50℃。The mixing temperature may be a conventional temperature in the field, preferably 10-30°C. The standing temperature can be a conventional temperature in the field, preferably -30°C-50°C.

本发明还提供了一种所述的通式I、通式II、通式III、通式IV、通式V或通式VI所示的金属铱络合物的制备方法，其包含下列步骤：有机溶剂中，在碱的存在下，将如式a所示的化合物与[Ir(cod)X¹]₂、如式b所示的化合物与[Ir(cod)X^1a]₂、如式c所示的化合物与[Ir(cod)X^1b]₂、如式d所示的化合物与[Ir(cod)X^1c]₂、如式e所示的化合物与[Ir(cod)X^1d]₂或如式f所示的化合物与[Ir(cod)X^1e]₂进行如下所示的络合反应；分别制得通式I、通式II、通式III、通式IV、通式V或通式VI所示的金属铱络合物；The present invention also provides a method for preparing the metal iridium complex shown in general formula I, general formula II, general formula III, general formula IV, general formula V or general formula VI, which comprises the following steps: In an organic solvent, in the presence of a base, mix the compound shown in formula a with [Ir(cod)X ¹ ] ₂ , the compound shown in formula b and [Ir(cod)X ^1a ] ₂ , in formula c The compound shown with [Ir(cod)X ^1b ] ₂ , the compound shown in formula d and [Ir(cod)X ^1c ] ₂ , the compound shown in formula e and [Ir(cod)X ^1d ] ₂ Or the compound shown in formula f and [Ir (cod) X ^1e ] ₂ carry out the complexation reaction shown below; Make general formula I, general formula II, general formula III, general formula IV, general formula V or Metal iridium complex compound shown in general formula VI;

其中，*标号、各基团定义均如前所述；Y为卤素、CF₃SO₃、OTf、BF₄或ClO₄。Wherein, the symbol * and the definition of each group are as described above; Y is halogen, CF ₃ SO ₃ , OTf, BF ₄ or ClO ₄ .

Y中，所述的卤素较佳地为氟、氯、溴或碘。[Ir(cod)X¹]₂～[Ir(cod)X^1e]₂中，cod是指1,5-环辛二烯。In Y, the halogen is preferably fluorine, chlorine, bromine or iodine. In [Ir(cod)X ¹ ] ₂ to [Ir(cod)X ^1e ] ₂ , cod means 1,5-cyclooctadiene.

所述的络合反应的方法和条件可为本领域常规的方法和条件。本发明优选下列方法：所述的有机溶剂较佳地为芳烃类溶剂、卤代烃类溶剂、醚类溶剂、酰胺类溶剂、烷烃类溶剂和腈类溶剂中的一种或多种，更佳地为醚类溶剂。所述的芳烃类溶剂较佳地为苯、甲苯和二甲苯中的一种或多种。所述的卤代烃类溶剂较佳地为四氯化碳(CCl₄)、二氯甲烷(DCM)和三氯甲烷(CHCl₃)中的一种或多种。所述的醚类溶剂较佳地为四氢呋喃(THF)、乙醚和1,4-二氧六环中的一种或多种，更佳地为四氢呋喃。所述的酰胺类溶剂较佳地为N,N-二甲基甲酰胺(DMF)。所述的烷烃类溶剂较佳地为环己烷、正戊烷、正己烷和正庚烷中的一种或多种。所述的腈类溶剂较佳地为乙腈。所述的碱可为本领域常规的碱，较佳地为无机碱和/或有机碱。所述的无机碱可为本领域此类反应常规的无机碱，较佳地为碳酸钠、碳酸钾、碳酸铯、磷酸钾、氢化钠、甲醇钠、乙醇钠、醋酸钠、叔丁醇钾、叔丁醇钠和叔丁醇锂中的一种或多种。所述的有机碱可为本领域此类反应常规的有机碱，较佳地为三乙胺、哌啶、吡啶、N,N-二甲基吡啶和2,6-二甲基吡啶中的一种或多种。所述的[Ir(cod)X¹]₂与如式a所示的化合物、[Ir(cod)X^1a]₂与如式b所示的化合物、[Ir(cod)X^1b]₂与如式c所示的化合物、[Ir(cod)X^1c]₂与如式d所示的化合物、[Ir(cod)X^1d]₂与如式e所示的化合物或[Ir(cod)X^1e]₂与如式f所示的化合物的摩尔比较佳地为1:1-1:3.5，更佳地为1:2-1:3.5。所述的[Ir(cod)X¹]₂、[Ir(cod)X^1a]₂、[Ir(cod)X^1b]₂、[Ir(cod)X^1c]₂、[Ir(cod)X^1d]₂或[Ir(cod)X^1e]₂与碱的摩尔比较佳地为1:1-1:20，更佳地为2:15-1:20。所述的有机溶剂与[Ir(cod)X¹]₂、[Ir(cod)X^1a]₂、[Ir(cod)X^1b]₂、[Ir(cod)X^1c]₂、[Ir(cod)X^1d]₂或[Ir(cod)X^1e]₂的体积质量比较佳地为0.1mL/mg～1mL/mg。所述的反应的温度较佳地为0℃-150℃，更佳地为25℃-125℃。所述的络合反应的时间较佳地为20-48小时。The methods and conditions of the complexation reaction can be conventional methods and conditions in the art. The present invention preferably following method: described organic solvent is preferably one or more in aromatic hydrocarbon solvent, halogenated hydrocarbon solvent, ether solvent, amide solvent, alkane solvent and nitrile solvent, more preferably The ground is an ether solvent. The aromatic solvent is preferably one or more of benzene, toluene and xylene. The halogenated hydrocarbon solvent is preferably one or more of carbon tetrachloride (CCl ₄ ), dichloromethane (DCM) and chloroform (CHCl ₃ ). The ether solvent is preferably one or more of tetrahydrofuran (THF), diethyl ether and 1,4-dioxane, more preferably tetrahydrofuran. The amide solvent is preferably N,N-dimethylformamide (DMF). The alkane solvent is preferably one or more of cyclohexane, n-pentane, n-hexane and n-heptane. The nitrile solvent is preferably acetonitrile. The base may be a conventional base in the art, preferably an inorganic base and/or an organic base. Described inorganic base can be the conventional inorganic base of this type of reaction in this area, is preferably sodium carbonate, potassium carbonate, cesium carbonate, potassium phosphate, sodium hydride, sodium methylate, sodium ethylate, sodium acetate, potassium tert-butoxide, One or more of sodium tert-butoxide and lithium tert-butoxide. The organic base can be a conventional organic base for this type of reaction in the art, preferably one of triethylamine, piperidine, pyridine, N,N-lutidine and 2,6-lutidine one or more species. The [Ir(cod)X ¹ ] ₂ and the compound shown in formula a, [Ir(cod)X ^1a ] ₂ and the compound shown in formula b, [Ir(cod)X ^1b ] ₂ and the compound shown in formula a The compound shown in formula c, [Ir(cod)X ^1c ] ₂ and the compound shown in formula d, [Ir(cod)X ^1d ] ₂ and the compound shown in formula e or [Ir(cod)X ^1e ] The molar ratio of ₂ to the compound represented by formula f is preferably 1:1-1:3.5, more preferably 1:2-1:3.5. The [Ir(cod)X ¹ ] ₂ , [Ir(cod)X ^1a ] ₂ , [Ir(cod)X ^1b ] ₂ , [Ir(cod)X ^1c ] ₂ , [Ir(cod)X ^1d ] 2 ] ₂ or [Ir(cod)X ^1e ] ₂ and the base molar ratio is preferably 1:1-1:20, more preferably 2:15-1:20. The organic solvent and [Ir(cod)X ¹ ] ₂ , [Ir(cod)X ^1a ] ₂ , [Ir(cod)X ^1b ] ₂ , [Ir(cod)X ^1c ] ₂ , [Ir(cod)X 1c ] 2 , [Ir(cod)X 1a ] 2 , )X ^1d ] ₂ or [Ir(cod)X ^1e ] ₂ preferably has a volume mass of 0.1 mL/mg-1 mL/mg. The temperature of the reaction is preferably 0°C-150°C, more preferably 25°C-125°C. The time for the complexation reaction is preferably 20-48 hours.

所述的反应结束后，其还可包含后处理的操作。所述的后处理的方法可为本领域后处理常规的方法，较佳地为将反应结束后的反应液，除溶剂后，粗产物经重结晶、薄层层析或柱层析分离纯化，即可。所述的重结晶的溶剂、所述的薄层层析展开剂，或所述的柱层析的洗脱液较佳地为极性溶剂与非极性溶剂的混合液。所述的极性溶剂较佳地为醇类溶剂和/或酯类溶剂。所述的醇类溶剂较佳地为甲醇、乙醇和异丙醇中的一种或多种。所述的酯类溶剂较佳地为乙酸乙酯。所述的所述的非极性溶剂较佳地为氯代烃类溶剂和/或烷烃类溶剂。所述的氯代烃类溶剂较佳地为二氯甲烷。所述的烷烃类溶剂较佳地为石油醚和/或正己烷。所述的重结晶的溶剂较佳地为二氯甲烷-正己烷、异丙醇-石油醚、乙酸乙酯-石油醚、乙酸乙酯-正己烷，和异丙醇-乙酸乙酯-石油醚中的一种或多种。所述的薄层层析的展开剂或者柱层析的洗脱液较佳地为异丙醇-石油醚、异丙醇-二氯甲烷、甲醇-二氯甲烷、乙酸乙酯-石油醚、乙酸乙酯-正己烷，和异丙醇-乙酸乙酯-石油醚中的一种或多种。所述的重结晶的溶剂、所述的薄层层析展开剂，或所述的柱层析的洗脱液中，所述的极性溶剂与所述的非极性溶剂的体积比较佳地为1:1-1:500。例如：乙酸乙酯：石油醚＝1:1-1:500，和异丙醇：石油醚＝1:1-1:500。After the reaction is finished, it may also include post-treatment operations. The post-treatment method can be a conventional post-treatment method in the art, preferably the reaction solution after the reaction is removed, and the crude product is separated and purified by recrystallization, thin-layer chromatography or column chromatography, That's it. The recrystallization solvent, the thin-layer chromatography developer, or the column chromatography eluent are preferably a mixture of polar solvents and non-polar solvents. The polar solvent is preferably an alcohol solvent and/or an ester solvent. The alcohol solvent is preferably one or more of methanol, ethanol and isopropanol. The ester solvent is preferably ethyl acetate. The said non-polar solvent is preferably a chlorinated hydrocarbon solvent and/or an alkane solvent. The chlorinated hydrocarbon solvent is preferably dichloromethane. The alkane solvent is preferably petroleum ether and/or n-hexane. The solvent of described recrystallization is preferably dichloromethane-n-hexane, isopropanol-petroleum ether, ethyl acetate-petroleum ether, ethyl acetate-n-hexane, and isopropanol-ethyl acetate-petroleum ether one or more of. The developing agent of described thin-layer chromatography or the eluent of column chromatography are preferably isopropanol-petroleum ether, isopropanol-methylene chloride, methanol-methylene chloride, ethyl acetate-petroleum ether, One or more of ethyl acetate-n-hexane, and isopropanol-ethyl acetate-petroleum ether. In the recrystallization solvent, the thin-layer chromatography developer, or the eluent of the column chromatography, the volume ratio of the polar solvent to the non-polar solvent is preferably 1:1-1:500. For example: ethyl acetate:petroleum ether=1:1-1:500, and isopropanol:petroleum ether=1:1-1:500.

本发明还提供了一种所述的通式I、通式II、通式III、通式IV、通式V或通式VI所示的金属铱络合物作为催化剂在不对称烯丙基取代反应中的应用。The present invention also provides a metal iridium complex shown in general formula I, general formula II, general formula III, general formula IV, general formula V or general formula VI as a catalyst in the asymmetric allyl substitution React application.

所述的不对称烯丙基取代反应，其优选包含以下步骤：有机溶剂中，在碱的作用下，在所述的通式I、通式II、通式III、通式IV、通式V或通式VI所示的金属铱络合物中的一种或多种的催化下，将如式S1所示的化合物进行如下所示的不对称烯丙基取代反应，制得如式P所示的苯并吲哚类化合物；其中，用*标注的碳为手性碳或非手性碳，当为手性碳时，所述的手性碳为S构型或R构型；The asymmetric allyl substitution reaction preferably comprises the following steps: in an organic solvent, under the action of a base, in the general formula I, general formula II, general formula III, general formula IV, general formula V Or under the catalysis of one or more of the metal iridium complexes shown in the general formula VI, the compound shown in the formula S1 is subjected to the asymmetric allyl substitution reaction shown below to obtain the compound shown in the formula P The benzindole compound shown; wherein, the carbon marked with * is a chiral carbon or an achiral carbon, and when it is a chiral carbon, the chiral carbon is an S configuration or an R configuration;

如式S1所示的化合物和如式P所示的化合物中，R_a1为单取代或多取代，相同或不同，选自下列取代基中的一个或多个：卤素、取代或未取代的C₁-C₄的烷基，或者取代或未取代的C₁-C₄的烷氧基；R_b1为取代或未取代的C₁-C₄的烷基，或者取代或未取代的C₂-C₄的烯基；R_c1为其中，M为O或NH；R_d1为C₁-C₄的烷基、被一个或多个卤素取代的C₁-C₄的烷基或C₁-C₄的烷氧基；R_e1为C₁-C₄的烷基或C₆-C₂₀芳基；R_a1和R_b1中，所述的取代的C₁-C₄的烷基或所述的取代的C₁-C₄的烷氧基中所述的取代是指被下列一个或多个取代基所取代：卤素(所述的卤素为F、Cl、Br或I)、C₁-C₄的烷氧基(所述的C₁-C₄的烷氧基较佳地为甲氧基、乙氧基、正丙氧基、异丙氧基、正丁氧基、异丁氧基或叔丁氧基)、C₁-C₄的烷基(所述的C₁-C₄的烷基较佳地为甲基、乙基、正丙基、异丙基、正丁基、异丁基或叔丁基)、C₆～C₂₀芳基(所述的C₆～C₂₀芳基较佳地为苯基，或被一个或多个C₁-C₄烷氧基取代的C₆-C₂₀芳基，当取代基为多个时，所述的取代基相同或不同(所述的被一个或多个C₁-C₄烷氧基取代的C₆-C₂₀芳基较佳地为对甲氧基苯基)，当取代基为多个时，所述的取代基相同或不同。In the compound shown in formula S1 and the compound shown in formula P, R _a1 is monosubstituted or multisubstituted, the same or different, and is selected from one or more of the following substituents: halogen, substituted or unsubstituted C ₁ -C ₄ alkyl, or substituted or unsubstituted C ₁ -C ₄ alkoxy; R _b1 is substituted or unsubstituted C ₁ -C ₄ alkyl, or substituted or unsubstituted C ₂ - Alkenyl of C ₄ ; R _c1 is Wherein, M is O or NH; R _d1 is C ₁ -C ₄ alkyl, C ₁ -C ₄ alkyl or C ₁ -C ₄ alkoxy substituted by one or more halogens; R _e1 is C ₁ -C ₄ alkyl or C ₆ -C ₂₀ aryl; R _a1 and R _b1 , the substituted C ₁ -C ₄ alkyl or the substituted C ₁ -C ₄ alkane The substitution described in the oxy group refers to being substituted by one or more of the following substituents: halogen (the said halogen is F, Cl, Br or I), C ₁ -C ₄ alkoxyl group (the said C ₁ -C ₄ alkoxy is preferably methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy or tert-butoxy), C ₁ -C ₄ alkyl (the C ₁ -C ₄ alkyl is preferably methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl or tert-butyl), C ₆ ~ C ₂₀ aryl (the C ₆ -C ₂₀ aryl is preferably phenyl, or a C ₆ -C ₂₀ aryl substituted by one or more C ₁ -C ₄ alkoxy groups, when the substituent is When multiple, the substituents are the same or different (the C ₆ -C ₂₀ aryl substituted by one or more C ₁ -C ₄ alkoxy groups is preferably p-methoxyphenyl), When there are multiple substituents, the substituents are the same or different.

R_a1中，所述的卤素较佳地为F、Cl、Br或I。In R _a1 , the halogen is preferably F, Cl, Br or I.

R_a1或R_b1中，所述的取代或未取代的C₁-C₄的烷基较佳地为取代或未取代的甲基、取代或未取代的乙基、取代或未取代的正丙基、取代或未取代的异丙基、取代或未取代的正丁基、取代或未取代的异丁基，或取代或未取代的叔丁基。所述的取代的甲基较佳地为苄基或对甲氧基苄基。In R _a1 or R _b1 , the substituted or unsubstituted C ₁ -C ₄ alkyl group is preferably substituted or unsubstituted methyl, substituted or unsubstituted ethyl, substituted or unsubstituted n-propyl substituted or unsubstituted isopropyl, substituted or unsubstituted n-butyl, substituted or unsubstituted isobutyl, or substituted or unsubstituted t-butyl. The substituted methyl group is preferably benzyl or p-methoxybenzyl.

R_a1中，所述的取代或未取代的C₁-C₄的烷氧基较佳地为取代或未取代的甲氧基、取代或未取代的乙氧基、取代或未取代的正丙氧基、取代或未取代的异丙氧基、取代或未取代的正丁氧基、取代或未取代的异丁氧基，或取代或未取代的叔丁氧基。In R _a1 , the substituted or unsubstituted C ₁ -C ₄ alkoxy is preferably substituted or unsubstituted methoxy, substituted or unsubstituted ethoxy, substituted or unsubstituted n-propyl Oxy, substituted or unsubstituted isopropoxy, substituted or unsubstituted n-butoxy, substituted or unsubstituted isobutoxy, or substituted or unsubstituted t-butoxy.

R_b1中，所述的C₂-C₄的烯基较佳地为乙烯基、1-丙烯基、2-丙烯基、1-丁烯基、2-丁烯基或3-丁烯基。In R _b1 , the C ₂ -C ₄ alkenyl is preferably vinyl, 1-propenyl, 2-propenyl, 1-butenyl, 2-butenyl or 3-butenyl.

R_d1或R_e1中，所述的C₁-C₄的烷基较佳地为甲基、乙基、正丙基、异丙基、正丁基、异丁基或叔丁基。In R _d1 or R _e1 , the C ₁ -C ₄ alkyl group is preferably methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl or tert-butyl.

R_d1中，所述的C₁-C₄的烷氧基较佳地为甲氧基、乙氧基、正丙氧基、异丙氧基、正丁氧基、异丁氧基或叔丁氧基。In R _d1 , the C ₁ -C ₄ alkoxy group is preferably methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy or tert-butyl Oxygen.

R_d1中，所述的被一个或多个卤素取代的C₁-C₄的烷基中所述的卤素较佳地是指氟、氯、溴或碘；所述的被一个或多个卤素取代的C₁-C₄的烷基中所述的C₁-C₄的烷基较佳地为甲基、乙基、正丙基、异丙基、正丁基、异丁基或叔丁基。所述的被一个或多个卤素取代的C₁-C₄的烷基较佳地为 In R _d1 , the said C ₁ -C ₄ alkyl group substituted by one or more halogens preferably refers to fluorine, chlorine, bromine or iodine; said one or more halogens The C ₁ -C ₄ alkyl group described in the substituted C ₁ -C ₄ alkyl group is preferably methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl or tert-butyl base. The C ₁ -C ₄ alkyl substituted by one or more halogens is preferably

R_e1中，所述的C₆-C₂₀芳基较佳地为苯基。In R _e1 , the C ₆ -C ₂₀ aryl is preferably phenyl.

所述的不对称烯丙基取代反应的方法可为本领域此类反应常规的方法，较佳地，仅在所述的通式I、通式II、通式III、通式IV、通式V或通式VI所示的金属铱络合物中的一种或多种的催化下进行，不再包含其他催化剂，例如铜类催化剂和/或钯类催化剂。所述的不对称烯丙基取代反应较佳地在气体保护下进行。所述的气体较佳地为惰性气体，例如氩气。其中，所述的有机溶剂可为本领域此类反应常规的有机溶剂，只要不影响反应进行即可，本发明中优选为芳烃类溶剂、卤代烃类溶剂、醚类溶剂、酰胺类溶剂、烷烃类溶剂和腈类溶剂中的一种或多种。所述的芳烃类溶剂较佳地为甲苯。所述的卤代烃类溶剂较佳地为二氯甲烷(DCM)和/或三氯甲烷(CHCl₃)。所述的醚类溶剂较佳地为四氢呋喃(THF)、乙醚和1,4-二氧六环中的一种或多种。所述的烷烃类溶剂较佳地为正己烷。所述的腈类溶剂较佳地为乙腈。所述的碱较佳地为有机碱和/或无机碱。所述的有机碱可为本领域常规的有机碱，较佳地为1,8-二氮杂二环十一碳-7-烯(DBU)、N,N-二异丙基乙胺(DIEA)、三乙胺(Et₃N)和1,4-二氮杂二环[2.2.2]辛烷(DABCO)中的一种或多种。所述的无机碱可为本领域常规的无机碱，较佳地为Cs₂CO₃、K₂CO₃、Na₂CO₃、Li₂CO₃、叔丁醇锂(^tBuOLi)、叔丁醇钠(^tBuONa)和叔丁醇钾(^tBuOK)中的一种或多种。所述的金属铱络合物与如式S1所示的化合物的摩尔比可为按照本领域常规此类反应常规的摩尔比进行选择，较佳地为0.01:1～0.1:1。所述的碱的用量与如式S1所示的化合物的摩尔比可为本领域常规的摩尔比，较佳地为0.1:1-1:1。所述的溶剂的用量以不影响反应的进行即可，较佳地，与如式A所示的化合物的体积质量比为10mL/g-100mL/g。所述的反应的温度较佳地为0-120℃，较佳地为25～85℃。所述的反应的进程可以采用本领域中的常规测试方法(如TLC、HPLC或NMR)进行监控，一般以如式S1所示的化合物消失时为反应终点，反应时间较佳地为2-48h。The method for the asymmetric allyl substitution reaction can be a conventional method for this type of reaction in the art, preferably, only in the general formula I, general formula II, general formula III, general formula IV, general formula V or one or more of the metal iridium complexes represented by the general formula VI are catalyzed, and no other catalysts are included, such as copper catalysts and/or palladium catalysts. The asymmetric allyl substitution reaction is preferably carried out under gas protection. The gas is preferably an inert gas, such as argon. Wherein, the organic solvent can be a conventional organic solvent for this type of reaction in the art, as long as it does not affect the reaction, it is preferably an aromatic hydrocarbon solvent, a halogenated hydrocarbon solvent, an ether solvent, an amide solvent, One or more of alkane solvents and nitrile solvents. The aromatic solvent is preferably toluene. The halogenated hydrocarbon solvent is preferably dichloromethane (DCM) and/or chloroform (CHCl ₃ ). The ether solvent is preferably one or more of tetrahydrofuran (THF), diethyl ether and 1,4-dioxane. The alkane solvent is preferably n-hexane. The nitrile solvent is preferably acetonitrile. The base is preferably an organic base and/or an inorganic base. The organic base can be a conventional organic base in the art, preferably 1,8-diazabicycloundec-7-ene (DBU), N,N-diisopropylethylamine (DIEA ), triethylamine (Et ₃ N) and 1,4-diazabicyclo[2.2.2]octane (DABCO). The inorganic base can be a conventional inorganic base in the art, preferably Cs ₂ CO ₃ , K ₂ CO ₃ , Na ₂ CO ₃ , Li ₂ CO ₃ , lithium tert-butoxide ( ^tBuOLi ), tert-butanol One or more of sodium ( ^tBuONa ) and potassium tert-butoxide ( ^tBuOK ). The molar ratio of the metal iridium complex to the compound represented by formula S1 can be selected according to the conventional molar ratio of this type of reaction in the art, preferably 0.01:1-0.1:1. The molar ratio of the amount of the base to the compound represented by formula S1 can be a conventional molar ratio in the art, preferably 0.1:1-1:1. The solvent can be used in an amount that does not affect the reaction. Preferably, the volume-to-mass ratio of the solvent to the compound represented by formula A is 10 mL/g-100 mL/g. The temperature of the reaction is preferably 0-120°C, more preferably 25-85°C. The process of the reaction can be monitored by conventional testing methods in the art (such as TLC, HPLC or NMR), generally when the compound shown in formula S1 disappears as the end point of the reaction, the reaction time is preferably 2-48h .

本发明还提供了一种如式P所示的苯并吲哚类化合物，其中，用*标注的碳为手性碳或非手性碳，当为手性碳时，所述的手性碳为S构型或R构型；The present invention also provides a benzindole compound as shown in formula P, wherein the carbon marked with * is a chiral carbon or an achiral carbon, and when it is a chiral carbon, the chiral carbon It is S configuration or R configuration;

其中，R_a1和R_b1的定义均同前所述；但是如式P所示的化合物不包含下列任一结构的化合物：Wherein, the definitions of R _a1 and R _b1 are the same as described above; but the compounds shown in formula P do not include compounds of any of the following structures:

所述的如式P所示的化合物，较佳地为如下任一化合物：The compound represented by formula P is preferably any of the following compounds:

在不违背本领域常识的基础上，上述各优选条件，可任意组合，即得本发明各较佳实例。On the basis of not violating common knowledge in the field, the above-mentioned preferred conditions can be combined arbitrarily to obtain preferred examples of the present invention.

本发明所用试剂和原料均市售可得。The reagents and raw materials used in the present invention are all commercially available.

本发明的积极进步效果在于：The positive progress effect of the present invention is:

(1)本发明中的含有手性三唑卡宾的金属铱络合物，在空气中稳定，便于保存。该金属铱络合物可以在空气中进行柱层析纯化，重结晶等操作，对产物没有影响。该金属铱络合物在空气中放置六个月，其纯度(>97％，核磁纯度)没有变化，再用于催化烯丙基取代反应的催化剂时，对目标化合物的收率和纯度均无影响，催化效果与新制备时相同。(1) The metal iridium complex containing chiral triazole carbene in the present invention is stable in air and convenient for preservation. The metal iridium complex can be purified by column chromatography and recrystallized in air without affecting the product. The metal iridium complex was placed in the air for six months, and its purity (>97%, nuclear magnetic purity) did not change, and when it was used as a catalyst for catalyzing the allyl substitution reaction, it had no effect on the yield and purity of the target compound. Influence, the catalytic effect is the same as when freshly prepared.

(2)本发明的金属铱络合物的制备方法的反应条件温和、操作简单、原料易得、收率高和后处理简单。(2) The preparation method of the metal iridium complex of the present invention has mild reaction conditions, simple operation, readily available raw materials, high yield and simple post-treatment.

(3)本发明中的含有手性三唑卡宾的金属铱络合物可以应用在金属铱催化的多种不同类型不对称分子间烯丙基取代反应和分子内取代反应之中，并且取得高产率、高区域选择性和高对映选择性，可以应用在更为复杂的底物反应中，极大的拓展不对称分子间烯丙基取代反应和分子内取代反应的使用范围。(3) The metal iridium complex containing chiral triazole carbene in the present invention can be applied in various types of asymmetric intermolecular allyl substitution reactions and intramolecular substitution reactions catalyzed by metal iridium, and achieve high yield High efficiency, high regioselectivity and high enantioselectivity, can be applied in more complex substrate reactions, greatly expanding the scope of use of asymmetric intermolecular allyl substitution reactions and intramolecular substitution reactions.

附图说明Description of drawings

图1为实施例3制得的化合物IIIa的单晶结构图。Figure 1 is a single crystal structure diagram of compound IIIa prepared in Example 3.

具体实施方式Detailed ways

下面通过实施例的方式进一步说明本发明，但并不因此将本发明限制在所述的实施例范围之中。下列实施例中未注明具体条件的实验方法，按照常规方法和条件，或按照商品说明书选择。The present invention is further illustrated below by means of examples, but the present invention is not limited to the scope of the examples. For the experimental methods that do not specify specific conditions in the following examples, select according to conventional methods and conditions, or according to the product instructions.

其中化合物a、b、c、d、e和f可根据本领域常规的方法制备得到，具体见(a)Chem.Commun.2008,2263.(b)J.Org.Chem.2005,70,5725.(c)Org.Biomol.Chem.2011,9,2072.(d)Org.Lett.2008,10,277.(e)Angew.Chem.Int.Ed.2002,41,1743.(f)J.Am.Chem.Soc.2007,129,10098.。Wherein compounds a, b, c, d, e and f can be prepared according to conventional methods in the art, specifically see (a) Chem.Commun.2008, 2263. (b) J.Org.Chem.2005,70,5725 .(c)Org.Biomol.Chem.2011,9,2072.(d)Org.Lett.2008,10,277.(e)Angew.Chem.Int.Ed.2002,41,1743.(f)J.Am .Chem.Soc.2007,129,10098.

实施例1通式I所示的金属铱络合物的合成The synthesis of the metal iridium complex shown in embodiment 1 general formula I

氩气保护下，在一个干燥的250毫升三口瓶中，加入[Ir(cod)Cl]₂(336mg,0.5mmol)，如式a所示的化合物和碱，加入有机溶剂，搅拌反应24小时，粗产物通过柱层析分离(乙酸乙酯/石油醚＝1:5)。化合物Ia-Ic和化合物If的具体反应条件参见表1。化合物Id-Ie，化合物Ig-Ik的制备方法和条件参照实施例1和表1，其中，表1中的摩尔比是指[Ir(cod)X¹]₂：化合物a：碱的摩尔比。Under the protection of argon, in a dry 250 ml three-necked flask, add [Ir(cod)Cl] ₂ (336 mg, 0.5 mmol), the compound shown in formula a and the base, add an organic solvent, and stir the reaction for 24 hours, The crude product was separated by column chromatography (ethyl acetate/petroleum ether=1:5). See Table 1 for the specific reaction conditions of Compounds Ia-Ic and Compound If. The preparation methods and conditions of compound Id-Ie and compound Ig-Ik refer to Example 1 and Table 1, wherein the molar ratio in Table 1 refers to the molar ratio of [Ir(cod)X ¹ ] ₂ :compound a:base.

表1Table 1

化合物IaCompound Ia

黄色固体，收率：54％.(纯度>97％，核磁纯度)Yellow solid, yield: 54%. (purity>97%, NMR purity)

¹H NMR(300MHz,CDCl₃)δ8.32(d,J＝7.2Hz,2H),7.49-7.46(m,3H),4.94(AB,J_AB＝15.0Hz,1H),4.80-4.71(m,3H),4.44-4.38(m,2H),3.89(d,J＝6.9Hz,1H),2.85-2.78(m,1H),2.36-1.67(m,8H),1.51-1.22(m,5H),1.06(s,3H),0.95(s,3H),0.88(s,3H). ¹ H NMR (300MHz, CDCl ₃ ) δ8.32 (d, J = 7.2Hz, 2H), 7.49-7.46 (m, 3H), 4.94 (AB, J _AB = 15.0Hz, 1H), 4.80-4.71 (m ,3H),4.44-4.38(m,2H),3.89(d,J＝6.9Hz,1H),2.85-2.78(m,1H),2.36-1.67(m,8H),1.51-1.22(m,5H ),1.06(s,3H),0.95(s,3H),0.88(s,3H).

¹³C NMR(100MHz,CDCl₃)δ181.5,149.3,140.2,128.44,128.38,128.2,124.4,123.9,85.1,84.6,61.4,59.4,54.5,52.0,50.1,47.6,33.2,32.51,32.49,29.9,28.5,25.4,22.0,21.2,11.4. ¹³ C NMR (100MHz, CDCl ₃ ) δ181.5, 149.3, 140.2, 128.44, 128.38, 128.2, 124.4, 123.9, 85.1, 84.6, 61.4, 59.4, 54.5, 52.0, 50.1, 47.6, 33.2, 52.51, 92.9, 2, 2 ,25.4,22.0,21.2,11.4.

元素分析：计算值(Calcd for)C₂₇H₃₅N₃ClOIr:C,50.26；H,5.47；N,6.51.实验值(Found):C,50.26；H,5.43；N,6.38.Elemental analysis: Calcd for C ₂₇ H ₃₅ N ₃ ClOIr: C, 50.26; H, 5.47; N, 6.51. Found: C, 50.26; H, 5.43; N, 6.38.

化合物IbCompound Ib

黄色固体，收率：44％.(纯度>97％，核磁纯度)Yellow solid, yield: 44%. (purity>97%, NMR purity)

¹H NMR(300MHz,CDCl₃)δ7.03(s,1H),6.90(s,1H),4.90(AB,J_AB＝14.7Hz,1H),4.62-4.53(m,4H),4.41(AB,J_AB＝14.7Hz,1H),3.95(d,J＝6.9Hz,1H),3.05(d,J＝8.4Hz,1H),2.67-2.63(m,1H),2.37(s,3H),2.36(s,3H),2.10-1.89(m,4H),1.84(s,3H),1.71-1.26(m,7H),1.09(d,J＝6.0Hz,1H),1.05(s,3H),0.95(s,3H),0.82(s,3H). ¹ H NMR (300MHz, CDCl ₃ ) δ7.03(s, 1H), 6.90(s, 1H), 4.90(AB, _JAB = 14.7Hz, 1H), 4.62-4.53(m, 4H), 4.41(AB ,J _AB =14.7Hz,1H),3.95(d,J=6.9Hz,1H),3.05(d,J=8.4Hz,1H),2.67-2.63(m,1H),2.37(s,3H), 2.36(s,3H),2.10-1.89(m,4H),1.84(s,3H),1.71-1.26(m,7H),1.09(d,J＝6.0Hz,1H),1.05(s,3H) ,0.95(s,3H),0.82(s,3H).

¹³C NMR(75MHz,CDCl₃)δ181.5,148.6,139.3,136.5,136.2,135.4,129.2,128.1,84.8,84.1,84.0,61.0,59.2,53.2,51.5,51.1,50.2,47.7,33.6,33.1,32.7,29.1,29.0,25.1,21.9,21.2,20.6,19.5,17.5,11.4. ¹³ C NMR (75MHz, CDCl ₃ ) δ181.5, 148.6, 139.3, 136.5, 136.2, 135.4, 129.2, 128.1, 84.8, 84.1, 84.0, 61.0, 59.2, 53.2, 51.5, 51.1, 50.2, 47.7, 33.32.6, 33.1, ,29.1,29.0,25.1,21.9,21.2,20.6,19.5,17.5,11.4.

元素分析：计算值(Calcd for)C₃₀H₄₁N₃ClOIr:C,52.42；H,6.01；N,6.11.实验值(Found):C,52.62；H,6.03；N,6.04.Elemental analysis: Calcd for C ₃₀ H ₄₁ N ₃ ClOIr: C, 52.42; H, 6.01; N, 6.11. Found: C, 52.62; H, 6.03; N, 6.04.

化合物IcCompound Ic

黄色固体，收率：40％.(纯度>97％，核磁纯度)Yellow solid, yield: 40%. (purity>97%, NMR purity)

¹H NMR(400MHz,CD₂Cl₂)δ9.43(s,2H),7.94(s,1H),5.01(AB,J_AB＝13.6Hz,1H),4.95-4.91(m,1H),4.76-4.71(m,1H),4.57(d,J＝4.4Hz,1H),4.43(AB,J_AB＝15.2Hz,1H),4.03-3.98(m,2H),2.85-2.80(m,1H),2.54(t,J＝7.2Hz,1H),2.35-2.27(m,1H),2.13-1.99(m,4H),1.87-1.81(m,1H),1.71(dt,J＝2.8,12.0Hz,1H),1.58-1.55(m,2H),1.51-1.47(m,1H),1.39-1.33(m,1H),1.30-1.26(m,1H),1.04(s,3H),0.90(s,3H),0.87(s,3H). ¹ H NMR (400MHz, CD ₂ Cl ₂ ) δ9.43(s,2H),7.94(s,1H),5.01(AB,J _AB =13.6Hz,1H),4.95-4.91(m,1H),4.76 -4.71(m,1H),4.57(d,J＝4.4Hz,1H),4.43(AB,J _AB ＝15.2Hz,1H),4.03-3.98(m,2H),2.85-2.80(m,1H) ,2.54(t,J=7.2Hz,1H),2.35-2.27(m,1H),2.13-1.99(m,4H),1.87-1.81(m,1H),1.71(dt,J=2.8,12.0Hz ,1H),1.58-1.55(m,2H),1.51-1.47(m,1H),1.39-1.33(m,1H),1.30-1.26(m,1H),1.04(s,3H),0.90(s ,3H),0.87(s,3H).

¹³C NMR(100MHz,CD₂Cl₂)δ186.3,149.9,141.5,131.8(q,J＝33.4Hz),124.9(m),123.9,121.4(m),87.6,87.1,85.4,62.7,59.6,55.0,52.3,51.2,50.2,48.7,34.5,33.0,32.4,31.0,28.1,26.9,21.6,20.6,11.3. ¹³ C NMR (100MHz, CD ₂ Cl ₂ ) δ186.3, 149.9, 141.5, 131.8 (q, J=33.4Hz), 124.9(m), 123.9, 121.4(m), 87.6, 87.1, 85.4, 62.7, 59.6, 55.0 ,52.3,51.2,50.2,48.7,34.5,33.0,32.4,31.0,28.1,26.9,21.6,20.6,11.3.

¹⁹F NMR(376MHz,CD₂Cl₂)δ-63.1(s). ¹⁹ F NMR (376MHz, CD ₂ Cl ₂ )δ-63.1(s).

元素分析：计算值(Calcd for)C₂₉H₃₃N₃F₆ClOIr:C,44.58；H,4.26；N,5.38.实验值(Found):C,44.45；H,4.34；N,5.12.Elemental analysis: Calcd for C ₂₉ H ₃₃ N ₃ F ₆ ClOIr: C, 44.58; H, 4.26; N, 5.38. Found: C, 44.45; H, 4.34; N, 5.12.

化合物IdCompound Id

黄色固体，收率：57％.(纯度>97％，核磁纯度)Yellow solid, yield: 57%. (purity>97%, NMR purity)

¹H NMR(400MHz,DMSO-d₆)δ8.57(d,J＝8.0Hz,1H),7.36(d,J＝7.6Hz,1H),7.30(t,J＝7.6Hz,1H),7.17(t,J＝7.2Hz,1H),6.02(d,J＝3.2Hz,1H),5.00(AB,J_AB＝15.6Hz,1H),4.94(t,J＝3.6Hz,1H),4.91(AB,J_AB＝16.0Hz,1H),4.60-4.56(m,1H),4.38-4.35(m,1H),3.46-3.41(m,2H),3.30-3.27(m,1H),3.04(AB,J_AB＝16.8Hz,1H)2.13-2.09(m,1H),2.00-1.88(m,3H),1.71-1.58(m,4H). ¹ H NMR (400MHz, DMSO-d ₆ )δ8.57(d, J=8.0Hz, 1H), 7.36(d, J=7.6Hz, 1H), 7.30(t, J=7.6Hz, 1H), 7.17 (t,J=7.2Hz,1H),6.02(d,J=3.2Hz,1H),5.00(AB,J _AB =15.6Hz,1H),4.94(t,J=3.6Hz,1H),4.91( AB,J _AB ＝16.0Hz,1H),4.60-4.56(m,1H),4.38-4.35(m,1H),3.46-3.41(m,2H),3.30-3.27(m,1H),3.04(AB ,J _AB ＝16.8Hz,1H)2.13-2.09(m,1H),2.00-1.88(m,3H),1.71-1.58(m,4H).

¹³C NMR(100MHz,DMSO-d₆)δ187.8,149.9,140.8,138.5,128.6,126.6,126.5,125.0,87.8,86.2,78.2,62.0,59.7,54.5,52.9,36.9,33.4,33.0,28.9,28.7,27.6. ¹³ C NMR (100MHz, DMSO-d ₆ ) δ187.8, 149.9, 140.8, 138.5, 128.6, 126.6, 126.5, 125.0, 87.8, 86.2, 78.2, 62.0, 59.7, 54.5, 52.9, 36.9, 33.4, 33.0, 28.9, 28. ,27.6.

¹⁹F NMR(376MHz,DMSO-d₆)δ-138.6(d,J＝23.3Hz),-144.6(d,J＝24.8Hz),-150.3(t,J＝22.6Hz),-161.9(t,J＝23.7Hz),-162.6(t,J＝23.3Hz). ¹⁹ F NMR (376MHz, DMSO-d ₆ ) δ-138.6(d, J=23.3Hz), -144.6(d, J=24.8Hz), -150.3(t, J=22.6Hz), -161.9(t, J=23.7Hz), -162.6(t, J=23.3Hz).

元素分析：计算值(Calcd for)C₂₆H₂₂N₃F₅ClOIr:C,43.67；H,3.10；N,5.88.实验值(Found):C,43.62；H,3.02；N,5.71.Elemental analysis: Calcd for C ₂₆ H ₂₂ N ₃ F ₅ ClOIr: C, 43.67; H, 3.10; N, 5.88. Found: C, 43.62; H, 3.02; N, 5.71.

化合物IeCompound Ie

黄色固体，收率：50％.(纯度>97％，核磁纯度)Yellow solid, yield: 50%. (purity>97%, NMR purity)

¹H NMR(300MHz,CDCl₃)δ8.32(d,J＝7.2Hz,2H),7.49-7.46(m,3H),4.94(AB,J_AB＝15.0Hz,1H),4.80-4.71(m,3H),4.44-4.38(m,2H),3.89(d,J＝6.9Hz,1H),3.62(s,3H),2.85-2.78(m,1H),2.36-1.67(m,7H),1.51-1.22(m,5H),1.06(s,3H),0.95(s,3H),0.88(s,3H). ¹ H NMR (300MHz, CDCl ₃ ) δ8.32 (d, J = 7.2Hz, 2H), 7.49-7.46 (m, 3H), 4.94 (AB, J _AB = 15.0Hz, 1H), 4.80-4.71 (m ,3H),4.44-4.38(m,2H),3.89(d,J＝6.9Hz,1H),3.62(s,3H),2.85-2.78(m,1H),2.36-1.67(m,7H), 1.51-1.22(m,5H),1.06(s,3H),0.95(s,3H),0.88(s,3H).

MS(ESI⁺):675(C₂₈H₃₇ClIrN₃O₂[M⁺]).MS(ESI ⁺ ):675(C ₂₈ H ₃₇ ClIrN ₃ O ₂ [M ⁺ ]).

化合物IfCompound If

黄色固体，收率：60％.(纯度>97％，核磁纯度)Yellow solid, yield: 60%. (purity>97%, NMR purity)

¹H NMR(300MHz,CDCl₃)δ8.32(d,J＝7.2Hz,2H),7.49-7.46(m,3H),4.94(AB,J_AB＝15.0Hz,1H),4.80-4.71(m,3H),4.44-4.38(m,2H),3.89(d,J＝6.9Hz,1H),3.51(s,3H),2.85-2.78(m,1H),2.36-1.67(m,8H),1.51-1.22(m,5H),1.06(s,3H),0.95(s,3H),0.88(s,3H). ¹ H NMR (300MHz, CDCl ₃ ) δ8.32 (d, J = 7.2Hz, 2H), 7.49-7.46 (m, 3H), 4.94 (AB, J _AB = 15.0Hz, 1H), 4.80-4.71 (m ,3H),4.44-4.38(m,2H),3.89(d,J＝6.9Hz,1H),3.51(s,3H),2.85-2.78(m,1H),2.36-1.67(m,8H), 1.51-1.22(m,5H),1.06(s,3H),0.95(s,3H),0.88(s,3H).

MS(ESI⁺):641(C₂₈H₃₈IrN₃O₂[M⁺]).MS (ESI ⁺ ): 641 (C ₂₈ H ₃₈ IrN ₃ O ₂ [M ⁺ ]).

化合物IgCompound Ig

黄色固体，收率：55％.(纯度>97％，核磁纯度)Yellow solid, yield: 55%. (purity>97%, NMR purity)

MS(ESI⁺):745(C₃₅H₃₉IrN₃O[M⁺]).MS(ESI ⁺ ):745(C ₃₅ H ₃₉ IrN ₃ O[M ⁺ ]).

化合物IhCompound Ih

化合物IiCompound Ii

黄色固体，收率：52％.(纯度>97％，核磁纯度)Yellow solid, yield: 52%. (purity>97%, NMR purity)

MS(ESI⁺):651(C₂₇H41₃₉IrN₃O[M⁺]).MS(ESI ⁺ ):651(C ₂₇ H41 ₃₉ IrN ₃ O[M ⁺ ]).

化合物IjCompound Ij

MS(ESI⁺):659(C₂₈H41₃₇IrN₃O[M⁺]).MS(ESI ⁺ ):659(C ₂₈ H41 ₃₇ IrN ₃ O[M ⁺ ]).

化合物IkCompound Ik

MS(ESI⁺):690(C₂₇H41₃₄ClIrN₄O₃[M⁺]).MS(ESI ⁺ ):690(C ₂₇ H41 ₃₄ ClIrN ₄ O ₃ [M ⁺ ]).

实施例2通式II所示的金属铱络合物的合成The synthesis of the metal iridium complex shown in embodiment 2 general formula II

氩气保护下，在一个干燥的250毫升三口瓶中，加入[Ir(cod)X^1a]₂(336mg,0.5mmol)，如式b所示的化合物和碱，有机溶剂，搅拌反应，粗产物通过柱层析分离(乙酸乙酯/石油醚:1:5)。化合物IIa-IIc和化合物IIf的具体反应条件参见表2。化合物IId-IIe，化合物IIg-IIu的制备方法和条件参照实施例2和表2，其中，表2中的摩尔比是指[Ir(cod)X^1a]₂：化合物b：碱的摩尔比。Under the protection of argon, in a dry 250ml three-necked flask, add [Ir(cod)X ^1a ] ₂ (336mg, 0.5mmol), the compound shown in formula b and base, organic solvent, stirring reaction, crude product Separation by column chromatography (ethyl acetate/petroleum ether: 1:5). See Table 2 for the specific reaction conditions of compounds IIa-IIc and compound IIf. The preparation methods and conditions of compound IId-IIe and compound IIg-IIu refer to Example 2 and Table 2, wherein the molar ratio in Table 2 refers to the molar ratio of [Ir(cod)X ^1a ] ₂ :compound b:base.

表2Table 2

化合物IIaCompound IIa

MS(ESI⁺):858(C₃₉H₄₂ClIrN₄O₂S[M⁺]).MS(ESI ⁺ ):858(C ₃₉ H ₄₂ ClIrN ₄ O ₂ S[M ⁺ ]).

化合物IIbCompound IIb

黄色固体，收率：56％.(纯度>97％，核磁纯度)Yellow solid, yield: 56%. (purity>97%, NMR purity)

MS(ESI⁺):900(C₄₂H₄₈ClIrN₄O₂S[M⁺]).MS(ESI ⁺ ):900(C ₄₂ H ₄₈ ClIrN ₄ O ₂ S[M ⁺ ]).

化合物IIcCompound IIc

MS(ESI⁺):994(C₄₁H₄₀ClF₆IrN₄O₂S[M⁺]).MS(ESI ⁺ ):994(C ₄₁ H ₄₀ ClF ₆ IrN ₄ O ₂ S[M ⁺ ]).

化合物IIdCompound IId

MS(ESI⁺):948(C₃₉H₃₇ClF₅IrN₄O₂S[M⁺]).MS(ESI ⁺ ):948(C ₃₉ H ₃₇ ClF ₅ IrN ₄ O ₂ S[M ⁺ ]).

化合物IIeCompound IIe

黄色固体，收率：53％.(纯度>97％，核磁纯度)Yellow solid, yield: 53%. (purity>97%, NMR purity)

MS(ESI⁺):888(C₃₂H₃₂ClIrN₄O₃S[M⁺]).MS(ESI ⁺ ):888(C ₃₂ H ₃₂ ClIrN ₄ O ₃ S[M ⁺ ]).

化合物IIfCompound IIf

MS(ESI⁺):854(C₃₂H₃₂ClIrN₄O₃S[M⁺]).MS(ESI ⁺ ):854(C ₃₂ H ₃₂ ClIrN ₄ O ₃ S[M ⁺ ]).

化合物IIgCompound IIg

MS(ESI⁺):974(C₄₈H₅₀ClIrN₄O₂S[M⁺]).MS(ESI ⁺ ):974(C ₄₈ H ₅₀ ClIrN ₄ O ₂ S[M ⁺ ]).

化合物IIhCompound IIh

化合物IIiCompound IIi

MS(ESI⁺):888(C₄₁H₄₈ClIrN₄O₂S[M⁺]).MS(ESI ⁺ ):888(C ₄₁ H ₄₈ ClIrN ₄ O ₂ S[M ⁺ ]).

化合物IIjCompound IIj

MS(ESI⁺):880(C₄₀H₅₂ClIrN₄O₂S[M⁺]).MS(ESI ⁺ ):880(C ₄₀ H ₅₂ ClIrN ₄ O ₂ S[M ⁺ ]).

化合物IIkCompound IIk

MS(ESI⁺):919(C₄₀H₄₅ClIrN₅O₄S[M⁺]).MS(ESI ⁺ ):919(C ₄₀ H ₄₅ ClIrN ₅ O ₄ S[M ⁺ ]).

化合物IIlCompound IIl

黄色固体，收率：59％.(纯度>97％，核磁纯度)Yellow solid, yield: 59%. (purity>97%, NMR purity)

MS(ESI⁺):776(C₃₂H₄₄ClIrN₄O₂S[M⁺]).MS(ESI ⁺ ):776(C ₃₂ H ₄₄ ClIrN ₄ O ₂ S[M ⁺ ]).

化合物IImCompound IIm

MS(ESI⁺):762(C₃₅H₄₂ClIrN₄O[M⁺]).MS(ESI ⁺ ):762(C ₃₅ H ₄₂ ClIrN ₄ O[M ⁺ ]).

化合物IInCompound IIn

MS(ESI⁺):792(C₃₆H₄₄ClIrN₄O₂[M⁺]).MS (ESI ⁺ ): 792 (C ₃₆ H ₄₄ ClIrN ₄ O ₂ [M ⁺ ]).

化合物IIoCompound IIo

MS(ESI⁺):898(C₃₇H₄₀ClF₆IrN₄O[M⁺]).MS(ESI ⁺ ):898(C ₃₇ H ₄₀ ClF ₆ IrN ₄ O[M ⁺ ]).

化合物IIpCompound IIp

MS(ESI⁺):804(C₃₈H₄₈ClIrN₄O[M⁺]).MS(ESI ⁺ ):804(C ₃₈ H ₄₈ ClIrN ₄ O[M ⁺ ]).

化合物IIqCompound IIq

MS(ESI⁺):862(C₄₁H₅₄ClIrN₄O₂[M⁺]).MS (ESI ⁺ ): 862 (C ₄₁ H ₅₄ ClIrN ₄ O ₂ [M ⁺ ]).

化合物IIrCompound IIr

MS(ESI⁺):858(C₃₈H₄₅ClF₃IrN₄O[M⁺]).MS(ESI ⁺ ):858(C ₃₈ H ₄₅ ClF ₃ IrN ₄ O[M ⁺ ]).

化合物IIsCompound IIs

黄色固体，收率：55％.(纯度数据>97％，核磁纯度)Yellow solid, yield: 55%. (Purity data>97%, NMR purity)

MS(ESI⁺):894(C₃₇H₄₅ClF₃IrN₄O₂S[M⁺]).MS(ESI ⁺ ):894(C ₃₇ H ₄₅ ClF ₃ IrN ₄ O ₂ S[M ⁺ ]).

化合物IItCompound IIt

MS(ESI⁺):1244(C₄₄H₄₅ClF₁₇IrN₄O₂S[M⁺]).MS(ESI ⁺ ):1244(C ₄₄ H ₄₅ ClF ₁₇ IrN ₄ O ₂ S[M ⁺ ]).

实施例3如式III所示的金属铱络合物的合成Embodiment 3 is as the synthesis of the metal iridium complex shown in formula III

氩气保护下，在一个干燥的250毫升三口瓶中，加入[Ir(cod)X^1b]₂(336mg,0.5mmol)，如式c所示的化合物和碱，有机溶剂，搅拌反应。粗产物通过柱层析分离(乙酸乙酯/石油醚:1:5)。化合物IIIa-IIIc和化合物IIIf的具体反应条件参见表3。化合物IIId-IIIe的制备方法和条件参照实施例3和表3，其中，表3中的摩尔比是指[Ir(cod)X^1b]₂：化合物c：碱的摩尔比。Under the protection of argon, [Ir(cod)X ^1b ] ₂ (336mg, 0.5mmol), a compound represented by formula c, a base, and an organic solvent were added to a dry 250ml three-necked flask, and the reaction was stirred. The crude product was separated by column chromatography (ethyl acetate/petroleum ether: 1:5). See Table 3 for the specific reaction conditions of compounds IIIa-IIIc and compound IIIf. The preparation method and conditions of compound IIId-IIIe refer to Example 3 and Table 3, wherein the molar ratio in Table 3 refers to the molar ratio of [Ir(cod)X ^1b ] ₂ :compound c:base.

表3table 3

化合物IIIaCompound IIIa

黄色固体，收率：61％.(纯度>97％，核磁纯度)Yellow solid, yield: 61%. (purity>97%, NMR purity)

MS(ESI⁺):579(C₂₂H₂₉ClIrN₃O[M⁺]).MS(ESI ⁺ ):579(C ₂₂ H ₂₉ ClIrN ₃ O[M ⁺ ]).

化合物IIIa单晶的制备方法：将100mg化合物IIIa溶解在5mL CH₂Cl₂中，然后往其中逐滴加入正己烷(2mL)，直至恰好出现浑浊为止。再往其中加入一滴CH₂Cl₂，将生成的沉淀再次溶解。将该溶液静置于-30℃冰箱中直到化合物IIIa单晶生成。The preparation method of Compound IIIa single crystal: 100 mg of Compound IIIa was dissolved in 5 mL of CH ₂ Cl ₂ , and then n-hexane (2 mL) was added dropwise thereto until just turbid. Then add a drop of CH ₂ Cl ₂ to it, and dissolve the formed precipitate again. The solution was left standing in a -30°C refrigerator until compound IIIa single crystals formed.

晶体数据：在使用辐射源为Cu-Kα的单晶X射线衍射光谱中，晶体属单斜系，空间群为P21，其晶胞参数：α＝90°Crystal data: In the single crystal X-ray diffraction spectrum using the radiation source Cu-Kα, the crystal belongs to the monoclinic system, the space group is P21, and its unit cell parameters are: α=90°

β＝92.5300(10)° β=92.5300(10)°

γ＝90° γ=90°

晶胞体积晶胞内不对称单位数Z＝2。unit cell volume The number of asymmetric units in the unit cell is Z=2.

化合物IIIbCompound IIIb

黄色固体，收率：63％.(纯度>97％，核磁纯度)Yellow solid, yield: 63%. (purity>97%, NMR purity)

MS(ESI⁺):621(C₂₅H₃₅ClIrN₃O[M⁺]).MS(ESI ⁺ ):621(C ₂₅ H ₃₅ ClIrN ₃ O[M ⁺ ]).

化合物IIIcCompound IIIc

MS(ESI⁺):715(C₂₄H₂₇ClF₆IrN₃O[M⁺]).MS(ESI ⁺ ):715(C ₂₄ H ₂₇ ClF ₆ IrN ₃ O[M ⁺ ]).

化合物IIIdCompound IIId

MS(ESI⁺):609(C₂₃H₃₁ClF₆IrN₃O₂[M⁺]).MS(ESI ⁺ ):609(C ₂₃ H ₃₁ ClF ₆ IrN ₃ O ₂ [M ⁺ ]).

化合物IIIeCompound IIIe

黄色固体，收率：62％.(纯度>97％，核磁纯度)Yellow solid, yield: 62%. (purity>97%, NMR purity)

MS(ESI⁺):669(C₂₂H₂₄ClF₅IrN₃O[M⁺]).MS(ESI ⁺ ):669(C ₂₂ H ₂₄ ClF ₅ IrN ₃ O[M ⁺ ]).

化合物IIIfCompound IIIf

MS(ESI⁺):665(C₂₃H₂₇F₅IrN₃O[M⁺]).MS(ESI ⁺ ):665(C ₂₃ H ₂₇ F ₅ IrN ₃ O[M ⁺ ]).

实施例4通式IV所示的金属铱络合物的合成The synthesis of the metal iridium complex shown in embodiment 4 general formula IV

氩气保护下，在一个干燥的250毫升三口瓶中，加入[Ir(cod)X^1c]₂(336mg,0.5mmol)，如式d所示的化合物和碱，有机溶剂，搅拌反应，粗产物通过柱层析分离(乙酸乙酯/石油醚:1:5)。化合物IVa-IVc和化合物IVf的具体反应条件参见表4。化合物IVd-IVe，化合物IVg-IVi的制备方法和条件参照实施例4和表4，其中，表4中的摩尔比是指[Ir(cod)X^1c]₂：化合物d：碱的摩尔比。Under the protection of argon, in a dry 250ml three-necked flask, add [Ir(cod)X ^1c ] ₂ (336mg, 0.5mmol), the compound shown in formula d and base, organic solvent, stir the reaction, the crude product Separation by column chromatography (ethyl acetate/petroleum ether: 1:5). See Table 4 for the specific reaction conditions of compounds IVa-IVc and compound IVf. The preparation methods and conditions of compounds IVd-IVe, compounds IVg-IVi refer to Example 4 and Table 4, wherein the molar ratio in Table 4 refers to the molar ratio of [Ir(cod)X ^1c ] ₂ :compound d:base.

表4Table 4

化合物VIaCompound VIa

MS(ESI⁺):821(C₃₈H₅₁ClIrN₃OSi[M⁺]).MS(ESI ⁺ ):821(C ₃₈ H ₅₁ ClIrN ₃ OSi[M ⁺ ]).

化合物VIbCompound VIb

MS(ESI⁺):863(C₄₁H₅₇ClIrN₃OSi[M⁺]).MS(ESI ⁺ ):863(C ₄₁ H ₅₇ ClIrN ₃ OSi[M ⁺ ]).

化合物VIcCompound VIc

MS(ESI⁺):957(C₄₀H₄₉ClF₆IrN₃OSi[M⁺]).MS(ESI ⁺ ):957(C ₄₀ H ₄₉ ClF ₆ IrN ₃ OSi[M ⁺ ]).

化合物VIdCompound VId

MS(ESI⁺):851(C₃₉H₅₃ClIrN₃O₂Si[M⁺]).MS(ESI ⁺ ):851(C ₃₉ H ₅₃ ClIrN ₃ O ₂ Si[M ⁺ ]).

化合物VIeCompound VIe

MS(ESI⁺):911(C₃₈H₄₆ClF₅IrN₃OSi[M⁺]).MS (ESI ⁺ ): 911 (C ₃₈ H ₄₆ ClF ₅ IrN ₃ OSi[M ⁺ ]).

化合物VIfCompound VIf

黄色固体，收率：53％.(纯度，>97％，核磁纯度)Yellow solid, yield: 53%. (purity, >97%, NMR purity)

MS(ESI⁺):817(C₃₉H₅₄ClIrN₃O₂Si[M⁺]).MS(ESI ⁺ ):817(C ₃₉ H ₅₄ ClIrN ₃ O ₂ Si[M ⁺ ]).

化合物VIgCompound VIg

MS(ESI⁺):859(C₄₂H₆₀ClIrN₃O₂Si[M⁺]).MS(ESI ⁺ ):859(C ₄₂ H ₆₀ ClIrN ₃ O ₂ Si[M ⁺ ]).

化合物VIhCompound VIh

MS(ESI⁺):641(C₂₆H₄₀ClFIrN₃O₂[M⁺]).MS (ESI ⁺ ): 641 (C ₂₆ H ₄₀ ClFIrN ₃ O ₂ [M ⁺ ]).

化合物VIiCompound VIi

实施例5如式V所示的金属铱络合物的合成Embodiment 5 is as the synthesis of the metal iridium complex compound shown in formula V

氩气保护下，在一个干燥的250毫升三口瓶中，加入[Ir(cod)X^1d]₂(336mg,0.5mmol)，如式e所示的化合物和碱，有机溶剂，搅拌反应，粗产物通过柱层析分离(乙酸乙酯/石油醚:1:5)。化合物Va-Vc和化合物Vf的具体反应条件参见表5。化合物Vd-Ve，化合物Vg的制备方法和条件参照实施例5和表5，其中，表5中的摩尔比是指[Ir(cod)X^1d]₂：化合物e：碱的摩尔比。Under the protection of argon, in a dry 250ml three-necked flask, add [Ir(cod)X ^1d ] ₂ (336mg, 0.5mmol), the compound shown in formula e and base, organic solvent, stirring reaction, crude product Separation by column chromatography (ethyl acetate/petroleum ether: 1:5). See Table 5 for the specific reaction conditions of compounds Va-Vc and compound Vf. The preparation methods and conditions of compound Vd-Ve and compound Vg refer to Example 5 and Table 5, wherein the molar ratio in Table 5 refers to the molar ratio of [Ir(cod)X ^1d ] ₂ :compound e:base.

表5table 5

化合物VaCompound Va

MS(ESI⁺):659(C₂₈H₃₇ClIrN₃O[M⁺]).MS(ESI ⁺ ):659(C ₂₈ H ₃₇ ClIrN ₃ O[M ⁺ ]).

化合物VbCompound Vb

MS(ESI⁺):701(C₃₁H₄₁ClIrN₃O[M⁺]).MS(ESI ⁺ ):701(C ₃₁ H ₄₁ ClIrN ₃ O[M ⁺ ]).

化合物VcCompound Vc

MS(ESI⁺):795(C₃₀H₃₅ClF₆IrN₃O[M⁺]).MS(ESI ⁺ ):795(C ₃₀ H ₃₅ ClF ₆ IrN ₃ O[M ⁺ ]).

化合物VdCompound Vd

MS(ESI⁺):689(C₂₉H₃₉ClIrN₃O₂[M⁺]).MS(ESI ⁺ ):689(C ₂₉ H ₃₉ ClIrN ₃ O ₂ [M ⁺ ]).

化合物VeCompound Ve

MS(ESI⁺):749(C₂₈H₃₂ClF₅IrN₃O[M⁺]).MS(ESI ⁺ ):749(C ₂₈ H ₃₂ ClF ₅ IrN ₃ O[M ⁺ ]).

化合物VfCompound Vf

MS(ESI⁺):655(C₂₉H₄₀IrN₃O₂[M⁺]).MS(ESI ⁺ ):655(C ₂₉ H ₄₀ IrN ₃ O ₂ [M ⁺ ]).

化合物VgCompound Vg

MS(ESI⁺):595(C₂₃H₃₃IrN₃O[M⁺]).MS(ESI ⁺ ):595(C ₂₃ H ₃₃ IrN ₃ O[M ⁺ ]).

实施例6通式VI所示的金属铱络合物的合成The synthesis of the metal iridium complex shown in embodiment 6 general formula VI

氩气保护下，在一个干燥的250毫升三口瓶中，加入[Ir(cod)X^1e]₂(336mg,0.5mmol)，如式f所示的化合物和碱，有机溶剂，搅拌下反应，粗产物通过柱层析分离(乙酸乙酯/石油醚:1:5)。化合物VIa-VIc和化合物VIf的具体反应条件参见表6。化合物VId-VIe的制备方法和条件参照实施例6和表6，其中，表6中的摩尔比是指[Ir(cod)X^1e]₂：化合物f：碱的摩尔比。Under the protection of argon, in a dry 250ml three-necked flask, add [Ir(cod)X ^1e ] ₂ (336mg, 0.5mmol), the compound shown in formula f and base, organic solvent, react under stirring, crude The product was isolated by column chromatography (ethyl acetate/petroleum ether: 1:5). See Table 6 for the specific reaction conditions of compounds VIa-VIc and compound VIf. The preparation methods and conditions of compounds VId-VIe refer to Example 6 and Table 6, wherein the molar ratio in Table 6 refers to the molar ratio of [Ir(cod)X ^1e ] ₂ : compound f: base.

表6Table 6

化合物VIaCompound VIa

MS(ESI⁺):671(C₂₉H₃₇ClIrN₃O[M⁺]).MS(ESI ⁺ ):671(C ₂₉ H ₃₇ ClIrN ₃ O[M ⁺ ]).

化合物VIbCompound VIb

橘黄色固体，收率：51％.(纯度>97％，核磁纯度)Orange solid, yield: 51%. (purity>97%, NMR purity)

¹H NMR(400MHz,CD₂Cl₂)δ8.43(d,J＝6.0Hz,1H),7.36-7.32(m,3H),7.07(s,1H),6.95(s,1H),6.91(d,J＝3.2Hz,1H),4.92(AB,J_AB＝16.0Hz,1H),4.83(AB,J_AB＝16.0Hz,1H),4.74-4.73(m,1H),4.60-4.58(m,1H),4.47-4.43(m,1H),3.34(dd,J＝4.0,16.8Hz,1H),3.23-3.15(m,2H),2.85(t,J＝6.8Hz,1H),2.37(s,6H),2.27-2.18(m,1H),2.15-2.08(m,1H),1.88(s,3H),1.88-1.86(m,1H),1.69-1.63(m,1H),1.54-1.48(m,3H),1.40-1.38(m,1H). ¹ H NMR (400MHz, CD ₂ Cl ₂ ) δ8.43(d, J=6.0Hz, 1H), 7.36-7.32(m, 3H), 7.07(s, 1H), 6.95(s, 1H), 6.91( d, J＝3.2Hz, 1H), 4.92(AB, J _AB ＝16.0Hz, 1H), 4.83(AB, J _AB ＝16.0Hz, 1H), 4.74-4.73(m, 1H), 4.60-4.58(m ,1H),4.47-4.43(m,1H),3.34(dd,J=4.0,16.8Hz,1H),3.23-3.15(m,2H),2.85(t,J=6.8Hz,1H),2.37( s,6H),2.27-2.18(m,1H),2.15-2.08(m,1H),1.88(s,3H),1.88-1.86(m,1H),1.69-1.63(m,1H),1.54- 1.48(m,3H),1.40-1.38(m,1H).

¹³C NMR(100MHz,CD₂Cl₂)δ182.1,148.4,140.8,140.1,139.5,136.9,136.7,136.1,129.6,128.9,128.6,126.9,126.0,125.6,87.4,84.6,79.0,62.4,61.2,56.5,52.7,37.7,34.6,33.0,30.3,28.1,21.3,19.7,17.9. ¹³ C NMR (100MHz, CD ₂ Cl ₂ ) δ182.1, 148.4, 140.8, 140.1, 139.5, 136.9, 136.7, 136.1, 129.6, 128.9, 128.6, 126.9, 126.0, 125.6, 87.4, 84.5, 79.6, 62.4, 6 ,52.7,37.7,34.6,33.0,30.3,28.1,21.3,19.7,17.9.

化合物VIcCompound VIc

MS(ESI⁺):807(C₃₁H₃₅ClF₆IrN₃O[M⁺]).MS(ESI ⁺ ):807(C ₃₁ H ₃₅ ClF ₆ IrN ₃ O[M ⁺ ]).

化合物VIdCompound VId

黄色固体，收率59％.(纯度>97％，核磁纯度)Yellow solid, yield 59%. (purity>97%, NMR purity)

MS(ESI⁺):701(C₃₀H₃₉ClF₆IrN₃O[M⁺]).MS(ESI ⁺ ):701(C ₃₀ H ₃₉ ClF ₆ IrN ₃ O[M ⁺ ]).

化合物VIeCompound VIe

¹³C NMR(100MHz,DMSO-d₆)δ187.8,149.9,140.8,138.5,128.6,126.6,126.5,125.0,87.8,86.2,78.2,62.0,59.7,54.5,52.9,36.9,33.4,33.0,28.9,28.7,27.6；¹⁹F NMR(376MHz,DMSO-d₆)δ-138.6(d,J＝23.3Hz),-144.6(d,J＝24.8Hz),-150.3(t,J＝22.6Hz),-161.9(t,J＝23.7Hz),-162.6(t,J＝23.3Hz). ¹³ C NMR (100MHz, DMSO-d ₆ ) δ187.8, 149.9, 140.8, 138.5, 128.6, 126.6, 126.5, 125.0, 87.8, 86.2, 78.2, 62.0, 59.7, 54.5, 52.9, 36.9, 33.4, 33.0, 28.9, 28. ,27.6; ¹⁹ F NMR (376MHz, DMSO-d ₆ )δ-138.6(d, J=23.3Hz),-144.6(d,J=24.8Hz),-150.3(t,J=22.6Hz),-161.9 (t, J=23.7Hz), -162.6(t, J=23.3Hz).

化合物VIfCompound VIf

MS(ESI⁺):684(C₃₁H₄₅IrN₃O₂[M⁺]).MS(ESI ⁺ ):684(C ₃₁ H ₄₅ IrN ₃ O ₂ [M ⁺ ]).

效果实施例1通式P所示的化合物的合成Synthesis of the compound shown in effect embodiment 1 general formula P

一般反应操作：氩气保护下，往Schlenk管中加入底物S1(75.6mg,0.2mmol)，金属依络合物催化剂(3.2mg,0.01mmol,5mol％)和碱(3.0mg,0.02mmol)于2.0mL二氯甲烷(CH₂Cl₂)中，室温下搅拌反应6小时。TLC跟踪反应完全后，用硅藻土过滤，减压除去溶剂，柱层析提纯(石油醚/乙酸乙酯＝5/1)。产物的ee由HPLC测定。其中，底物S1、催化剂、碱等条件具体见表7，表7中的摩尔比是指S1：碱：催化剂的摩尔比。表7中，摩尔比是指摩尔比是指S1：碱：催化剂的摩尔比。General reaction procedure: Under the protection of argon, add substrate S1 (75.6mg, 0.2mmol), metal complex catalyst (3.2mg, 0.01mmol, 5mol%) and base (3.0mg, 0.02mmol) into a Schlenk tube In 2.0 mL of dichloromethane (CH ₂ Cl ₂ ), the reaction was stirred at room temperature for 6 hours. After the completion of the reaction traced by TLC, filter with celite, remove the solvent under reduced pressure, and purify by column chromatography (petroleum ether/ethyl acetate=5/1). The ee of the product was determined by HPLC. Wherein, conditions such as substrate S1, catalyst, and base are specifically shown in Table 7, and the molar ratio in Table 7 refers to the molar ratio of S1:base:catalyst. In Table 7, the molar ratio refers to the molar ratio of S1:base:catalyst.

表7Table 7

化合物P1Compound P1

浅黄色油状物，收率：81％，ee值为92％[Daicel Chiralcel OD-H,正己烷(hexane)/2-丙醇(2-propanol)＝90/10,v＝1.0ml·min^-1,λ＝254nm,t(minor)＝20.38min,t(major)＝31.75min].Pale yellow oil, yield: 81%, ee value: 92% [Daicel Chiralcel OD-H, n-hexane (hexane)/2-propanol (2-propanol) = 90/10, v = 1.0ml·min ^{- 1} ,λ=254nm,t(minor)=20.38min,t(major)=31.75min].

[α]_D ²⁰+6.4(c1.00,CH₂Cl₂).[α] _D ²⁰ +6.4(c1.00, CH ₂ Cl ₂ ).

¹H NMR(300MHz,CDCl₃)δ3.43(d,J＝12.6Hz,1H),3.93(dd,J＝12.6,4.5Hz,1H),4.54-4.68(m,2H),4.87-5.00(m,2H),5.08(d,J＝10.5Hz,1H),5.73(ddd,J＝16.8,10.2,5.4Hz,1H),7.15(t,J＝6.9Hz,1H),7.21-7.38(m,8H),7.72(d,J＝7.8Hz,1H). ¹ H NMR (300MHz, CDCl ₃ ) δ3.43 (d, J = 12.6Hz, 1H), 3.93 (dd, J = 12.6, 4.5Hz, 1H), 4.54-4.68 (m, 2H), 4.87-5.00 ( m, 2H), 5.08(d, J=10.5Hz, 1H), 5.73(ddd, J=16.8, 10.2, 5.4Hz, 1H), 7.15(t, J=6.9Hz, 1H), 7.21-7.38(m ,8H),7.72(d,J=7.8Hz,1H).

化合物P2Compound P2

黄色固体，收率：77％，ee值为91％[Daicel ChiralpakAD-H,正己烷(hexane)/2-丙醇(2-propanol)＝80/20,v＝1.0ml·min^-1,λ＝254nm,t(major)＝26.51min,t(minor)＝33.90min].Yellow solid, yield: 77%, ee value: 91% [Daicel ChiralpakAD-H, n-hexane (hexane)/2-propanol (2-propanol) = 80/20, v = 1.0ml·min ^-1 ,λ =254nm,t(major)=26.51min,t(minor)=33.90min].

[α]_D ¹⁶+8.7(c1.00,CH₂Cl₂).[α] _D ¹⁶ +8.7(c1.00, CH ₂ Cl ₂ ).

¹H NMR(300MHz,CDCl₃)δ3.45(dd,J＝12.6,2.1Hz,1H),3.94(dd,J＝12.9,5.1Hz,1H),4.57(d,J＝16.8Hz,2H),4.59(d,J＝14.7Hz,2H),5.10(d,J＝9.9Hz,1H),5.70(ddd,J＝16.8,10.5,5.4Hz,1H),7.12(d,J＝9.0Hz,1H),7.24-7.40(m,7H),7.85(s,1H)；¹³C NMR(75MHz,CDCl₃)δ49.4,49.5,53.0,105.8,111.5,113.9,118.3,125.0,127.5,127.8,128.5,128.6,128.9,129.6,133.5,134.7,136.1,159.3. ¹ H NMR (300MHz, CDCl ₃ ) δ3.45 (dd, J=12.6, 2.1Hz, 1H), 3.94 (dd, J=12.9, 5.1Hz, 1H), 4.57 (d, J=16.8Hz, 2H) ,4.59(d,J=14.7Hz,2H),5.10(d,J=9.9Hz,1H),5.70(ddd,J=16.8,10.5,5.4Hz,1H),7.12(d,J=9.0Hz, 1H),7.24-7.40(m,7H),7.85(s,1H); ¹³ C NMR(75MHz,CDCl ₃ )δ49.4,49.5,53.0,105.8,111.5,113.9,118.3,125.0,127.5,127.8, 128.5, 128.6, 128.9, 129.6, 133.5, 134.7, 136.1, 159.3.

IR(薄膜):ν_max(cm^-1)＝3064,1639,1547,1448,1429,1251,1173,933,802,732,697.IR (thin film): ν _max (cm ^-1 )＝3064,1639,1547,1448,1429,1251,1173,933,802,732,697.

HRMS-ESI计算值(Calcd for)C₂₀H₁₈BrN₂O(M⁺+H):381.0597.实验值(Found):381.0599.HRMS-ESI calculated value (Calcd for) C ₂₀ H ₁₈ BrN ₂ O (M ⁺ +H): 381.0597. Experimental value (Found): 381.0599.

m.p.＝135-136℃.m.p.=135-136°C.

化合物P3Compound P3

浅黄色油状物，收率：78％，ee值为92％[Daicel ChiralpakAD-H,正己烷(hexane)/2-丙醇(2-propanol)＝80/20,v＝1.0ml·min^-1,λ＝254nm,t(major)＝17.92min,t(minor)＝24.91min].Pale yellow oil, yield: 78%, ee value 92% [Daicel ChiralpakAD-H, n-hexane (hexane)/2-propanol (2-propanol) = 80/20, v = 1.0ml·min ^-1 ,λ=254nm,t(major)=17.92min,t(minor)=24.91min].

[α]_D ¹⁷+12.3(c1.00,CH₂Cl₂).[α] _D ¹⁷ +12.3(c1.00, CH ₂ Cl ₂ ).

¹H NMR(300MHz,CDCl₃)δ3.45(d,J＝13.2Hz,1H),3.93(dd,J＝13.2,4.8Hz,1H),4.60(d,J＝14.7Hz,1H),4.62(d,J＝17.1Hz,1H),4.83-4.99(m,2H),5.12(d,J＝10.5Hz,1H),5.72(ddd,J＝15.6,9.9,5.1Hz,1H),7.12(d,J＝8.7Hz,1H),7.25(s,1H),7.27-7.38(m,6H),7.63(d,J＝8.4Hz,1H)；¹³C NMR(75MHz,CDCl₃)δ49.5,49.6,53.0,106.7,110.0,118.4,121.7,123.6,125.9,127.8,128.5,128.6,129.3,130.5,133.4,136.1,136.4,159.5. ¹ H NMR (300MHz, CDCl ₃ ) δ3.45 (d, J=13.2Hz, 1H), 3.93 (dd, J=13.2, 4.8Hz, 1H), 4.60 (d, J=14.7Hz, 1H), 4.62 (d,J=17.1Hz,1H),4.83-4.99(m,2H),5.12(d,J=10.5Hz,1H),5.72(ddd,J=15.6,9.9,5.1Hz,1H),7.12( d, J＝8.7Hz, 1H), 7.25(s, 1H), 7.27-7.38(m, 6H), 7.63(d, J＝8.4Hz, 1H); ¹³ C NMR (75MHz, CDCl ₃ ) δ49.5 ,49.6,53.0,106.7,110.0,118.4,121.7,123.6,125.9,127.8,128.5,128.6,129.3,130.5,133.4,136.1,136.4,159.5.

IR(薄膜):ν_max(cm^-1)＝2918,2850,1652,1645,1564,1471,1347,1057,951,735,700.IR (thin film):ν _max (cm ^-1 )＝2918,2850,1652,1645,1564,1471,1347,1057,951,735,700.

HRMS-ESI计算值(Calcd for)C₂₀H₁₈ClN₂O(M⁺+H):337.1102.实验值(Found):337.1104.HRMS-ESI calculated value (Calcd for) C ₂₀ H ₁₈ ClN ₂ O (M ⁺ +H): 337.1102. Experimental value (Found): 337.1104.

化合物P4Compound P4

黄色固体，收率：84％，ee值为89％[Daicel ChiralpakAD-H,正己烷(hexane)/2-丙醇(2-propanol)＝80/20,v＝1.0ml·min^-1,λ＝254nm,t(major)＝20.09min,t(minor)＝25.97min].Yellow solid, yield: 84%, ee value 89% [Daicel ChiralpakAD-H, n-hexane (hexane)/2-propanol (2-propanol) = 80/20, v = 1.0ml·min ^-1 ,λ =254nm,t(major)=20.09min,t(minor)=25.97min].

[α]_D ¹⁷+3.1(c1.00,CH₂Cl₂).[α] _D ¹⁷ +3.1(c1.00, CH ₂ Cl ₂ ).

¹H NMR(400MHz,CDCl₃)δ3.44(d,J＝12.0,1.6Hz,1H),3.92(dd,J＝12.8,4.4Hz,1H),4.57-4.64(m,2H),4.89-4.96(m,2H),5.09(d,J＝10.4Hz,1H),5.72(ddd,J＝16.8,10.4,5.2Hz,1H),7.03(dt,J＝8.8,2.4Hz,1H),7.17(dd,J＝9.2,4.4Hz,1H),7.24-7.36(m,7H). ¹ H NMR (400MHz, CDCl ₃ ) δ3.44 (d, J=12.0, 1.6Hz, 1H), 3.92 (dd, J=12.8, 4.4Hz, 1H), 4.57-4.64 (m, 2H), 4.89- 4.96(m,2H),5.09(d,J=10.4Hz,1H),5.72(ddd,J=16.8,10.4,5.2Hz,1H),7.03(dt,J=8.8,2.4Hz,1H),7.17 (dd,J=9.2,4.4Hz,1H),7.24-7.36(m,7H).

¹³C NMR(75MHz,CDCl₃)δ49.5,49.6,53.1,106.2,106.3,106.8,107.1,110.9,113.6,118.2,127.5,127.6,127.7,128.4,128.6,130.1,132.8,133.7,136.2,156.9,159.3,159.4. ¹³ C NMR (75MHz, CDCl ₃ ) δ49.5, 49.6, 53.1, 106.2, 106.3, 106.8, 107.1, 110.9, 113.6, 118.2, 127.5, 127.6, 127.7, 128.4, 128.6, 130.1, 132.8, 1392.7, 156.6 ,159.3,159.4.

IR(薄膜):ν_max(cm^-1)＝3030,2922,1640,1549,1496,1466,1361,1250,1189,928,800,735.IR (thin film): ν _max (cm ^-1 ) = 3030, 2922, 1640, 1549, 1496, 1466, 1361, 1250, 1189, 928, 800, 735.

HRMS-ESI计算值(Calcd for)C₂₀H₁₈FN₂O(M⁺+H):321.1398.实验值(Found):321.1398.HRMS-ESI calculated value (Calcd for) C ₂₀ H ₁₈ FN ₂ O (M ⁺ +H): 321.1398. Experimental value (Found): 321.1398.

m.p.＝127-128℃.m.p.＝127-128℃.

化合物P5Compound P5

黄色固体，收率：86％，ee值为93％[Daicel ChiralpakAD-H,正己烷(hexane)/2-丙醇(2-propanol)＝80/20,v＝1.0ml·min^-1,λ＝230nm,t(major)＝24.02min,t(minor)＝29.46min].Yellow solid, yield: 86%, ee value: 93% [Daicel ChiralpakAD-H, n-hexane (hexane)/2-propanol (2-propanol) = 80/20, v = 1.0ml·min ^-1 ,λ =230nm,t(major)=24.02min,t(minor)=29.46min].

[α]_D ²¹+7.0(c1.00,CH₂Cl₂).[α] _D ²¹ +7.0(c1.00, CH ₂ Cl ₂ ).

¹H NMR(400MHz,CDCl₃)δ2.43(s,3H),3.42(dd,J＝12.4,2.0Hz,1H),3.92(dd,J＝12.8,4.8Hz,1H),4.57-4.64(m,2H),4.89-4.97(m,2H),5.09(d,J＝10.4Hz,1H),5.72(ddd,J＝15.6,10.0,5.2Hz,1H),7.09-7.16(m,2H),7.24-7.36(m,6H),7.50(s,1H). ¹ H NMR (400MHz, CDCl ₃ ) δ2.43(s, 3H), 3.42(dd, J=12.4, 2.0Hz, 1H), 3.92(dd, J=12.8, 4.8Hz, 1H), 4.57-4.64( m,2H),4.89-4.97(m,2H),5.09(d,J=10.4Hz,1H),5.72(ddd,J=15.6,10.0,5.2Hz,1H),7.09-7.16(m,2H) ,7.24-7.36(m,6H),7.50(s,1H).

¹³C NMR(75MHz,CDCl₃)δ21.4,49.5,49.7,52.9,106.1,109.7,118.0,122.1,126.5,127.6,127.7,128.4,128.5,128.6,130.1,133.9,134.7,136.4,159.9. ¹³ C NMR (75MHz, CDCl ₃ ) δ21.4, 49.5, 49.7, 52.9, 106.1, 109.7, 118.0, 122.1, 126.5, 127.6, 127.7, 128.4, 128.5, 128.6, 130.1, 133.9, 134.7, 136.4, 159.9

IR(薄膜):ν_max(cm^-1)＝3053,2919,1635,1549,1428,1357,1253,1184,934,809,737,697.IR (thin film):ν _max (cm ^-1 )＝3053,2919,1635,1549,1428,1357,1253,1184,934,809,737,697.

HRMS-ESI计算值(Calcd for)C₂₁H₂₁N₂O(M⁺+H):317.1648.实验值(Found):317.1652.HRMS-ESI calculated value (Calcd for) C ₂₁ H ₂₁ N ₂ O (M ⁺ +H): 317.1648. Experimental value (Found): 317.1652.

m.p.＝142-143℃.m.p.=142-143°C.

化合物P6Compound P6

白色固体，收率：87％，ee值为94％[Daicel ChiralpakAD-H,正己烷(hexane)/2-丙醇(2-propanol)＝80/20,v＝1.0ml·min^-1,λ＝230nm,t(major)＝28.39min,t(minor)＝45.66min].White solid, yield: 87%, ee value 94% [Daicel ChiralpakAD-H, n-hexane (hexane)/2-propanol (2-propanol) = 80/20, v = 1.0ml·min ^-1 ,λ =230nm,t(major)=28.39min,t(minor)=45.66min].

[α]_D ²⁰+3.8(c1.00,CH₂Cl₂).[α] _D ²⁰ +3.8(c1.00, CH ₂ Cl ₂ ).

¹H NMR(400MHz,CDCl₃)δ3.42(dd,J＝12.4,2.0Hz,1H),3.84(s,3H),3.92(dd,J＝12.4,4.8Hz,1H),4.61(d,J＝14.8Hz,1H),4.62(d,J＝16.8Hz,1H),4.87-4.96(m,2H),5.08(d,J＝10.4Hz,1H),5.72(ddd,J＝15.6,10.4,5.2Hz,1H),6.96(dd,J＝9.2,3.2Hz,1H),7.10-7.16(m,2H),7.24-7.34(m,6H). ¹ H NMR (400MHz, CDCl ₃ ) δ3.42(dd, J=12.4, 2.0Hz, 1H), 3.84(s, 3H), 3.92(dd, J=12.4, 4.8Hz, 1H), 4.61(d, J=14.8Hz, 1H), 4.62(d, J=16.8Hz, 1H), 4.87-4.96(m, 2H), 5.08(d, J=10.4Hz, 1H), 5.72(ddd, J=15.6, 10.4 ,5.2Hz,1H),6.96(dd,J=9.2,3.2Hz,1H),7.10-7.16(m,2H),7.24-7.34(m,6H).

¹³C NMR(75MHz,CDCl₃)δ49.4,49.7,53.1,55.6,102.8,106.1,110.9,116.0,118.0,127.6,127.8,128.4,128.6,129.0,131.6,134.0,136.4,154.7,159.8. ¹³ C NMR (75MHz, CDCl ₃ ) δ49.4, 49.7, 53.1, 55.6, 102.8, 106.1, 110.9, 116.0, 118.0, 127.6, 127.8, 128.4, 128.6, 129.0, 131.6, 134.0, 136.4, 154.7, 159.8

IR(薄膜):ν_max(cm^-1)＝3065,2935,1633,1545,1358,1230,1215,1034,834,813,703.IR (thin film):ν _max (cm ^-1 )＝3065,2935,1633,1545,1358,1230,1215,1034,834,813,703.

HRMS-ESI计算值(Calcd for)C₂₁H₂₁N₂O₂(M⁺+H):333.1598.实验值(Found):333.1600.HRMS-ESI calculated value (Calcd for) C ₂₁ H ₂₁ N ₂ O ₂ (M ⁺ +H): 333.1598. Experimental value (Found): 333.1600.

m.p.＝148-149℃.m.p.=148-149°C.

化合物P7Compound P7

无色油状物，收率：75％，ee值为92％[Daicel ChiralpakAD-H,正己烷(hexane)/2-丙醇(2-propanol)＝80/20,v＝1.0ml·min^-1,λ＝230nm,t(major)＝18.96min,t(minor)＝24.65min].Colorless oil, yield: 75%, ee value 92% [Daicel ChiralpakAD-H, n-hexane (hexane)/2-propanol (2-propanol) = 80/20, v = 1.0ml·min ^-1 ,λ=230nm,t(major)=18.96min,t(minor)=24.65min].

[α]_D ¹⁶+16.2(c1.00,CH₂Cl₂).[α] _D ¹⁶ +16.2(c1.00, CH ₂ Cl ₂ ).

¹H NMR(400MHz,CDCl₃)δ3.44(d,J＝12.9Hz,1H),3.92(dd,J＝12.6,4.5Hz,1H),4.59(d,J＝14.7Hz,1H),4.61(d,J＝16.8Hz,1H),4.85-4.98(m,2H),5.12(d,J＝10.8Hz,1H),5.71(ddd,J＝16.2,10.2,5.1Hz,1H),7.20-7.38(m,7H),7.41(s,1H),7.57(d,J＝8.4Hz,1H). ¹ H NMR (400MHz, CDCl ₃ ) δ3.44 (d, J=12.9Hz, 1H), 3.92 (dd, J=12.6, 4.5Hz, 1H), 4.59 (d, J=14.7Hz, 1H), 4.61 (d,J=16.8Hz,1H),4.85-4.98(m,2H),5.12(d,J=10.8Hz,1H),5.71(ddd,J=16.2,10.2,5.1Hz,1H),7.20- 7.38(m,7H),7.41(s,1H),7.57(d,J=8.4Hz,1H).

¹³C NMR(100MHz，CDCl₃)δ49.5，49.6，53.0，106.7，113.0，118.3，118.4，123.9，124.2，126.2,127.8,128.5,128.6,129.2,133.4,136.1,136.8,159.4. ¹³ C NMR (100MHz, CDCl ₃ ) δ49.5, 49.6, 53.0, 106.7, 113.0, 118.3, 118.4, 123.9, 124.2, 126.2, 127.8, 128.5, 128.6, 129.2, 133.4, 136.1, 136.8, 159.4.

IR(薄膜):ν_max(cm^-1)＝3080,2925,1644,1545,1494,1430,1355,1270,1149,928,821,744；HRMS-ESI计算值(Calcd for)C₂₀H₁₈BrN₂O(M⁺+H):381.0597.实验值(Found):381.0599.IR (thin film): ν _max (cm ^-1 ) = 3080, 2925, 1644, 1545, 1494, 1430, 1355, 1270, 1149, 928, 821, 744; HRMS-ESI calculated value (Calcd for) C ₂₀ H ₁₈ BrN ₂ O( M ⁺ +H): 381.0597. Experimental value (Found): 381.0599.

化合物P8Compound P8

黄色固体，收率：75％，ee值为91％[Daicel ChiralpakAD-H,正己烷(hexane)/2-丙醇(2-propanol)＝80/20,v＝1.0ml·min^-1,λ＝230nm,t(major)＝23.53min,t(minor)＝29.22min]；[α]_D ²⁶+10.2(c1.00,CH₂Cl₂).Yellow solid, yield: 75%, ee value: 91% [Daicel ChiralpakAD-H, n-hexane (hexane)/2-propanol (2-propanol) = 80/20, v = 1.0ml·min ^-1 ,λ =230nm, t(major)=23.53min, t(minor)=29.22min]; [α] _D ²⁶ +10.2(c1.00, CH ₂ Cl ₂ ).

¹H NMR(400MHz,CDCl₃)δ3.45(dd,J＝12.6,1.8Hz,1H),3.94(dd,J＝12.9,5.1Hz,1H),4.53-4.64(m,2H),4.89-4.98(m,2H),5.10(d,J＝9.9Hz,1H),5.71(ddd,J＝15.6,10.5,5.4Hz,1H),7.13-7.19(m,1H),7.20-7.38(m,7H),7.68(s,1H). ¹ H NMR (400MHz, CDCl ₃ ) δ3.45 (dd, J = 12.6, 1.8Hz, 1H), 3.94 (dd, J = 12.9, 5.1Hz, 1H), 4.53-4.64 (m, 2H), 4.89- 4.98(m,2H),5.10(d,J=9.9Hz,1H),5.71(ddd,J=15.6,10.5,5.4Hz,1H),7.13-7.19(m,1H),7.20-7.38(m, 7H), 7.68(s, 1H).

¹³C NMR(75MHz,CDCl₃)δ49.5,49.6,53.0,105.9,111.1,118.3,121.9,125.0,126.4,127.8,128.2,128.5,128.6,129.8,133.5,134.4,136.1,159.4. ¹³ C NMR (75MHz, CDCl ₃ ) δ49.5, 49.6, 53.0, 105.9, 111.1, 118.3, 121.9, 125.0, 126.4, 127.8, 128.2, 128.5, 128.6, 129.8, 133.5, 134.4, 136.1, 159.4.

IR(薄膜):ν_max(cm^-1)＝3086,2924,1649,1548,1474,1420,1250,1061,919,801,745.IR (thin film): ν _max (cm ^-1 ) = 3086, 2924, 1649, 1548, 1474, 1420, 1250, 1061, 919, 801, 745.

HRMS-ESI计算值(Calcd for)C₂₀H₁₈ClN₂O(M⁺+H):337.1102.实验值(Found):337.1108.m.p.＝127-128℃.HRMS-ESI calculated value (Calcd for) C ₂₀ H ₁₈ ClN ₂ O (M ⁺ +H): 337.1102. Experimental value (Found): 337.1108.mp＝127-128℃.

化合物P9：Compound P9:

黄色油状物，收率：89％，ee值为89％[Daicel ChiralpakAD-H,正己烷(hexane)/2-丙醇(2-propanol)＝80/20,v＝1.0ml·min^-1,λ＝230nm,t(major)＝14.51min,t(minor)＝19.40min].Yellow oil, yield: 89%, ee value 89% [Daicel ChiralpakAD-H, n-hexane (hexane)/2-propanol (2-propanol) = 80/20, v = 1.0ml·min ^-1 , λ=230nm, t(major)=14.51min, t(minor)=19.40min].

[α]_D ²⁵+21.9(c1.00,CH₂Cl₂).[α] _D ²⁵ +21.9(c1.00, CH ₂ Cl ₂ ).

¹H NMR(400MHz,CDCl₃)δ3.42(dd,J＝12.9,2.1Hz,1H),3.83(s,3H),3.92(dd,J＝12.6,4.5Hz,1H),4.59(d,J＝15.0Hz,1H),4.61(d,J＝16.5Hz,1H),5.10(d,J＝9.9Hz,1H),5.72(ddd,J＝15.6,10.5,5.1Hz,1H),6.63(s,1H),6.82(dd,J＝8.7,2.1Hz,1H),7.24-7.37(m，6H)，7.59(d，J＝8.7Hz，1H). ¹ H NMR (400MHz, CDCl ₃ ) δ3.42(dd, J=12.9, 2.1Hz, 1H), 3.83(s, 3H), 3.92(dd, J=12.6, 4.5Hz, 1H), 4.59(d, J=15.0Hz, 1H), 4.61(d, J=16.5Hz, 1H), 5.10(d, J=9.9Hz, 1H), 5.72(ddd, J=15.6, 10.5, 5.1Hz, 1H), 6.63( s, 1H), 6.82(dd, J=8.7, 2.1Hz, 1H), 7.24-7.37(m, 6H), 7.59(d, J=8.7Hz, 1H).

¹³C NMR(75MHz,CDCl₃)δ49.4,49.7,52.8,55.5,92.3,107.0,111.7,118.1,121.7,123.5,127.6,127.7,128.5,128.6,133.7,136.5,137.1,158.3,159.9. ¹³ C NMR (75MHz, CDCl ₃ ) δ49.4, 49.7, 52.8, 55.5, 92.3, 107.0, 111.7, 118.1, 121.7, 123.5, 127.6, 127.7, 128.5, 128.6, 133.7, 136.5, 137.1, 158.3, 159.9.

IR(薄膜):ν_max(cm^-1)＝3292,2924,1640,1544,1496,1312,1210,1028,812,703.IR (thin film): ν _max (cm ^-1 )＝3292,2924,1640,1544,1496,1312,1210,1028,812,703.

HRMS-ESI计算值(Calcd for)C₂₁H₂₁N₂O₂(M⁺+H):333.1598.实验值(Found):333.1599.HRMS-ESI calculated value (Calcd for) C ₂₁ H ₂₁ N ₂ O ₂ (M ⁺⁺ H): 333.1598. Experimental value (Found): 333.1599.

化合物P10Compound P10

白色固体，收率：77％，ee值为90％[Daicel ChiralcelOD-H,正己烷(hexane)/2-丙醇(2-propanol)＝80/20,v＝1.0ml·min^-1,λ＝230nm,t(minor)＝13.30min,t(major)＝27.78min].White solid, yield: 77%, ee value: 90% [Daicel ChiralcelOD-H, n-hexane (hexane)/2-propanol (2-propanol) = 80/20, v = 1.0ml·min ^-1 ,λ =230nm,t(minor)=13.30min,t(major)=27.78min].

[α]_D ¹⁸-13.9(c1.00,CH₂Cl₂).¹H NMR(400MHz,CDCl₃)δ3.15(s,3H),3.50(dd,J＝12.8,2.4Hz,1H),4.08(dd,J＝12.8,4.8Hz,1H),4.76(d,J＝16.0Hz,1H),4.99-5.05(m,1H),5.17(d,J＝10.0Hz,1H),5.95(ddd,J＝15.6,10.0,5.6Hz,1H),7.12-7.18(m,1H),7.24-7.32(m,3H),7.71(d,J＝8.0Hz,1H).[α] _D ¹⁸ -13.9 (c1.00, CH ₂ Cl ₂ ). ¹ H NMR (400MHz, CDCl ₃ ) δ 3.15 (s, 3H), 3.50 (dd, J=12.8, 2.4Hz, 1H), 4.08(dd,J=12.8,4.8Hz,1H),4.76(d,J=16.0Hz,1H),4.99-5.05(m,1H),5.17(d,J=10.0Hz,1H),5.95(ddd ,J=15.6,10.0,5.6Hz,1H),7.12-7.18(m,1H),7.24-7.32(m,3H),7.71(d,J=8.0Hz,1H).

¹³C NMR(100MHz,CDCl₃)δ34.4,52.7,53.0,106.1,110.0,118.2,120.7,122.6,124.4,127.4,128.7,133.8,136.1,160.0. ¹³ C NMR (100MHz, CDCl ₃ ) δ34.4, 52.7, 53.0, 106.1, 110.0, 118.2, 120.7, 122.6, 124.4, 127.4, 128.7, 133.8, 136.1, 160.0.

IR(薄膜):ν_max(cm^-1)＝3083,2926,1644,1551,1454,1399,1326,1268,936,812,752,744.IR (thin film):ν _max (cm ^-1 )＝3083,2926,1644,1551,1454,1399,1326,1268,936,812,752,744.

HRMS-ESI计算值(Calcd for)C₁₄H₁₅N₂O(M⁺+H):227.1179.实验值(Found):227.1175；HRMS-ESI calculated value (Calcd for) C ₁₄ H ₁₅ N ₂ O (M ⁺ +H): 227.1179. Experimental value (Found): 227.1175;

m.p.＝127-128℃.m.p.＝127-128℃.

化合物P11Compound P11

白色固体，收率：82％，ee值为92％[Daicel ChiralcelOD-H,正己烷(hexane)/2-丙醇(2-propanol)＝85/15,v＝1.0ml·min^-1,λ＝230nm,t(minor)＝16.68min,t(major)＝34.39min]；[α]_D ²⁷-22.1(c1.00,CH₂Cl₂).White solid, yield: 82%, ee value 92% [Daicel ChiralcelOD-H, n-hexane (hexane)/2-propanol (2-propanol) = 85/15, v = 1.0ml·min ^-1 ,λ =230nm, t(minor)=16.68min, t(major)=34.39min]; [α] _D ²⁷ -22.1(c1.00, CH ₂ Cl ₂ ).

¹H NMR(300MHz，CDCl₃)δ3.51(dd，J＝12.9，2.4Hz，1H)，3.91-4.04(m，2H)，4.40(dd,J＝15.6,5.7Hz,1H),4.69(d,J＝17.4Hz,1H),4.98-5.08(m,1H),5.16(d,J＝10.2Hz,1H),5.25(d,J＝9.3Hz,1H),5.28(d,J＝17.1Hz,1H),5.71-5.98(m,2H),7.11-7.20(m,1H),7.23-7.35(m,3H),7.71(d,J＝7.8Hz,1H). ¹ H NMR (300MHz, CDCl ₃ ) δ3.51(dd, J=12.9, 2.4Hz, 1H), 3.91-4.04(m, 2H), 4.40(dd, J=15.6, 5.7Hz, 1H), 4.69( d,J=17.4Hz,1H),4.98-5.08(m,1H),5.16(d,J=10.2Hz,1H),5.25(d,J=9.3Hz,1H),5.28(d,J=17.1 Hz,1H),5.71-5.98(m,2H),7.11-7.20(m,1H),7.23-7.35(m,3H),7.71(d,J=7.8Hz,1H).

¹³C NMR(100MHz,CDCl₃)δ48.4,49.6,52.9,106.4,110.0,118.2,118.6,120.7,122.6,124.5,127.4,128.6,132.5,133.8,136.0,159.5. ¹³ C NMR (100MHz, CDCl ₃ ) δ48.4, 49.6, 52.9, 106.4, 110.0, 118.2, 118.6, 120.7, 122.6, 124.5, 127.4, 128.6, 132.5, 133.8, 136.0, 159.5.

IR(薄膜):ν_max(cm^-1)＝3050,2906,1641,1544,1456,1356,1243,1145,933,921,815,756.IR (thin film): ν _max (cm ^-1 ) = 3050, 2906, 1641, 1544, 1456, 1356, 1243, 1145, 933, 921, 815, 756.

HRMS-ESI计算值(Calcd for)C₁₆H₁₇N₂O(M⁺+H):253.1335.实验值(Found):253.1336.HRMS-ESI calculated value (Calcd for) C ₁₆ H ₁₇ N ₂ O (M ⁺ +H): 253.1335. Experimental value (Found): 253.1336.

m.p.＝115-116℃.m.p.=115-116°C.

化合物P12Compound P12

浅黄色油状物，收率：95％，ee值为93％[Daicel ChiralpakAD-H,正己烷(hexane)/2-丙醇(2-propanol)＝80/20,v＝1.0ml·min^-1,λ＝230nm,t(major)＝24.83min,t(minor)＝34.87min].Pale yellow oil, yield: 95%, ee value 93% [Daicel ChiralpakAD-H, n-hexane (hexane)/2-propanol (2-propanol) = 80/20, v = 1.0ml·min ^-1 ,λ=230nm,t(major)=24.83min,t(minor)=34.87min].

[α]_D ¹⁷-4.4(c1.00,CH₂Cl₂).[α] _D ¹⁷ -4.4(c1.00, CH ₂ Cl ₂ ).

¹H NMR(300MHz,CDCl₃)δ3.43(d,J＝13.2Hz,1H),3.78(s,3H),3.94(dd,J＝12.9,5.1Hz,1H),4.52(d,J＝14.7Hz,1H),4.58(d,J＝17.7Hz,1H),4.89(d,J＝14.7Hz,1H),4.94-5.00(m,1H),5.07(d,J＝10.5Hz,1H),5.71(ddd,J＝15.9,10.5,5.4Hz,1H),6.85(d,J＝8.4Hz,1H),7.14(t,J＝7.8Hz,1H),7.21-7.33(m,4H),7.34(s,1H),7.72(d,J＝7.8Hz,1H). ¹ H NMR (300MHz, CDCl ₃ ) δ3.43(d, J=13.2Hz, 1H), 3.78(s, 3H), 3.94(dd, J=12.9, 5.1Hz, 1H), 4.52(d, J= 14.7Hz, 1H), 4.58(d, J=17.7Hz, 1H), 4.89(d, J=14.7Hz, 1H), 4.94-5.00(m, 1H), 5.07(d, J=10.5Hz, 1H) ,5.71(ddd,J=15.9,10.5,5.4Hz,1H),6.85(d,J=8.4Hz,1H),7.14(t,J=7.8Hz,1H),7.21-7.33(m,4H), 7.34(s,1H),7.72(d,J=7.8Hz,1H).

效果实施例2Effect Example 2

一般反应操作：氩气保护下，往Schlenk管中加入底物S1(75.6mg,0.2mmol)，3a(5.8mg,0.01mmol,5mol％)和DBU(3.0mg,0.02mmol)于2.0mL二氯甲烷(CH₂Cl₂)中，室温下搅拌反应6小时。TLC跟踪反应完全后，用硅藻土过滤，减压除去溶剂，柱层析提纯(石油醚/乙酸乙酯＝5/1)。产物的ee由HPLC测定。表8中，摩尔比是指S1：碱：催化剂的摩尔比。General reaction operation: under argon protection, add substrate S1 (75.6mg, 0.2mmol), 3a (5.8mg, 0.01mmol, 5mol%) and DBU (3.0mg, 0.02mmol) in 2.0mL dichloro In methane (CH ₂ Cl ₂ ), the reaction was stirred at room temperature for 6 hours. After the completion of the reaction traced by TLC, filter with celite, remove the solvent under reduced pressure, and purify by column chromatography (petroleum ether/ethyl acetate=5/1). The ee of the product was determined by HPLC. In Table 8, the molar ratio refers to the molar ratio of S1:base:catalyst.

表8Table 8

化合物P13Compound P13

浅黄色油状物，收率：83％，ee值为99％[Daicel Chiralcel OD-H,正己烷(hexane)/2-丙醇(2-propanol)＝90/10,v＝1.0ml·min^-1,λ＝254nm,t(major)＝19.86min,t(minor)＝34.51min]；[α]_D ²⁸-6.5(c1.00,CH₂Cl₂).Pale yellow oil, yield: 83%, ee value: 99% [Daicel Chiralcel OD-H, n-hexane (hexane)/2-propanol (2-propanol) = 90/10, v = 1.0ml·min ^{- 1} ,λ=254nm,t(major)=19.86min,t(minor)=34.51min]; [α] _D ²⁸ -6.5(c1.00,CH ₂ Cl ₂ ).

化合物P14Compound P14

黄色固体，收率：87％，ee值为98％[Daicel ChiralpakAD-H,正己烷(hexane)/2-丙醇(2-propanol)＝80/20,v＝1.0ml·min^-1,λ＝254nm,t(minor)＝23.86min,t(major)＝30.53min].Yellow solid, yield: 87%, ee value: 98% [Daicel ChiralpakAD-H, n-hexane (hexane)/2-propanol (2-propanol) = 80/20, v = 1.0ml·min ^-1 ,λ =254nm,t(minor)=23.86min,t(major)=30.53min].

[α]_D ²⁶-10.2(c1.00,CH₂Cl₂).[α] _D ²⁶ -10.2(c1.00, CH ₂ Cl ₂ ).

¹H NMR(300MHz,CDCl₃)δ3.45(dd,J＝12.6,2.1Hz,1H),3.94(dd,J＝12.9,5.1Hz,1H),4.57(d,J＝16.8Hz,2H),4.59(d,J＝14.7Hz,2H),5.10(d,J＝9.9Hz,1H),5.70(ddd,J＝16.8,10.5,5.4Hz,1H),7.12(d,J＝9.0Hz,1H),7.24-7.40(m,7H),7.85(s,1H). ¹ H NMR (300MHz, CDCl ₃ ) δ3.45 (dd, J=12.6, 2.1Hz, 1H), 3.94 (dd, J=12.9, 5.1Hz, 1H), 4.57 (d, J=16.8Hz, 2H) ,4.59(d,J=14.7Hz,2H),5.10(d,J=9.9Hz,1H),5.70(ddd,J=16.8,10.5,5.4Hz,1H),7.12(d,J=9.0Hz, 1H),7.24-7.40(m,7H),7.85(s,1H).

¹³C NMR(75MHz,CDCl₃)δ49.4,49.5,53.0,105.8,111.5,113.9,118.3,125.0,127.5,127.8,128.5,128.6,128.9,129.6,133.5,134.7,136.1,159.3. ¹³ C NMR (75MHz, CDCl ₃ ) δ49.4, 49.5, 53.0, 105.8, 111.5, 113.9, 118.3, 125.0, 127.5, 127.8, 128.5, 128.6, 128.9, 129.6, 133.5, 134.7, 136.1, 159.3.

IR(薄膜):ν_max(cm^-1)＝3064,1639,1547,1448,1429,1251,1173,933,802,732,697；HRMS-ESI计算值(Calcd for)C₂₀H₁₈BrN₂O(M⁺+H):381.0597.实验值(Found):381.0599.IR (thin film): ν _max (cm ^-1 ) = 3064, 1639, 1547, 1448, 1429, 1251, 1173, 933, 802, 732, 697; HRMS-ESI calculated value (Calcd for) C ₂₀ H ₁₈ BrN ₂ O(M ⁺ +H ):381.0597. Experimental value (Found): 381.0599.

m.p.＝135-136℃.m.p.=135-136°C.

化合物P15Compound P15

浅黄色油状物，收率：91％，ee值为98％[Daicel ChiralpakAD-H,正己烷(hexane)/2-丙醇(2-propanol)＝80/20,v＝1.0ml·min^-1,λ＝254nm,t(minor)＝16.81min,t(major)＝22.81min].Pale yellow oil, yield: 91%, ee value: 98% [Daicel ChiralpakAD-H, n-hexane (hexane)/2-propanol (2-propanol) = 80/20, v = 1.0ml·min ^-1 ,λ=254nm,t(minor)=16.81min,t(major)=22.81min].

[α]_D ²⁶-13.7(c1.00,CH₂Cl₂).[α] _D ²⁶ -13.7(c1.00, CH ₂ Cl ₂ ).

¹H NMR(300MHz,CDCl₃)δ3.45(d,J＝13.2Hz,1H),3.93(dd,J＝13.2,4.8Hz,1H),4.60(d,J＝14.7Hz,1H),4.62(d,J＝17.1Hz,1H),4.83-4.99(m,2H),5.12(d,J＝10.5Hz,1H),5.72(ddd,J＝15.6,9.9,5.1Hz,1H),7.12(d,J＝8.7Hz,1H),7.25(s,1H),7.27-7.38(m,6H),7.63(d,J＝8.4Hz,1H). ¹ H NMR (300MHz, CDCl ₃ ) δ3.45 (d, J=13.2Hz, 1H), 3.93 (dd, J=13.2, 4.8Hz, 1H), 4.60 (d, J=14.7Hz, 1H), 4.62 (d,J=17.1Hz,1H),4.83-4.99(m,2H),5.12(d,J=10.5Hz,1H),5.72(ddd,J=15.6,9.9,5.1Hz,1H),7.12( d,J=8.7Hz,1H),7.25(s,1H),7.27-7.38(m,6H),7.63(d,J=8.4Hz,1H).

¹³C NMR(75MHz,CDCl₃)δ49.5,49.6,53.0,106.7,110.0,118.4,121.7,123.6,125.9,127.8，128.5，128.6，129.3，130.5，133.4，136.1，136.4，159.5. ¹³ C NMR (75MHz, CDCl ₃ ) δ49.5, 49.6, 53.0, 106.7, 110.0, 118.4, 121.7, 123.6, 125.9, 127.8, 128.5, 128.6, 129.3, 130.5, 133.4, 136.1, 136.4, 159.5.

化合物P16Compound P16

黄色固体，收率：84％，ee值为98％[Daicel ChiralpakAD-H,正己烷(hexane)/2-丙醇(2-propanol)＝80/20,v＝1.0ml·min^-1,λ＝254nm,t(minor)＝18.42min,t(minor)＝23.58min]；[α]_D ²³-3.7(c1.00,CH₂Cl₂).Yellow solid, yield: 84%, ee value: 98% [Daicel ChiralpakAD-H, n-hexane (hexane)/2-propanol (2-propanol) = 80/20, v = 1.0ml·min ^-1 ,λ =254nm, t(minor)=18.42min, t(minor)=23.58min]; [α] _D ²³ -3.7(c1.00, CH ₂ Cl ₂ ).

¹H NMR(400MHz,CDCl₃)δ3.44(d,J＝12.0,1.6Hz,1H),3.92(dd,J＝12.8,4.4Hz,1H),4.57-4.64(m,2H),4.89-4.96(m,2H),5.09(d,J＝10.4Hz,1H),5.72(ddd,J＝16.8,10.4,5.2Hz,1H),7.03(dt,J＝8.8,2.4Hz,1H),7.17(dd,J＝9.2,4.4Hz,1H),7.24-7.36(m,7H)；¹³C NMR(75MHz,CDCl₃)δ49.5,49.6,53.1,106.2,106.3,106.8,107.1,110.9,113.6,118.2,127.5,127.6,127.7,128.4,128.6,130.1,132.8,133.7,136.2,156.9,159.3,159.4. ¹ H NMR (400MHz, CDCl ₃ ) δ3.44 (d, J=12.0, 1.6Hz, 1H), 3.92 (dd, J=12.8, 4.4Hz, 1H), 4.57-4.64 (m, 2H), 4.89- 4.96(m,2H),5.09(d,J=10.4Hz,1H),5.72(ddd,J=16.8,10.4,5.2Hz,1H),7.03(dt,J=8.8,2.4Hz,1H),7.17 (dd, J=9.2, 4.4Hz, 1H), 7.24-7.36 (m, 7H); ¹³ C NMR (75MHz, CDCl ₃ ) δ49.5, 49.6, 53.1, 106.2, 106.3, 106.8, 107.1, 110.9, 113.6 ,118.2,127.5,127.6,127.7,128.4,128.6,130.1,132.8,133.7,136.2,156.9,159.3,159.4.

m.p.＝127-128℃.m.p.＝127-128℃.

化合物P17Compound P17

黄色固体，收率：87％，ee值为99％[Daicel ChiralpakAD-H,正己烷(hexane)/2-丙醇(2-propanol)＝80/20,v＝1.0ml·min^-1,λ＝230nm,t(minor)＝22.30min,t(major)＝27.39min].Yellow solid, yield: 87%, ee value: 99% [Daicel ChiralpakAD-H, n-hexane (hexane)/2-propanol (2-propanol) = 80/20, v = 1.0ml·min ^-1 ,λ =230nm,t(minor)=22.30min,t(major)=27.39min].

[α]_D ²⁵-5.8(c1.00,CH₂Cl₂).[α] _D ²⁵ -5.8(c1.00, CH ₂ Cl ₂ ).

¹H NMR(400MHz,CDCl₃)δ2.43(s,3H),3.42(dd,J＝12.4,2.0Hz,1H),3.92(dd,J＝12.8,4.8Hz,1H),4.57-4.64(m,2H),4.89-4.97(m,2H),5.09(d,J＝10.4Hz,1H),5.72(ddd,J＝15.6，10.0，5.2Hz，1H)，7.09-7.16(m，2H)，7.24-7.36(m，6H)，7.50(s，1H)；¹³C NMR(75MHz,CDCl₃)δ21.4,49.5,49.7,52.9,106.1,109.7,118.0,122.1,126.5,127.6,127.7,128.4,128.5,128.6,130.1,133.9,134.7,136.4,159.9. ¹ H NMR (400MHz, CDCl ₃ ) δ2.43(s, 3H), 3.42(dd, J=12.4, 2.0Hz, 1H), 3.92(dd, J=12.8, 4.8Hz, 1H), 4.57-4.64( m, 2H), 4.89-4.97(m, 2H), 5.09(d, J=10.4Hz, 1H), 5.72(ddd, J=15.6, 10.0, 5.2Hz, 1H), 7.09-7.16(m, 2H) , 7.24-7.36 (m, 6H), 7.50 (s, 1H); ¹³ C NMR (75MHz, CDCl ₃ ) δ21.4, 49.5, 49.7, 52.9, 106.1, 109.7, 118.0, 122.1, 126.5, 127.6, 127.7, 128.4, 128.5, 128.6, 130.1, 133.9, 134.7, 136.4, 159.9.

m.p.＝142-143℃.m.p.=142-143°C.

化合物P18Compound P18

白色固体，收率：79％，ee值为98％[Daicel ChiralpakAD-H,正己烷(hexane)/2-丙醇(2-propanol)＝80/20,v＝1.0ml·min^-1,λ＝230nm,t(minor)＝26.64min,t(major)＝30.33min].White solid, yield: 79%, ee value: 98% [Daicel ChiralpakAD-H, n-hexane (hexane)/2-propanol (2-propanol) = 80/20, v = 1.0ml·min ^-1 ,λ =230nm,t(minor)=26.64min,t(major)=30.33min].

[α]_D ²³-4.9(c1.00,CH₂Cl₂).[α] _D ²³ -4.9(c1.00, CH ₂ Cl ₂ ).

m.p.＝148-149℃.m.p.=148-149°C.

化合物P19Compound P19

无色油状物，收率：91％，ee值为99％[Daicel ChiralpakAD-H,正己烷(hexane)/2-丙醇(2-propanol)＝80/20，v＝1.0ml·min^-1，λ＝230nm，t(minor)＝18.25min，t(major)＝23.05min].Colorless oil, yield: 91%, ee value 99% [Daicel ChiralpakAD-H, n-hexane (hexane)/2-propanol (2-propanol) = 80/20, v = 1.0ml·min ^-1 , λ=230nm, t(minor)=18.25min, t(major)=23.05min].

[α]_D ²⁸-16.6(c1.00,CH₂Cl₂).[α] _D ²⁸ -16.6(c1.00, CH ₂ Cl ₂ ).

¹³C NMR(100MHz,CDCl₃)δ49.5,49.6,53.0,106.7,113.0,118.3,118.4,123.9,124.2,126.2,127.8,128.5,128.6,129.2,133.4,136.1,136.8,159.4. ¹³ C NMR (100MHz, CDCl ₃ ) δ49.5, 49.6, 53.0, 106.7, 113.0, 118.3, 118.4, 123.9, 124.2, 126.2, 127.8, 128.5, 128.6, 129.2, 133.4, 136.1, 136.8, 159.4.

IR(薄膜):ν_max(cm^-1)＝3080,2925,1644,1545,1494,1430,1355,1270,1149,928,821,744.IR (thin film): ν _max (cm ^-1 ) = 3080, 2925, 1644, 1545, 1494, 1430, 1355, 1270, 1149, 928, 821, 744.

化合物P20Compound P20

黄色固体，收率：86％，ee值为98％[Daicel ChiralpakAD-H,正己烷(hexane)/2-丙醇(2-propanol)＝80/20,v＝1.0ml·min^-1,λ＝230nm,t(minor)＝21.57min,t(major)＝26.72min].Yellow solid, yield: 86%, ee value: 98% [Daicel ChiralpakAD-H, n-hexane (hexane)/2-propanol (2-propanol) = 80/20, v = 1.0ml·min ^-1 ,λ =230nm,t(minor)=21.57min,t(major)=26.72min].

[α]_D ²⁶-9.9(c1.00,CH₂Cl₂).[α] _D ²⁶ -9.9(c1.00, CH ₂ Cl ₂ ).

IR(薄膜):ν_max(cm^-1)＝3086,2924,1649,1548,1474,1420,1250,1061,919,801,745；HRMS-ESI计算值(Calcd for)C₂₀H₁₈ClN₂O(M⁺+H):337.1102.实验值(Found):337.1108.IR (thin film): ν _max (cm ^-1 ) = 3086, 2924, 1649, 1548, 1474, 1420, 1250, 1061, 919, 801, 745; HRMS-ESI calculated value (Calcd for) C ₂₀ H ₁₈ ClN ₂ O(M ⁺ +H): 337.1102. Experimental value (Found): 337.1108.

m.p.＝127-128℃.m.p.＝127-128℃.

化合物P21Compound P21

黄色油状物，收率：77％，ee值为98％[Daicel ChiralpakAD-H,正己烷(hexane)/2-丙醇(2-propanol)＝80/20,v＝1.0ml·min^-1,λ＝230nm,t(minor)＝22.72min,t(major)＝29.24min].Yellow oil, yield: 77%, ee value 98% [Daicel ChiralpakAD-H, n-hexane (hexane)/2-propanol (2-propanol) = 80/20, v = 1.0ml·min ^-1 , λ=230nm, t(minor)=22.72min, t(major)=29.24min].

[α]_D ²²-24.2(c1.00,CH₂Cl₂).[α] _D ²² -24.2(c1.00, CH ₂ Cl ₂ ).

¹H NMR(400MHz,CDCl₃)δ3.42(dd,J＝12.9,2.1Hz,1H),3.83(s,3H),3.92(dd,J＝12.6,4.5Hz,1H),4.59(d,J＝15.0Hz,1H),4.61(d,J＝16.5Hz,1H),5.10(d,J＝9.9Hz,1H),5.72(ddd,J＝15.6,10.5,5.1Hz,1H),6.63(s,1H),6.82(dd,J＝8.7,2.1Hz,1H),7.24-7.37(m,6H),7.59(d,J＝8.7Hz,1H). ¹ H NMR (400MHz, CDCl ₃ ) δ3.42(dd, J=12.9, 2.1Hz, 1H), 3.83(s, 3H), 3.92(dd, J=12.6, 4.5Hz, 1H), 4.59(d, J=15.0Hz, 1H), 4.61(d, J=16.5Hz, 1H), 5.10(d, J=9.9Hz, 1H), 5.72(ddd, J=15.6, 10.5, 5.1Hz, 1H), 6.63( s,1H),6.82(dd,J=8.7,2.1Hz,1H),7.24-7.37(m,6H),7.59(d,J=8.7Hz,1H).

化合物P22Compound P22

白色固体，收率：81％，ee值为96％[Daicel ChiralcelOD-H,正己烷(hexane)/2-丙醇(2-propanol)＝80/20,v＝1.0ml·min^-1,λ＝230nm,t(major)＝11.80min,t(minor)＝25.48min].White solid, yield: 81%, ee value: 96% [Daicel ChiralcelOD-H, n-hexane (hexane)/2-propanol (2-propanol) = 80/20, v = 1.0ml·min ^-1 ,λ =230nm,t(major)=11.80min,t(minor)=25.48min].

[α]_D ²³+15.8(c1.00,CH₂Cl₂).¹H NMR(400MHz,CDCl₃)δ3.15(s,3H),3.50(dd,J＝12.8,2.4Hz,1H),4.08(dd,J＝12.8,4.8Hz,1H),4.76(d,J＝16.0Hz,1H),4.99-5.05(m,1H),5.17(d,J＝10.0Hz,1H),5.95(ddd,J＝15.6,10.0,5.6Hz,1H),7.12-7.18(m,1H),7.24-7.32(m,3H),7.71(d,J＝8.0Hz,1H).[α] _D ²³ +15.8 (c1.00, CH ₂ Cl ₂ ). ¹ H NMR (400MHz, CDCl ₃ ) δ 3.15 (s, 3H), 3.50 (dd, J＝12.8, 2.4Hz, 1H), 4.08(dd,J=12.8,4.8Hz,1H),4.76(d,J=16.0Hz,1H),4.99-5.05(m,1H),5.17(d,J=10.0Hz,1H),5.95(ddd ,J=15.6,10.0,5.6Hz,1H),7.12-7.18(m,1H),7.24-7.32(m,3H),7.71(d,J=8.0Hz,1H).

HRMS-ESI计算值(Calcd for)C₁₄H₁₅N₂O(M⁺+H):227.1179.实验值(Found):227.1175.HRMS-ESI calculated value (Calcd for) C ₁₄ H ₁₅ N ₂ O (M ⁺ +H): 227.1179. Experimental value (Found): 227.1175.

m.p.＝127-128℃.m.p.＝127-128℃.

化合物P23Compound P23

白色固体，收率：74％，ee值为98％[Daicel ChiralcelOD-H,正己烷(hexane)/2-丙醇(2-propanol)＝85/15,v＝1.0ml·min^-1,λ＝230nm,t(major)＝15.58min,t(minor)＝31.85min].White solid, yield: 74%, ee value: 98% [Daicel ChiralcelOD-H, n-hexane (hexane)/2-propanol (2-propanol) = 85/15, v = 1.0ml·min ^-1 ,λ =230nm,t(major)=15.58min,t(minor)=31.85min].

[α]_D ²⁵+29.7(c1.00,CH₂Cl₂).[α] _D ²⁵ +29.7(c1.00, CH ₂ Cl ₂ ).

¹H NMR(300MHz,CDCl₃)δ3.51(dd,J＝12.9,2.4Hz,1H),3.91-4.04(m,2H),4.40(dd,J＝15.6,5.7Hz,1H),4.69(d,J＝17.4Hz,1H),4.98-5.08(m,1H),5.16(d,J＝10.2Hz,1H),5.25(d,J＝9.3Hz,1H),5.28(d,J＝17.1Hz,1H),5.71-5.98(m,2H),7.11-7.20(m,1H),7.23-7.35(m,3H),7.71(d,J＝7.8Hz,1H). ¹ H NMR (300MHz, CDCl ₃ ) δ3.51(dd, J=12.9, 2.4Hz, 1H), 3.91-4.04(m, 2H), 4.40(dd, J=15.6, 5.7Hz, 1H), 4.69( d,J=17.4Hz,1H),4.98-5.08(m,1H),5.16(d,J=10.2Hz,1H),5.25(d,J=9.3Hz,1H),5.28(d,J=17.1 Hz,1H),5.71-5.98(m,2H),7.11-7.20(m,1H),7.23-7.35(m,3H),7.71(d,J=7.8Hz,1H).

m.p.＝115-116℃.m.p.=115-116°C.

化合物P24Compound P24

浅黄色油状物，收率：89％，ee值为99％[Daicel ChiralpakAD-H,正己烷(hexane)/2-丙醇(2-propanol)＝80/20,v＝1.0ml·min^-1,λ＝230nm,t(minor)＝23.23min,t(major)＝35.43min].Pale yellow oil, yield: 89%, ee value: 99% [Daicel ChiralpakAD-H, n-hexane (hexane)/2-propanol (2-propanol) = 80/20, v = 1.0ml·min ^-1 ,λ=230nm,t(minor)=23.23min,t(major)=35.43min].

[α]_D ²⁸+4.0(c1.00,CH₂Cl₂).[α] _D ²⁸ +4.0(c1.00, CH ₂ Cl ₂ ).

¹H NMR(300MHz，CDCl₃)δ3.43(d，J＝13.2Hz，1H)，3.78(s，3H)，3.94(dd，J＝12.9，5.1Hz,1H),4.52(d,J＝14.7Hz,1H),4.58(d,J＝17.7Hz,1H),4.89(d,J＝14.7Hz,1H),4.94-5.00(m,1H),5.07(d,J＝10.5Hz,1H),5.71(ddd,J＝15.9,10.5,5.4Hz,1H),6.85(d,J＝8.4Hz,1H),7.14(t,J＝7.8Hz,1H),7.21-7.33(m,4H),7.34(s,1H),7.72(d,J＝7.8Hz,1H). ¹ H NMR (300MHz, CDCl ₃ ) δ3.43(d, J=13.2Hz, 1H), 3.78(s, 3H), 3.94(dd, J=12.9, 5.1Hz, 1H), 4.52(d, J= 14.7Hz, 1H), 4.58(d, J=17.7Hz, 1H), 4.89(d, J=14.7Hz, 1H), 4.94-5.00(m, 1H), 5.07(d, J=10.5Hz, 1H) ,5.71(ddd,J=15.9,10.5,5.4Hz,1H),6.85(d,J=8.4Hz,1H),7.14(t,J=7.8Hz,1H),7.21-7.33(m,4H), 7.34(s,1H),7.72(d,J=7.8Hz,1H).

效果实施例3将IIIa放置空气6个月后，测试其在如式P所示的化合物合成中的催化作用Effect Example 3 After placing IIIa in the air for 6 months, test its catalytic effect in the synthesis of compounds shown in formula P

一般反应操作：氩气保护下，往Schlenk管中加入底物S1(75.6mg,0.2mmol)，IIIa(放置于空气中六个月后，5.8mg,0.01mmol,5mol％)和DBU(3.0mg,0.02mmol)于2.0mL二氯甲烷(CH₂Cl₂)中，室温下搅拌反应6小时。TLC跟踪反应完全后，用硅藻土过滤，减压除去溶剂，柱层析提纯(石油醚/乙酸乙酯＝5/1)。产物的ee由HPLC测定。General reaction operation: under argon protection, add substrate S1 (75.6mg, 0.2mmol), IIIa (after six months in air, 5.8mg, 0.01mmol, 5mol%) and DBU (3.0mg , 0.02 mmol) in 2.0 mL of dichloromethane (CH ₂ Cl ₂ ), stirred at room temperature for 6 hours. After the completion of the reaction traced by TLC, filter with celite, remove the solvent under reduced pressure, and purify by column chromatography (petroleum ether/ethyl acetate=5/1). The ee of the product was determined by HPLC.

化合物P25Compound P25

浅黄色油状物，收率：82％，ee值为99％[Daicel Chiralcel OD-H,正己烷(hexane)/2-丙醇(2-propanol)＝90/10,v＝1.0ml·min^-1,λ＝254nm,t(major)＝19.86min,t(minor)＝34.51min]；[α]_D ²⁸-6.5(c1.00,CH₂Cl₂).Pale yellow oil, yield: 82%, ee value: 99% [Daicel Chiralcel OD-H, n-hexane (hexane)/2-propanol (2-propanol) = 90/10, v = 1.0ml·min ^{- 1} ,λ=254nm,t(major)=19.86min,t(minor)=34.51min]; [α] _D ²⁸ -6.5(c1.00,CH ₂ Cl ₂ ).

效果实施例3Effect Example 3

将化合物Ia-Ik、化合物IIa-IIu、化合物IIIa-IIIf、化合物IVa-IVi、化合物Va-Vg、化合物VIa-VIe分别放置空气中6个月后，参照效果实施例1和效果实施例2中如式P所示化合物的制备方法，测定本发明通式I～VI所示的金属铱络合物的催化作用。Compound Ia-Ik, Compound IIa-IIu, Compound IIIa-IIIf, Compound IVa-IVi, Compound Va-Vg, Compound VIa-VIe were respectively placed in the air for 6 months, referring to Effect Example 1 and Effect Example 2 As in the preparation method of the compound represented by the formula P, the catalytic effect of the metal iridium complex represented by the general formulas I to VI of the present invention is determined.

表9Table 9

化合物compound 催化剂catalyst 收率yield ee值(％)ee value (%) 编号Numbering 催化剂catalyst 收率yield ee值(％)ee value (%) P1P1 IaIa 8181 9292 P12P12 IVcIVc 9595 9393

P2P2 IbIb 7777 9292 P14P14 IIIaIIIa 8787 9898 P3P3 IkIk 7878 9292 P16P16 IIIbIIIb 8484 9898 P4P4 VgVg 8484 8989 P18P18 IIIeIIIe 7979 9898 P8P8 IIhIIh 7575 9191 P23P23 IIIfIIIf 7474 9898 P10P10 IIkIIk 7777 9090 // // // //

对比实施例1Comparative Example 1

氩气保护下，往Schlenk管中加入底物S1(75.6mg,0.2mmol)，7a(6.6mg,0.01mmol,5mol％)和DBU(3.0mg,0.02mmol)于2.0mL二氯甲烷(CH₂Cl₂)中，室温下搅拌反应24小时，TLC检测没有目标产物生成。Under argon protection, the substrate S1 (75.6mg, 0.2mmol), 7a (6.6mg, 0.01mmol, 5mol%) and DBU (3.0mg, 0.02mmol) in 2.0mL dichloromethane (CH ₂ Cl ₂ ), stirred and reacted at room temperature for 24 hours, no target product was detected by TLC.

对比实施例2Comparative Example 2

氩气保护下，往Schlenk管中加入底物S1(75.6mg,0.2mmol)，7b(7.6mg,0.01mmol,5mol％)和DBU(3.0mg,0.02mmol)于2.0mL二氯甲烷(CH₂Cl₂)中，室温下搅拌反应24小时，TLC检测没有目标产物生成。Under the protection of argon, the substrate S1 (75.6mg, 0.2mmol), 7b (7.6mg, 0.01mmol, 5mol%) and DBU (3.0mg, 0.02mmol) were added in 2.0mL dichloromethane (CH ₂ Cl ₂ ), stirred and reacted at room temperature for 24 hours, no target product was detected by TLC.

Claims

1. A metal iridium complex compound shown in general formula I, general formula II, general formula III, general formula IV, general formula V or general formula VI, wherein the carbon marked with * is chiral carbon or achiral Carbon, when chiral carbon, said chiral carbon is S configuration or R configuration;

Wherein, R ¹ , R ^1a , R ^1b , R ^1c , R ^1d and R ^1e are independently C ₃ -C ₆ cycloalkyl, substituted or unsubstituted C ₆ -C ₂₀ aryl;

R ² , R ^2' , R ^2a , R ^2a' , R ^2b , R ^2b' , R ^2c and R ^2c' are independently hydrogen, C ₁ -C ₈ alkyl, substituted or unsubstituted C ₆ aryl ; or R ² and R ^2' and their connected carbon atoms together form a C ₅ -C ₈ cycloalkyl group;

^R3 is Among them, R _a is C ₁ -C ₈ perfluoroalkyl, substituted or unsubstituted C ₆ aryl; R _b is C ₁ -C ₈ alkyl, C ₁ -C ₈ alkoxy, C ₁ -C ₈ perfluoroalkyl;

R ⁴ , R ^4a and R ^4b are independently hydrogen, C ₁ -C ₈ alkyl or Wherein, R _c , R _c 'or R _c ” are independently C ₁ -C ₈ alkyl groups;

R ⁵ is hydrogen, halogen;

X ¹ , X ^1a , X ^1b , X ^1c , X ^1d and X ^1e are independently halogen or C ₁ -C ₈ alkoxy;

Wherein, the substitution in the substituted C ₆ -C ₂₀ aryl refers to being substituted by one or more of the following substituents: C ₁ -C ₁₆ alkoxy, C ₁ -C ₁₆ alkane Group, C ₁ -C ₁₆ fluoroalkyl group, nitro group, when there are multiple substituents, the substituents are the same or different.

2. the metal iridium complex shown in general formula I as claimed in claim 1, general formula II, general formula III, general formula IV, general formula V or general formula VI, is characterized in that,

When the substitution in the substituted C ₆ -C ₂₀ aryl group is substituted by a C ₁ -C ₁₆ alkoxy group, the C ₁ -C ₁₆ alkoxy group is methoxy , ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy or tert-butoxy;

And/or, when the substituent is a C ₁ -C ₁₆ alkyl group, the C ₁ -C ₁₆ alkyl group is methyl, ethyl, n-propyl, isopropyl, n-butyl , isobutyl or tert-butyl;

And/or, when the substitution in the substituted C ₆ -C ₂₀ aryl group is substituted by a C ₁ -C ₁₆ fluoroalkyl group, the C ₁ -C ₁₆ fluoro Alkyl refers to a C ₁ -C ₁₆ fluoroalkyl group substituted by one or more fluorine atoms; said C ₁ -C ₁₆ fluoroalkyl group is trifluoromethyl.

3. the metal iridium complex compound shown in general formula I as claimed in claim 1, general formula II, general formula III, general formula IV, general formula V or general formula VI, is characterized in that,

R2, R2', ^R2a , ^R2a ^' , ^R2b , ^R2b' , ^R2c , ^R2c ^' , _Rb , R4, ^R4a , ^R4b , ^Rc , _Rc ', _Rc _" Among them, the C ₁ -C ₈ alkyl group is methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl or tert-butyl;

And/or, in R ¹ , R ^1a , R ^1b , R ^1c , R ^1d , R ^1e , the C ₃ -C ₆ cycloalkyl group is cyclopropyl, cyclobutyl, cyclopentyl or cyclo Hexyl;

And/or, in R _a , R _b , the C ₁ -C ₈ perfluoroalkyl group is in, including the respective isomeric forms;

And/or, R ¹ , R ^1a , R ^1b , R ^1c , R ^1d , R ^1e , R ² , R ² ', R ^2a , R ^2a' , R ^2b , R ^2b' , R ^2c , R ^2c' , In R _a and , the substituted or unsubstituted C ₆ -C ₂₀ aryl is substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted 9-anthracenyl, or substituted Or unsubstituted 9-phenanthrenyl; the substituted phenyl is

And/or, among R _b , X ¹ , X ^1a , X ^1b , X ^1c , X ^1d and X ^1e , the C ₁ -C ₈ alkoxy group is methoxy, ethoxy, n-propoxy , isopropoxy, n-butoxy, isobutoxy or tert-butoxy;

And/or, in X ¹ , X ^1a , X ^1b , X ^1c , X ^1d and X ^1e , the halogen is fluorine, chlorine, bromine or iodine;

And/or, when R ² and R ^2′ and their connected carbon atoms together form a C ₅ -C ₈ cycloalkyl group, the C ₅ -C ₈ cycloalkyl group is cyclopentyl or cyclohexyl.

4. the metal iridium complex shown in general formula II, general formula III, general formula IV or general formula V as claimed in claim 1, is characterized in that,

R ³ , the

and/or, R ³ , the

and/or, R ⁴ , the

5. the metal iridium complex compound shown in general formula I as claimed in claim 1, general formula II, general formula III, general formula IV, general formula V or general formula VI, is characterized in that,

In the metal complex compound represented by general formula I, R ¹ is a C ₃ -C ₆ cycloalkyl group or a substituted or unsubstituted C ₆ -C ₂₀ aryl group; X ¹ is a halogen or C ₁ -C ₈ alkoxy;

And/or, in the metal complex compound represented by general formula II, R ^1a is a C ₃ -C ₆ cycloalkyl group or a substituted or unsubstituted C ₆ -C ₂₀ aryl group; R ² and R ^2' independently substituted or unsubstituted C ₆ aryl; or R ² and R ^2' and their connected carbon atoms together form a C ₅ -C ₈ cycloalkyl; R ³ is Among them, R _a is C ₁ -C ₈ perfluoroalkyl, substituted or unsubstituted C ₆ aryl; R _b is C ₁ -C ₈ alkyl, C ₁ -C ₈ alkoxy, C ₁ -C ₈ perfluoroalkyl; X ^1a is halogen or C ₁ -C ₈ alkoxy;

And/or, in the metal complex compound represented by general formula III, R ^1b is a substituted or unsubstituted C ₆ aryl group; R ^2a , R ^2a' and R ⁴ are independently C ₁ -C ₈ alkane Base; X ^1b is halogen;

And/or, in the metal complex compound shown in general formula IV, R ^1c is a substituted or unsubstituted C ₆ aryl group; R ^2b and R ^2b' are independently C ₁ -C ₈ alkyl, substituted Or unsubstituted C ₆ aryl; R ^4a is independently C ₁ -C ₈ alkyl or Wherein, R _c , R _c ' and R _c " are independently C ₁ -C ₈ alkyl; R ⁵ is hydrogen or halogen; X ^1c is halogen or C ₁ -C ₈ alkoxy;

And/or, in the metal complex compound represented by general formula V, R ^1d is a substituted or unsubstituted C ₆ aryl group; R ^2c , R ^2c' and R ^4b are independently hydrogen, C ₁ -C ₈ Alkyl, substituted or unsubstituted C ₆ aryl; X ^1d is halogen or C ₁ -C ₈ alkoxy;

And/or, in the metal complexes represented by the general formula VI, R ^1e is a substituted or unsubstituted C ₆ aryl group; X ^1e is a halogen or a C ₁ -C ₈ alkoxy group.

6. the metal iridium complex shown in general formula I, general formula II, general formula III, general formula IV, general formula V or general formula VI as claimed in claim 1, is characterized in that, shown in general formula I The metal complexes of are any of the following compounds:

The metal complex shown in general formula II, it is following any compound:

The metal complex shown in general formula III, it is following any compound:

The metal complex compound shown in general formula IV, it is following any compound:

The metal complex shown in general formula V, it is following any compound:

The metal complex shown in general formula VI, it is following any structure:

7. a metal iridium complex IIIa single crystal is characterized in that, in the single crystal X-ray diffraction spectrum that uses radiation source as Cu-K α, crystal belongs to monoclinic system, and space group is P21, and its unit cell parameter: α=90°, β=92.5300(10)°, γ=90°, unit cell volume The number of asymmetric units in the unit cell Z=2;

8. the preparation method of metal iridium complex IIIa single crystal as claimed in claim 7, is characterized in that, comprises the following steps: after metal iridium complex IIIa is mixed with benign solvent, poor solvent is added dropwise, until just If turbidity appears, add a benign solvent dropwise and let it stand.

9. A preparation method of the metal iridium complex shown in general formula I, general formula II, general formula III, general formula IV, general formula V or general formula VI as claimed in any one of claims 1 to 6 , characterized in that it comprises the following steps: in an organic solvent, in the presence of a base, the compound shown in formula a and [Ir(cod)X ¹ ] ₂ , the compound shown in formula b and [Ir(cod) X ^1a ] ₂ , the compound shown in formula c and [Ir(cod)X ^1b ] ₂ , the compound shown in formula d and [Ir(cod)X ^1c ] ₂ , the compound shown in formula e and [ Ir(cod)X ^1d ] ₂ or the compound shown in formula f and [Ir(cod)X ^1e ] ₂ carry out the complexation reaction shown below; Make general formula I, general formula II, general formula III, The metal iridium complex shown in general formula IV, general formula V or general formula VI;

Wherein, the mark * and the definition of each group are as described in any one of claims 1-6; Y is halogen, CF ₃ SO ₃ , OTf, BF ₄ or ClO ₄ .

10. preparation method as claimed in claim 9 is characterized in that, described organic solvent is one in aromatic hydrocarbon solvent, halogenated hydrocarbon solvent, ether solvent, amide solvent, alkane solvent and nitrile solvent One or more; The aromatic hydrocarbon solvent is preferably one or more of benzene, toluene and xylene; The halogenated hydrocarbon solvent is preferably carbon tetrachloride, methylene chloride and One or more of chloroform; the ether solvent is preferably one or more of tetrahydrofuran, ether and 1,4-dioxane; the amide solvent is preferably It is N,N-dimethylformamide; the alkane solvent is preferably one or more of cyclohexane, n-pentane, n-hexane and n-heptane; the nitrile solvent is preferably Ground is acetonitrile;

And/or, the base is an inorganic base or an organic base, and the inorganic base is preferably sodium carbonate, potassium carbonate, cesium carbonate, potassium phosphate, sodium hydride, sodium methylate, sodium ethylate, sodium acetate, tert-butyl One or more of potassium alkoxide, sodium tert-butoxide and lithium tert-butoxide; the organic base is preferably triethylamine, piperidine, pyridine, N,N-lutidine and 2,6 - one or more of lutidines;

And/or, the [Ir(cod)X ¹ ] ₂ and the compound shown in formula a, [Ir(cod)X ^1a ] ₂ and the compound shown in formula b, [Ir(cod)X ^1b ] ₂ and the compound shown in formula c, [Ir(cod)X ^1c ] ₂ and the compound shown in formula d, [Ir(cod)X ^1d ] ₂ and the compound shown in formula e or [Ir( The molar ratio of cod)X ^1e ] ₂ to the compound shown in formula f is 1:1-1:3.5; preferably 1:2-1:3.5;

And/or, said [Ir(cod)X ¹ ] ₂ , [Ir(cod)X ^1a ] ₂ , [Ir(cod)X ^1b ] ₂ , [Ir(cod)X ^1c ] ₂ , [Ir( The molar ratio of cod)X ^1d ] ₂ or [Ir(cod)X ^1e ] ₂ to base is 1:1-1:20; preferably 2:15-1:20;

And/or, the organic solvent and [Ir(cod)X ¹ ] ₂ , [Ir(cod)X ^1a ] ₂ , [Ir(cod)X ^1b ] ₂ , [Ir(cod)X ^1c ] ₂ , The volume to mass ratio of [Ir(cod)X ^1d ] ₂ or [Ir(cod)X ^1e ] ₂ is 0.1mL/mg-1mL/mg;

And/or, the temperature of the complexation reaction is 0°C-150°C; preferably 25°C-125°C;

And/or, the complexation reaction time is 24-48 hours.

11. a metal iridium complex shown in general formula I, general formula II, general formula III, general formula IV, general formula V or general formula VI as catalyzer as any one of claim 1～6 Applications in asymmetric allyl substitution reactions.

12. The application according to claim 11, characterized in that the asymmetric allyl substitution reaction comprises the following steps: in an organic solvent, under the action of a base, in any one of claims 1 to 6 Under the catalysis of one or more of the metal iridium complexes shown in the general formula I, general formula II, general formula III, general formula IV, general formula V or general formula VI, it will be as shown in formula S1 The compound is subjected to the asymmetric allyl substitution reaction shown below to obtain the benzindole compound shown in the formula P; wherein, the carbon marked with * is a chiral carbon or an achiral carbon, when it is chiral When a chiral carbon is present, the chiral carbon is in the S configuration or the R configuration;

In the compound shown in formula S1 and the compound shown in formula P, R _a1 is monosubstituted or multisubstituted, the same or different, and is selected from one or more of the following substituents: halogen, substituted or unsubstituted C ₁ -C ₄ alkyl, or substituted or unsubstituted C ₁ -C ₄ alkoxy; R _b1 is substituted or unsubstituted C ₁ -C ₄ alkyl, or substituted or unsubstituted C ₂ - Alkenyl of C ₄ ; R _c1 is Wherein, M is NH or O; R _d1 is C ₁ -C ₄ alkyl, C ₁ -C ₄ alkyl or C ₁ -C ₄ alkoxy substituted by one or more halogens; R _e1 is C ₁ -C ₄ alkyl or C ₆ -C ₂₀ aryl; R _a1 and R _b1 , the substituted C ₁ -C ₄ alkyl or the substituted C ₁ -C ₄ alkane The substitution mentioned in the oxy refers to being substituted by one or more of the following substituents: halogen, C ₁ -C ₄ alkoxy, C ₁ -C ₄ alkyl, C ₆ ~C ₂₀ aryl, or For a C ₆ -C ₂₀ aryl group substituted by one or more C ₁ -C ₄ alkoxy groups, when there are multiple substituents, the substituents are the same or different.

13. The application of claim 12, wherein

When the substituted C ₁ -C ₄ alkyl or the substituted C ₁ -C ₄ alkoxy is substituted by halogen, the halogen is F, Cl, Br or I;

When the substituted C ₁ -C ₄ alkyl or the substituted C ₁ -C ₄ alkoxy is substituted by C ₁ -C ₄ alkoxy, the The C ₁ -C ₄ alkoxy group is methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy or tert-butoxy;

When the substituted C ₁ -C ₄ alkyl group or the substituted C ₁ -C ₄ alkoxy group is substituted by a C ₁ -C ₄ alkyl group, the The C ₁ -C ₄ alkyl group is methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl or tert-butyl;

When the substituted C ₁ -C ₄ alkyl group or the substituted C ₁ -C ₄ alkoxy group is substituted by a C ₆ -C ₂₀ aryl group, the The C ₆ -C ₂₀ aryl is phenyl;

When the substituted C ₁ -C ₄ alkyl or the substituted C ₁ -C ₄ alkoxy is substituted by one or more C ₁ -C ₄ alkoxy When C ₆ -C ₂₀ aryl is substituted, the C ₆ -C ₂₀ aryl substituted by one or more C ₁ -C ₄ alkoxy is p-methoxyphenyl.

14. The application of claim 12, wherein

In R _a1 , the halogen is F, Cl, Br or I;

And/or, in R _a1 , the substituted or unsubstituted C ₁ -C ₄ alkyl is substituted or unsubstituted methyl, substituted or unsubstituted ethyl, substituted or unsubstituted n-propyl, Substituted or unsubstituted isopropyl, substituted or unsubstituted n-butyl, substituted or unsubstituted isobutyl, or substituted or unsubstituted tert-butyl; the substituted methyl is benzyl or p-methyl Oxybenzyl;

And/or, in R _a1 , the substituted or unsubstituted C ₁ -C ₄ alkoxy is substituted or unsubstituted methoxy, substituted or unsubstituted ethoxy, substituted or unsubstituted normal Propoxy, substituted or unsubstituted isopropoxy, substituted or unsubstituted n-butoxy, substituted or unsubstituted isobutoxy, or substituted or unsubstituted t-butoxy;

And/or, in R _b1 , the C ₂ -C ₄ alkenyl is vinyl, 1-propenyl, 2-propenyl, 1-butenyl, 2-butenyl or 3-butenyl ;

And/or, in R _d1 or R _e1 , the C ₁ -C ₄ alkyl group is methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl or tert-butyl;

And/or, in R _d1 , the said C ₁ -C ₄ alkyl substituted by one or more halogens said halogen refers to fluorine, chlorine, bromine or iodine; said one or more The C ₁ -C ₄ alkyl described in the halogen-substituted C ₁ -C ₄ alkyl is methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl or tert-butyl; The C ₁ -C ₄ alkyl substituted by one or more halogens is preferably

And/or, in R _d1 , the C ₁ -C ₄ alkoxy group is methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy or tert butoxy;

And/or, in R _e1 , the C ₆ -C ₂₀ aryl is phenyl.

15. The application according to claim 12, characterized in that, in the asymmetric allyl substitution reaction, the organic solvent is an aromatic hydrocarbon solvent, a halogenated hydrocarbon solvent, an ether solvent, an amide solvent One or more in , alkane solvent and nitrile solvent; Described aromatic hydrocarbon solvent is preferably toluene; Described halogenated hydrocarbon solvent is preferably dichloromethane and/or trichloromethane; Described ether solvent is preferably one or more in THF, diethyl ether and 1,4-dioxane; Described alkane solvent is preferably normal hexane; Described nitrile solvent is more Preferably acetonitrile;

And/or, the base is an organic base and/or an inorganic base, and the organic base is preferably 1,8-diazabicycloundec-7-ene, N,N-diisopropyl One or more of ethylamine, triethylamine and 1,4-diazabicyclo[2.2.2]octane; the inorganic base is preferably Cs ₂ CO ₃ , K ₂ CO ₃ , Na ₂ CO ₃ , Li ₂ CO ₃ , lithium tert-butoxide, sodium tert-butoxide and potassium tert-butoxide.