A polysubstituted alkylarylazo compound, its synthesis method and application

Abstract

The present invention discloses a polysubstituted alkylaryl azo compound, its synthesis method, and application. The present invention provides polysubstituted alkylaryl azo compounds as shown in Formula I and Formula II. Using propargyl reagents and hydrazones as substrates and various nitrogen heterocyclic carbene (NHC) ligands, allene products or propargyl-substituted products can be prepared with high selectivity, all of which contain azo functional groups. The polysubstituted alkylaryl azo compounds prepared by the present invention provide a technical solution that is completely different from the prior art for preparing polysubstituted α-quaternary carbon amine compounds, achieving good yield and selectivity. #imgabs0#

Description

Technical Field

[0001] The present invention relates to a polysubstituted alkylarylazo compound, a synthesis method and application thereof. Background Art

[0002] Allenyl-substituted products I and propargyl-substituted products II are very useful synthons, and the rich functional groups in these products can be further transformed. For example, these alkylarylazo compounds can be further converted into α-quaternary amines, providing a method for the synthesis of natural products or pharmaceutically active molecules. The azo functional groups in these alkylarylazo compounds can also be used as luminescent groups in photochemical research [(a) Movassaghi, M.; Ahmad, O.K.; Lathrop, S.P. J. Am. Chem. Soc. 2011, 133, 13002–13005. (b) Lindovska, P.; Movassaghi, M. J. Am. Chem. Soc. 2017, 139, 17590–17596.].

[0003]

[0004] Among them, R 1 , R 3 , R 4 is various aryl, heteroaryl, alkenyl or alkyl substituents; R 2 are various alkyl, cycloalkyl and silicon substituents; R 5 are various aryl and heteroaryl substituents.

[0005] Currently, the synthesis methods for this type of α-quaternary carbon amines are relatively limited [(a) Hager, A.; Vrielink, N.; Hager, D.; Lefranc, J.; Trauner, D. Nat. Prod. Rep. 2016, 33, 491–522. (b) Pierrot, D.; Marek, I. Angew. Chem. Int. Ed. 2020, 59, 36–49.]. Previously, the method commonly used in the literature was to achieve this by the addition reaction of allenyl metal reagents and propargyl metal reagents to imines. In this type of reaction, the allenyl metal reagents and propargyl metal reagents serve as nucleophiles, and the imines serve as electrophiles.

[0006]

[0007] For example, the following literature results show that the product structure is limited, and the yield and regioselectivity are poor.

[0008]

[0009] When constructing two consecutive tertiary or quaternary carbon products with significant steric hindrance, the above method often fails to proceed smoothly, and the resulting product has poor diastereoselectivity and regioselectivity, that is, the product is a mixture of allene and propargyl substituted products.

[0010] The allenyl substituted product I and the propargyl substituted product II can be further transformed, thus enriching the further application of this type of α-quaternary carbon amine. At present, there are many studies on palladium-catalyzed allenylation and propargyl substitution reactions [(a) Tsuji, J.; Watanabe, H.; Minami, I.; Shimizu, IJ Am. Chem. Soc. 1985, 107, 2196. (b) Kenny, M.; Schroder, SP.; Taylor, NJ; Jackson, P.; Kitson, DJ; V.Synthesis 2018,50,1796,and references cited therein.(c)Smith,MK;Tunge,JAOrg.Lett.2017,19,5497.(d)Wu,P.;Jia,M.;Lin,W.;Ma,S.Org.Lett.2018,20,554.(e)Guo,L.- N.; Duan, S. Eur. J. Org. Chem. 2004, 2004, 1175. (h) Tsuji, J.; Mandai, T. Angew. Chem. Int. Ed. Engl. 1995, 34, 2589. (i) Ding, C.-H.; Hou, X.-L. Chem. Rev. 2011, 111, 1914.], however, there are still many problems: 1) the ratio of the allene product to the propargyl substituted product is poor, and a mixture of the two is often obtained; 2) when constructing a product with two consecutive chiral carbons, the reaction efficiency is poor and the diastereoselectivity of the product is also poor.

[0011] Currently, there are not many methods reported in the literature for the synthesis of this type of alkylarylazo compounds. Most of the synthetic methods are based on the addition reaction of diazonium salts to unsaturated bonds [(a) Blank, O.; Heinrich, M.R.Eur. J. Org. Chem. 2006, 4331–4334; (b) Heinrich, M.R.; Blank, O.; Wofel, S. Org. Lett. 2006, 8, 3323–3325; Blank, O.; (c) Raschke, N.; Heinrich, M.R. Tetrahedron Lett. 2010, 51, 1758–1760; (d) Blank, O.; Wetzel, A.; Ullrich, D.; Heinrich, M.R.Eur. J. Org.Chem.2008,3179–3189; (e) Liu, C.; Lv, J.; Luo, S.; Cheng, J.-P.Org.Lett.2014, 16, 5458-5461. (f) Zhang, Y.; Huang, C.; Lin, X.; Hu, Q.; Hu, B.; Zhou, Y.; Zhu, G. Org.Le tt.2019, 21, 2261-2264. (g) Nelson, HM; Patel, JS; Shunatona, HP; Toste, FDChem. Sci. 2015, 6, 170–173. (h) Stephens, DE; Larionov, OVEur. However, these synthetic methods have their insurmountable limitations: narrow substrate range, low raw material utilization, cumbersome process, and no effective synthetic method for this type of azo products (allenyl substituted product I and propargyl substituted product II).

[0012] Therefore, there is currently a lack of efficient synthetic methods for preparing α-quaternary carbon amines and allenyl-substituted products I and propargyl-substituted products II. Summary of the Invention

[0013] The technical problem to be solved by the present invention is to overcome the problem of insufficient preparation methods of polysubstituted alkyl aryl azo compounds and α-quaternary carbon amines in the prior art; and provide a polysubstituted alkyl aryl azo compound, its synthesis method and application. The method provided by the present invention is very simple and efficient, and can prepare polysubstituted alkyl (can construct two consecutive tertiary carbons and quaternary carbons with large steric hindrance) aryl azo compounds with high yield and high diastereoselectivity, and can prepare allene products or propargyl substituted products with high selectivity by using different nitrogen heterocyclic carbene (NHC) ligands, and the prepared products all contain azo functional groups. The polysubstituted alkyl aryl azo compound prepared by the present invention provides a technical solution that is completely different from the prior art concept to prepare polysubstituted α-quaternary carbon amine compounds, and achieves good yield and selectivity.

[0014] The present invention solves the above technical problems through the following technical solutions.

[0015] The present invention provides a polysubstituted alkylaryl azo compound as shown in Formula I and Formula II:

[0016]

[0017] Among them, R 1 are independently H, C1-C 10 Alkyl, one or more R 1a Substituted C1-C 10 Alkyl, C2-C 10 Alkenyl, one or more R 1b Substituted C2-C 10 Alkenyl, C6-C 14 The aryl group, one or more R 1c Substituted C6-C 14 aryl, 5-10 membered heteroaryl or one or more R 1d substituted 5-10 membered heteroaryl; when there are multiple substituents, they are the same or different; the 5-10 membered heteroaryl and the one or more R 1d In the 5-10 membered heteroaryl group of the substituted 5-10 membered heteroaryl group, the heteroatom is selected from one or more of N, O and S, and the number of the heteroatoms is 1, 2, 3 or 4;

[0018] R 2 Independently C1-C 10 Alkyl, one or more R 2a Substituted C1-C 10 Alkyl, C3-C 10 Cycloalkyl, one or more R 2b Substituted C3-C 10 Cycloalkyl or When there are multiple substituents, they may be the same or different;

[0019] R 3 and R 4 Independently C1-C 10 Alkyl, one or more R 3a Substituted C1-C 10 Alkyl, C2-C 10 Alkenyl, one or more R 3b Substituted C2-C 10 Alkenyl, C6-C 14 The aryl group, one or more R 3c Substituted C6-C 14 aryl, 5-10 membered heteroaryl or one or more R 3d Substituted 5-10 membered heteroaryl; when there are multiple substituents, they are the same or different; the 5-10 membered heteroaryl may be replaced by one or more R 3d In the 5-10 membered heteroaryl group of the substituted 5-10 membered heteroaryl group, the heteroatom is selected from one or more of N, O and S, and the number of the heteroatoms is 1, 2, 3 or 4;

[0020] Or, R 3 and R 4 connected, independently forming with the carbon to which it is connected: C3-C 10 The cycloalkyl group or one or more R 4a Substituted C3-C 10 When there are multiple substituents, they may be the same or different;

[0021] R 5 Independently C6-C 14 The aryl group, one or more R 5a Substituted C6-C 14 aryl, 5-10 membered heteroaryl or one or more R 5b substituted 5-10 membered heteroaryl; when there are multiple substituents, they are the same or different; the 5-10 membered heteroaryl and the one or more R 5b In the 5-10 membered heteroaryl group of the substituted 5-10 membered heteroaryl group, the heteroatom is selected from one or more of N, O and S, and the number of the heteroatoms is 1, 2, 3 or 4;

[0022] R 1a 、R 1b 、R 1c 、R 1d 、R 2a 、R 2b 、R 3a 、R 3b 、R 3c 、R 3d 、R4a 、R 5a and R 5b are independently CN, halogen, C1-C6 alkyl, C1-C6 alkyl-O-, C1-C6 alkyl-OC(=O)-, -O-(C1-C4 alkylene)-O-, phenyl or The C1-C6 alkyl, C1-C6 alkyl-O-, C1-C6 alkyl-OC(=O)-, -O-(C1-C4 alkylene)-O- and phenyl groups are optionally substituted by one or more substituents R 7a Replacement, R 7a are independently CN, halogen, C1-C6 alkyl or C1-C6 alkyl-O-; when there are multiple substituents, they are the same or different;

[0023] R 2c 、R 2d 、R 2e 、R 6a 、R 6b and R 6c are independently C1-C6 alkyl;

[0024] The carbon atom marked with "*" indicates that when it is a chiral carbon atom, it is in S configuration, R configuration or a mixture thereof.

[0025] In certain preferred embodiments of the present invention, certain groups in the polysubstituted alkylarylazo compounds of Formula I and Formula II are defined as follows (unmentioned groups are the same as those described in any embodiment of the present application):

[0026] When R 1 Independently C1-C 10 The alkyl group or one or more R 1a Substituted C1-C 10 When the alkyl group is C1-C 10 The alkyl group and one or more R 1a Substituted C1-C 10 The C1-C 10 The alkyl group is C1-C4 alkyl (for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl or tert-butyl); for example, methyl, n-propyl or isopropyl.

[0027] In certain preferred embodiments of the present invention, certain groups in the polysubstituted alkylarylazo compounds of Formula I and Formula II are defined as follows (unmentioned groups are the same as those described in any embodiment of the present application):

[0028] When R 1 Independently C2-C 10 The alkenyl group or one or more R 1b Substituted C2-C10 When the alkenyl group, the C2-C 10 The alkenyl group and one or more R 1b Substituted C2-C 10 The C2-C 10 The alkenyl group is a C2-C4 alkenyl group {such as ethenyl, propenyl (such as 1-propenyl or 2-propenyl) or butenyl (such as 2-butenyl, 1-butenyl or butadienyl)}; for example, allyl (-CH2CH=CH2).

[0029] In certain preferred embodiments of the present invention, certain groups in the polysubstituted alkylarylazo compounds of Formula I and Formula II are defined as follows (unmentioned groups are the same as those described in any embodiment of the present application):

[0030] When R 1 Independently C6-C 14 The aryl group or one or more R 1c Substituted C6-C 14 When the aryl group is C6-C 14 The aryl group and one or more R 1c Substituted C6-C 14 The C6-C 14 The aryl group is phenyl or naphthyl.

[0031] In certain preferred embodiments of the present invention, certain groups in the polysubstituted alkylarylazo compounds of Formula I and Formula II are defined as follows (unmentioned groups are the same as those described in any embodiment of the present application):

[0032] When R 1 is independently a 5-10 membered heteroaryl or is replaced by one or more R 1d When the 5-10 membered heteroaryl is substituted, the 5-10 membered heteroaryl may be replaced by one or more R 1d In the 5-10 membered heteroaryl group of the substituted 5-10 membered heteroaryl group, the heteroatom is selected from one or more of N, O and S, and the number of heteroatoms is 1, 2 or 3; for example, furyl, thienyl, benzofuranyl or indolyl.

[0033] In certain preferred embodiments of the present invention, certain groups in the polysubstituted alkylarylazo compounds of Formula I and Formula II are defined as follows (unmentioned groups are the same as those described in any embodiment of the present application):

[0034] When R 2 Independently C1-C 10 The alkyl group or one or more R 2a Substituted C1-C 10 When the alkyl group is C1-C 10The alkyl group and one or more R 2a Substituted C1-C 10 The C1-C 10 The alkyl group is C1-C4 alkyl (eg methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl or tert-butyl); for example n-butyl.

[0035] In certain preferred embodiments of the present invention, certain groups in the polysubstituted alkylarylazo compounds of Formula I and Formula II are defined as follows (unmentioned groups are the same as those described in any embodiment of the present application):

[0036] When R 2 Independently C3-C 10 The cycloalkyl group or one or more R 2b Substituted C3-C 10 When the cycloalkyl group is 10 The cycloalkyl group and one or more R 2b Substituted C3-C 10 The C3-C 10 The cycloalkyl group is a C3-C6 cycloalkyl group (for example, cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl), for example, cyclopentyl or cyclohexyl.

[0037] In certain preferred embodiments of the present invention, certain groups in the polysubstituted alkylarylazo compounds of Formula I and Formula II are defined as follows (unmentioned groups are the same as those described in any embodiment of the present application):

[0038] When R 3 and R 4 Independently C1-C 10 The alkyl group or one or more R 3a Substituted C1-C 10 When the alkyl group is C1-C 10 The alkyl group and one or more R 3a Substituted C1-C 10 The C1-C 10 The alkyl group is C1-C4 alkyl (for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl or tert-butyl); for example, methyl, ethyl or isobutyl.

[0039] In certain preferred embodiments of the present invention, certain groups in the polysubstituted alkylarylazo compounds of Formula I and Formula II are defined as follows (unmentioned groups are the same as those described in any embodiment of the present application):

[0040] When R 3 and R 4 Independently C2-C 10The alkenyl group or one or more R 3b Substituted C2-C 10 When the alkenyl group, the C2-C 10 The alkenyl group and one or more R 3b Substituted C2-C 10 The C2-C 10 The alkenyl group is a C2-C4 alkenyl group {such as ethenyl, propenyl (such as 1-propenyl or 2-propenyl) or butenyl (such as 2-butenyl, 1-butenyl or butadienyl)}; for example, allyl (-CH2CH=CH2).

[0041] In certain preferred embodiments of the present invention, certain groups in the polysubstituted alkylarylazo compounds of Formula I and Formula II are defined as follows (unmentioned groups are the same as those described in any embodiment of the present application):

[0042] When R 3 and R 4 Independently C6-C 14 The aryl group or one or more R 3c Substituted C6-C 14 When the aryl group is C6-C 14 The aryl group and one or more R 3c Substituted C6-C 14 The C6-C 14 The aryl group is phenyl or naphthyl (e.g.

[0043] In certain preferred embodiments of the present invention, certain groups in the polysubstituted alkylarylazo compounds of Formula I and Formula II are defined as follows (unmentioned groups are the same as those described in any embodiment of the present application):

[0044] When R 3 and R 4 is independently a 5-10 membered heteroaryl or is replaced by one or more R 3d When the 5-10 membered heteroaryl is substituted, the 5-10 membered heteroaryl and one or more R 3d In the 5-10 membered heteroaryl group of the substituted 5-10 membered heteroaryl group, the heteroatom is selected from one or more of N, O and S, and the number of heteroatoms is 1, 2 or 3; for example, furyl (for example ), thienyl (e.g. ), benzofuranyl (e.g. ) or indolyl (e.g. ).

[0045] In certain preferred embodiments of the present invention, certain groups in the polysubstituted alkylarylazo compounds of Formula I and Formula II are defined as follows (unmentioned groups are the same as those described in any embodiment of the present application):

[0046] When R 3 and R 4 connected, independently forming with the carbon to which it is connected: C3-C 10 The cycloalkyl group or one or more R 4a Substituted C3-C 10 When the cycloalkyl group is 10 The cycloalkyl group and one or more R 4a Substituted C3-C 10 The C3-C 10 The cycloalkyl group is a C3-C6 cycloalkyl group (eg cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl), for example cyclohexyl.

[0047] In certain preferred embodiments of the present invention, certain groups in the polysubstituted alkylarylazo compounds of Formula I and Formula II are defined as follows (unmentioned groups are the same as those described in any embodiment of the present application):

[0048] When R 5 Independently C6-C 14 The aryl group or one or more R 5a Substituted C6-C 14 When the aryl group is 14 The aryl group and one or more R 5a Substituted C6-C 14 The C6-C 14 The aryl group is phenyl or naphthyl (e.g.

[0049] In certain preferred embodiments of the present invention, certain groups in the polysubstituted alkylarylazo compounds of Formula I and Formula II are defined as follows (unmentioned groups are the same as those described in any embodiment of the present application):

[0050] When R 5 is independently a 5-10 membered heteroaryl or is replaced by one or more R 5b When the 5-10 membered heteroaryl is substituted, the 5-10 membered heteroaryl and one or more R 5b In the 5-10 membered heteroaryl group of the substituted 5-10 membered heteroaryl group, the heteroatom is selected from one or more of N, O and S, and the number of heteroatoms is 1, 2 or 3; for example, furyl, thienyl, benzofuranyl or indolyl.

[0051] In certain preferred embodiments of the present invention, certain groups in the polysubstituted alkylarylazo compounds of Formula I and Formula II are defined as follows (unmentioned groups are the same as those described in any embodiment of the present application):

[0052] When R 1a 、R 1b 、R 1c 、R 1d 、R 2a 、R 2b 、R 2c 、R 2d 、R 2e 、R 3a 、R 3b 、R 3c 、R 3d 、R 4a 、R 5a 、R 5b 、R 6a 、R 6b and R 6c When the group is independently C1-C6 alkyl, C1-C6 alkyl-O- or C1-C6 alkyl-OC(=O)-, the C1-C6 alkyl in the C1-C6 alkyl, C1-C6 alkyl-O- and C1-C6 alkyl-OC(=O)- is C1-C4 alkyl (for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl or tert-butyl); for example, methyl or tert-butyl.

[0053] In certain preferred embodiments of the present invention, certain groups in the polysubstituted alkylarylazo compounds of Formula I and Formula II are defined as follows (unmentioned groups are the same as those described in any embodiment of the present application):

[0054] When R 1a 、R 1b 、R 1c 、R 1d 、R 2a 、R 2b 、R 3a 、R 3b 、R 3c 、R 3d 、R 4a 、R 5a 、R 5b and R 7a When independently halogen, the halogen is fluorine, chlorine, bromine or iodine, for example fluorine or chlorine.

[0055] In certain preferred embodiments of the present invention, certain groups in the azo compounds shown in Formula I and Formula II are defined as follows (unmentioned groups are the same as those described in any embodiment of the present application):

[0056] When R1a 、R 1b 、R 1c 、R 1d 、R 2a 、R 2b 、R 3a 、R 3b 、R 3c 、R 3d 、R 4a 、R 5a and R 5b When independently -O-(C1-C4 alkylene)-O-, the C1-C4 alkylene is methylene, ethylene (e.g., -CH2CH2- or -CH(CH3)-) or isopropylidene (e.g., -CH(CH3)CH2- or -C(CH3)2-); for example, methylene or ethylene.

[0057] In certain preferred embodiments of the present invention, certain groups in the polysubstituted alkylarylazo compounds of Formula I and Formula II are defined as follows (unmentioned groups are the same as those described in any embodiment of the present application):

[0058] When R 7a When they are independently C1-C6 alkyl or C1-C6 alkyl-O-, the C1-C6 alkyl in the C1-C6 alkyl and C1-C6 alkyl-O- is C1-C4 alkyl (e.g., methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl or tert-butyl); for example, methyl.

[0059] In certain preferred embodiments of the present invention, certain groups in the polysubstituted alkylarylazo compounds of Formula I and Formula II are defined as follows (unmentioned groups are the same as those described in any embodiment of the present application):

[0060] When R 1 Independently by one or more R 1a Substituted C1-C 10 When the alkyl group is 1a Phenyl or (e.g. tert-butyldimethylsilyloxy (TBSO-)).

[0061] In certain preferred embodiments of the present invention, certain groups in the polysubstituted alkylarylazo compounds of Formula I and Formula II are defined as follows (unmentioned groups are the same as those described in any embodiment of the present application):

[0062] When R 2 Independently hour, It is trimethylsilyl (TMS).

[0063] In certain preferred embodiments of the present invention, certain groups in the polysubstituted alkylarylazo compounds of Formula I and Formula II are defined as follows (unmentioned groups are the same as those described in any embodiment of the present application):

[0064] When R 3 and R 4 Independently by one or more R 3a Substituted C1-C 10 When the alkyl group is 3a is phenyl or R 7a Substituted phenyl, such as R 7a It is C1-C6 alkyl-O- (for example, 4-methoxy).

[0065] In certain preferred embodiments of the present invention, certain groups in the polysubstituted alkylarylazo compounds of Formula I and Formula II are defined as follows (unmentioned groups are the same as those described in any embodiment of the present application):

[0066] When R 3 and R 4 Independently by one or more R 3c Substituted C6-C 14 When the aryl group is 3c It is CN, halogen (e.g., fluorine, chlorine), C1-C6 alkyl (e.g., methyl), C1-C6 alkyl-O-(e.g., methoxy), C1-C6 alkyl-OC(=O)-(e.g., methyl-OC(=O)-) or -O-(C1-C4 alkylene)-O-(e.g., -O-(CH2)-O-).

[0067] In certain preferred embodiments of the present invention, certain groups in the polysubstituted alkylarylazo compounds of Formula I and Formula II are defined as follows (unmentioned groups are the same as those described in any embodiment of the present application):

[0068] R 1 are independently H, C1-C 10 Alkyl, one or more R 1a Substituted C1-C 10 Alkyl, C2-C 10 The alkenyl group or one or more R 1b Substituted C2-C 10 Alkenyl; for example, H, C1-C 10 Alkyl, one or more R 1a Substituted C1-C 10 Alkyl or C2-C 10 of alkenyl.

[0069] In certain preferred embodiments of the present invention, certain groups in the polysubstituted alkylarylazo compounds of Formula I and Formula II are defined as follows (unmentioned groups are the same as those described in any embodiment of the present application):

[0070] R 2 Independently C1-C 10 Alkyl, one or more R 2a Substituted C1-C 10 Alkyl, C3-C 10 Cycloalkyl or

[0071] In certain preferred embodiments of the present invention, certain groups in the polysubstituted alkylarylazo compounds of Formula I and Formula II are defined as follows (unmentioned groups are the same as those described in any embodiment of the present application):

[0072] R 3 and R 4 Independently C1-C 10 Alkyl, one or more R 3a Substituted C1-C 10 Alkyl, C6-C 14 The aryl group, one or more R 3c Substituted C6-C 14 aryl, 5-10 membered heteroaryl or one or more R 3d substituted 5-10 membered heteroaryl;

[0073] For example, R 3 and R 4 One of them is independently C1-C 10 Alkyl, one or more R 3a Substituted C1-C 10 Alkyl; R 3 and R 4 The other one of them is independently C1-C 10 Alkyl, one or more R 3a Substituted C1-C 10 Alkyl, C6-C 14 The aryl group, one or more R 3c Substituted C6-C 14 aryl, 5-10 membered heteroaryl or one or more R 3d substituted 5-10 membered heteroaryl; for example, one or more R 3a Substituted C1-C 10 Alkyl, C6-C 14 The aryl group, one or more R 3c Substituted C6-C 14aryl, 5-10 membered heteroaryl or one or more R 3d Substituted 5-10 membered heteroaryl.

[0074] In certain preferred embodiments of the present invention, certain groups in the polysubstituted alkylarylazo compounds of Formula I and Formula II are defined as follows (unmentioned groups are the same as those described in any embodiment of the present application):

[0075] R 5 Independently C6-C 14 The aryl group, one or more R 5a Substituted C6-C 14 Aryl; for example, C6-C 14 of aromatic groups.

[0076] In certain preferred embodiments of the present invention, in the polysubstituted alkylaryl azo compound as shown in Formula I,

[0077] When the carbon atoms with "*" at positions 1 and 2 are both chiral carbon atoms, and according to the "sequence rule" of the substituents, R 4 Prioritizes R 3 When , it is as shown below:

[0078] and / or its enantiomers.

[0079] In certain preferred embodiments of the present invention, in the polysubstituted alkylaryl azo compound as shown in Formula II,

[0080] When the carbon atoms with "*" at positions 1 and 2 are both chiral carbon atoms, and according to the "sequence rule" of the substituents, R 4 Prioritizes R 3 When , it is as shown below:

[0081] and / or its enantiomers.

[0082] In certain preferred embodiments of the present invention, certain groups in the polysubstituted alkylarylazo compounds of Formula I and Formula II are defined as follows (unmentioned groups are the same as those described in any embodiment of the present application):

[0083] R 1 and independently H, methyl, n-propyl, isopropyl, allyl, tert-butyldimethylsilyloxy-substituted methyl (TBSO-CH2-) or benzyl.

[0084] In certain preferred embodiments of the present invention, certain groups in the polysubstituted alkylarylazo compounds of Formula I and Formula II are defined as follows (unmentioned groups are the same as those described in any embodiment of the present application):

[0085] R 2 are independently trimethylsilyl (TMS), n-butyl, cyclopentyl or cyclohexyl.

[0086] In certain preferred embodiments of the present invention, certain groups in the polysubstituted alkylarylazo compounds of Formula I and Formula II are defined as follows (unmentioned groups are the same as those described in any embodiment of the present application):

[0087] R 3 and R 4 are independently methyl, ethyl, isobutyl, benzyl, phenyl, 4-fluorophenyl, 4-chlorophenyl, 4-methoxyphenyl, 4-methoxyacylphenyl, 4-cyano-phenyl, 3-methylphenyl, 3-methoxyphenyl, 2-fluoro-phenyl, 2-methoxyphenyl,

[0088] In certain preferred embodiments of the present invention, certain groups in the polysubstituted alkylarylazo compounds of Formula I and Formula II are defined as follows (unmentioned groups are the same as those described in any embodiment of the present application):

[0089] When R 3 and R 4 When the C3-C7 cycloalkyl group is connected to each other to form a C3-C7 cycloalkyl group, the C3-C7 cycloalkyl group is independently a cyclohexyl group.

[0090] In certain preferred embodiments of the present invention, certain groups in the polysubstituted alkylarylazo compounds of Formula I and Formula II are defined as follows (unmentioned groups are the same as those described in any embodiment of the present application):

[0091] R 5 are independently phenyl.

[0092] In certain preferred embodiments of the present invention, the polysubstituted alkylarylazo compound as shown in Formula I is selected from the following group or its enantiomers:

[0093]

[0094]

[0095] In certain preferred embodiments of the present invention, the polysubstituted alkylarylazo compound as shown in Formula II is selected from the following group or its enantiomers:

[0096]

[0097]

[0098] The second aspect of the present invention provides a method for preparing the polysubstituted alkylarylazo compound of formula I and / or formula II according to the first aspect of the present invention, the method comprising the following steps:

[0099] Step 1: In a solvent, a hydrazone as shown in Formula IV is subjected to a hydrogen extraction reaction with a strong base to obtain a mixture A;

[0100] Step 2: In the presence of an NHC-Pd catalyst system and a base, the mixture A and a propargyl reagent represented by Formula III are subjected to a coupling reaction as shown below to obtain a polysubstituted alkylaryl azo compound represented by Formula I and / or Formula II;

[0101] The nitrogen heterocyclic carbene is as shown in Formula V;

[0102]

[0103] Wherein, X is a halogen;

[0104] R 8a and R 8a’ are independently H or phenyl;

[0105] Or, R 8a and R 8a’ connected to it Together they form a benzene ring;

[0106] R 8b and R 8b’ Independently C5-C 10 The polycyclic cycloalkyl group or one or more R 10a Substituted C5-C 10 When there are multiple substituents, they may be the same or different;

[0107] n1 is independently 0, 1, 2 or 3;

[0108] R 9a 、R 9b and R 9c are independently halogen, C1-C6 alkyl, 10c Substituted C1-C6 alkyl, C3-C7 cycloalkyl, one or more R 10b Substituted C3-C7 cycloalkyl; when there are multiple substituents, they may be the same or different;

[0109] R 9d are independently H, C1-C6 alkyl or one or more R 10d Substituted C1-C6 alkyl; when there are multiple substituents, they may be the same or different;

[0110] R 9e Independently C6-C 14 The aryl group or one or more R 10e Substituted C6-C 14 When there are multiple substituents, they may be the same or different;

[0111] R 10a 、R 10b 、R 10c 、R 10d and R 10e are independently C1-C6 alkyl or phenyl;

[0112] Indicates a single bond or a double bond;

[0113] The remaining groups R 1 、R 2 、R 3 、R 4 、R 5 and “*” are as defined in the first aspect of the present invention.

[0114] In one embodiment of the present invention, the solvent can be a conventional solvent used in this type of reaction, such as one or a combination of two or more of an aromatic hydrocarbon solvent, an ether solvent, a halogenated hydrocarbon solvent, and a cycloalkane solvent. The aromatic hydrocarbon solvent can be one or a combination of two or more of toluene, xylene, and mesitylene; the ether solvent can be one or a combination of two or more of tetrahydrofuran, diethyl ether, and dioxane; the halogenated hydrocarbon solvent can be dichloromethane and / or chloroform; and the cycloalkane solvent can be cyclohexane. Another example is toluene. The amount of the solvent used is not specifically limited, provided it does not affect the reaction. For example, the mass volume ratio of the propargyl reagent represented by Formula III to the solvent can be 1 g / L to 50 g / L (e.g., 5 g / L to 20 g / L), or the molar volume ratio of the hydrazone represented by Formula IV to the solvent can be 0.01 mol / L to 10 mol / L (e.g., 0.05 mol / L to 0.2 mol / L).

[0115] In one embodiment of the present invention, the nitrogen heterocyclic carbene-palladium catalyst system may be a mixture of a metal palladium precursor and a nitrogen heterocyclic carbene ligand precursor as shown in formula V';

[0116] wherein Y is independently Cl, OTf or BF4; for example, Cl or BF4.

[0117] The metal palladium precursor is selected from the group consisting of one or a combination of two or more of Pd(OAc)2, Pd2(dba)3 (tris(dibenzylideneacetone)dipalladium), Pd(dba)2 (bis(dibenzylideneacetone)palladium), Pd2(dba)3·CHCl3, [Pd(C3H5)Cl]2 (allylpalladium(II) chloride dimer), [Pd(cinnammyl)Cl]2 (palladium(π-cinnammyl) chloride dimer) and Pd(PPh3)4; for example, [Pd(η 3 -C3H5)Cl]2.

[0118] In one embodiment of the present invention, the nitrogen heterocyclic carbene-palladium catalytic system is a complex of the metal palladium precursor and the nitrogen heterocyclic carbene ligand precursor as shown in formula V' (ie, nitrogen heterocyclic carbene-palladium complex).

[0119] In one embodiment of the present invention, the molar ratio of the nitrogen heterocyclic carbene ligand precursor represented by formula V' to the metal palladium precursor can be a conventional molar ratio in the art, for example (1-3):1; preferably 2:1.

[0120] In one embodiment of the present invention, the molar ratio of the hydrazone represented by Formula IV to the metal palladium precursor can be a conventional molar ratio in the art, for example, 2:(0.01-0.5).

[0121] In one embodiment of the present invention, in step 1, the strong base may be a conventional strong base in this type of reaction in the art, such as an alkali metal amide or an alkali metal alkyl; for example, LiHMDS (lithium bis(trimethylsilyl)amide), NaHMDS, KHMDS, LDA (lithium diisopropylamide), n BuLi and One or a combination of two or more thereof; for example, LiHMDS.

[0122] In one embodiment of the present invention, in step 2, the base may be an alkali metal alkylate, an alkali metal alkyl alcoholate or an alkali metal amide; for example t BuOK, t BuOLi, t BuONa, LDA, and n One or a combination of two or more of BuLi; for example t Bu OK.

[0123] In one embodiment of the present invention, the molar ratio of the hydrazone of Formula IV to the propargyl reagent of Formula III can be a conventional molar ratio in the art, for example, 2:(1-2).

[0124] In one embodiment of the present invention, in step 1, the molar ratio of the hydrazone represented by formula IV to the strong base can be a conventional molar ratio in the art, for example, 1:1.

[0125] In one embodiment of the present invention, in step 2, the molar ratio of the nitrogen heterocyclic carbene ligand precursor to the base can be a conventional molar ratio in the art, such as 1:(1-5), or 1:2.5.

[0126] In one embodiment of the present invention, in step 1, the reaction temperature is -10°C to 80°C, for example, 0-30°C.

[0127] In one embodiment of the present invention, in step 2, the reaction temperature is 0°C to 80°C, for example, 10-30°C.

[0128] The progress of the coupling reaction can be monitored by conventional monitoring methods in the art (e.g., TLC, HPLC, NMR, or GC). The reaction endpoint is generally determined when the hydrazone of Formula IV and the propargyl reagent of Formula III disappear or cease to react. The reaction time can be 2 to 24 hours, for example, 12 to 24 hours.

[0129] In one embodiment of the present invention, the preparation method may further include post-treatment, which may be conventional post-treatment in the art, for example, comprising the following steps: after completion of the coupling reaction, quenching (e.g., adding water), and separation by thin layer chromatography and / or column chromatography. The eluent for the column chromatography may be ethyl acetate.

[0130] In certain preferred embodiments of the present invention, certain groups in the propargyl reagent shown in III are defined as follows (unmentioned groups are the same as those described in any embodiment of the present application),

[0131] Said X is chlorine or bromine.

[0132] In certain preferred embodiments of the present invention, certain groups in the nitrogen heterocyclic carbene as shown in Formula V are defined as follows (unmentioned groups are the same as those described in any embodiment of the present application),

[0133] R 8b and R 8b’ Independently C5-C 10 The polycyclic cycloalkyl group or one or more R 10a Substituted C5-C 10 When the polycyclic cycloalkyl group is C5-C 10 The polycyclic cycloalkyl group and one or more R 10a Substituted C5-C 10 The C5-C 10 The polycyclic cycloalkyl group of is adamantyl group (e.g. ) or bicyclo[3.1.1]heptyl (e.g. For example

[0134] In certain preferred embodiments of the present invention, certain groups in the nitrogen heterocyclic carbene as shown in Formula V are defined as follows (unmentioned groups are the same as those described in any embodiment of the present application),

[0135] n1 is independently 0 or 1.

[0136] In certain preferred embodiments of the present invention, certain groups in the nitrogen heterocyclic carbene as shown in Formula V are defined as follows (unmentioned groups are the same as those described in any embodiment of the present application),

[0137] When R 9a 、R 9b and R 9c is independently a C1-C6 alkyl group or is replaced by one or more R 10c When the C1-C6 alkyl group is substituted, the C1-C6 alkyl group is replaced by one or more R 10c The C1-C6 alkyl group in the substituted C1-C6 alkyl group is a C1-C4 alkyl group (for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl or tert-butyl); for example, methyl or isopropyl.

[0138] In certain preferred embodiments of the present invention, certain groups in the nitrogen heterocyclic carbene as shown in Formula V are defined as follows (unmentioned groups are the same as those described in any embodiment of the present application),

[0139] When R 9a 、R 9b and R 9c When independently halogen, the halogen is chlorine or fluorine; for example, fluorine.

[0140] In certain preferred embodiments of the present invention, certain groups in the nitrogen heterocyclic carbene as shown in Formula V are defined as follows (unmentioned groups are the same as those described in any embodiment of the present application),

[0141] When R 9a 、R 9b and R 9c is independently a C3-C7 cycloalkyl group or is replaced by one or more R 10b When the C3-C7 cycloalkyl group is substituted, the C3-C7 cycloalkyl group and one or more R 10b The C3-C7 cycloalkyl group in the substituted C3-C7 cycloalkyl group is cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl, for example cyclohexyl.

[0142] In certain preferred embodiments of the present invention, certain groups in the nitrogen heterocyclic carbene as shown in Formula V are defined as follows (unmentioned groups are the same as those described in any embodiment of the present application),

[0143] When R 9d is independently a C1-C6 alkyl group or is replaced by one or more R 10d When the C1-C6 alkyl group is substituted, the C1-C6 alkyl group is replaced by one or more R 10d The C1-C6 alkyl group in the substituted C1-C6 alkyl group is a C1-C4 alkyl group (e.g., methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl or tert-butyl); for example, methyl or tert-butyl.

[0144] In certain preferred embodiments of the present invention, certain groups in the nitrogen heterocyclic carbene as shown in Formula V are defined as follows (unmentioned groups are the same as those described in any embodiment of the present application),

[0145] When R 9e Independently C6-C 14 The aryl group or one or more R 10e Substituted C6-C 14 When the aryl group is C6-C 14 The aryl group and one or more R 10e Substituted C6-C 14 The C6-C 14 The aryl group is phenyl or naphthyl (for example

[0146] In certain preferred embodiments of the present invention, certain groups in the nitrogen heterocyclic carbene as shown in Formula V are defined as follows (unmentioned groups are the same as those described in any embodiment of the present application),

[0147] When R 10a 、R 10c 、R 10d and R 10e When they are independently C1-C6 alkyl, the C1-C6 alkyl is C1-C4 alkyl (such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl or tert-butyl); for example, methyl or isopropyl.

[0148] In certain preferred embodiments of the present invention, certain groups in the nitrogen heterocyclic carbene (NHC) ligand precursor as shown in Formula V are defined as follows (unmentioned groups are the same as those described in any embodiment of the present application),

[0149] R 9a 、R 9b and R 9c is independently fluoro, methyl, isopropyl, benzhydryl or cyclohexyl.

[0150] In certain preferred embodiments of the present invention, certain groups in the nitrogen heterocyclic carbene (NHC) ligand precursor as shown in Formula V are defined as follows (unmentioned groups are the same as those described in any embodiment of the present application),

[0151] R 9d is independently H, methyl or tert-butyl.

[0152] In certain preferred embodiments of the present invention, certain groups in the nitrogen heterocyclic carbene (NHC) ligand precursor as shown in Formula V are defined as follows (unmentioned groups are the same as those described in any embodiment of the present application),

[0153] R 9e are independently phenyl, 2-methylphenyl or naphthyl.

[0154] In certain preferred embodiments of the present invention, certain groups in the nitrogen heterocyclic carbene (NHC) ligand precursor as shown in Formula V are defined as follows (unmentioned groups are the same as those described in any embodiment of the present application),

[0155] R 8b and R 8b’ Independently C5-C 10 The polycyclic cycloalkyl group or one or more R 10a Substituted C5-C 10 of a polycyclic cycloalkyl group.

[0156] In certain preferred embodiments of the present invention, certain groups in the nitrogen heterocyclic carbene (NHC) ligand precursor as shown in Formula V are defined as follows (unmentioned groups are the same as those described in any embodiment of the present application),

[0157] R 8b and R 8b’ Independently

[0158] In certain preferred embodiments of the present invention, certain groups in the nitrogen heterocyclic carbene (NHC) ligand precursor as shown in Formula V are defined as follows (unmentioned groups are the same as those described in any embodiment of the present application),

[0159] R 8b and R 8b’ Independently C5-C 10 The polycyclic cycloalkyl group or one or more R 10a Substituted C5-C 10 of a polycyclic cycloalkyl group.

[0160] In certain preferred embodiments of the present invention, certain groups in the nitrogen heterocyclic carbene (NHC) ligand precursor as shown in Formula V are defined as follows (unmentioned groups are the same as those described in any embodiment of the present application),

[0161] In certain preferred embodiments of the present invention, the ligand precursor of the nitrogen heterocyclic carbene as shown in Formula V is:

[0162]

[0163] or a combination thereof; for example Preferred

[0164] In certain preferred embodiments of the present invention,

[0165] When R 8b and R 8b’ At least one of which is independently When the above steps are repeated, a polysubstituted alkylarylazo compound as shown in Formula I and / or Formula II can be obtained.

[0166] In certain preferred embodiments of the present invention,

[0167] When R 8b and R 8b’ Independently C5-C 10 The polycyclic cycloalkyl group or one or more R 10a Substituted C5-C 10 The polycyclic cycloalkyl group of R 9a and R 9b When it is a methyl group, a multi-substituted alkylarylazo compound as shown in Formula II can be obtained.

[0168] In certain preferred embodiments of the present invention, when R 8b and R 8b’ Independently When R 9a and R 9b When it is a secondary carbon group or a tertiary carbon group, a product mainly composed of a polysubstituted alkyl aryl azo compound as shown in formula I is obtained (that is, the molar ratio of the polysubstituted alkyl aryl azo compound as shown in formula I to the polysubstituted alkyl aryl azo compound as shown in formula II is greater than 1:1); for example, the molar ratio of the polysubstituted alkyl aryl azo compound as shown in formula I to the polysubstituted alkyl aryl azo compound as shown in formula II is greater than 2:1, preferably greater than 9:1, more preferably greater than 15:1, and most preferably greater than 98:1; for example, the nitrogen heterocyclic carbene (NHC) ligand precursor is Preferably

[0169] In certain preferred embodiments of the present invention, when R 8b and R 8b’ Independently C5-C 10 The polycyclic cycloalkyl group or one or more R 10a Substituted C5-C 10 When the polycyclic cycloalkyl group is a polycyclic cycloalkyl group, a product mainly composed of a polysubstituted alkylaryl azo compound as shown in Formula II is obtained (i.e., the molar ratio of the polysubstituted alkylaryl azo compound as shown in Formula II to the polysubstituted alkylaryl azo compound as shown in Formula I is greater than 1:1); for example, the molar ratio of the polysubstituted alkylaryl azo compound as shown in Formula II to the polysubstituted alkylaryl azo compound as shown in Formula I is greater than 98:1; preferably, there is substantially no polysubstituted alkylaryl azo compound as shown in Formula I. For example, the nitrogen heterocyclic carbene (NHC) ligand precursor is Preferably

[0170] In certain preferred embodiments of the present invention, when the propargyl reagent shown in formula III is in the following configuration, and according to the "sequence rule" of the substituents, R 4 Prioritizes R 3 When the polysubstituted alkylarylazo compound shown in Formula I or Formula II is obtained, the polysubstituted alkylarylazo compound shown in Formula I or Formula II is obtained.

[0171]

[0172] Alternatively, when the propargyl reagent shown in formula III is in the following configuration, and according to the "order rule" of substituents, R 4 Prioritizes R 3 When the polysubstituted alkylarylazo compound shown in Formula I or Formula II is obtained, the polysubstituted alkylarylazo compound shown in Formula I or Formula II is obtained.

[0173]

[0174] The present invention also provides a use of the polysubstituted alkylarylazo compound as shown in Formula I or Formula II in the preparation of an α-quaternary carbon amine compound; the method comprises the following steps:

[0175] In a solvent, in the presence of a reducing agent, a multi-substituted alkylaryl azo compound as shown in Formula I or Formula II is subjected to a reduction reaction as shown below to obtain an α-quaternary carbon amine compound as shown in Formula VI or Formula VII;

[0176]

[0177] Among them, each group R 1 、R 2 、R 3 、R 4 and R 5 is as defined in the first aspect of the present invention.

[0178] In certain preferred embodiments of the present invention, the reducing agent can be a conventional reducing agent in this type of azo reduction reaction in the art, as long as it does not affect the allene bond or the acetylene bond; for example: Zn / HCl or SnCl2 / HCl, for example, zinc powder / hydrochloric acid.

[0179] In certain preferred embodiments of the present invention, the solvent may be a conventional solvent used in this type of azo reduction reaction in the art, such as an alcohol solvent; for example, methanol.

[0180] In certain preferred embodiments of the present invention, when the reducing agent is zinc powder / hydrochloric acid, the molar ratio of the zinc powder to the polysubstituted alkylaryl azo compound of Formula I or the polysubstituted alkylaryl azo compound of Formula II can be a conventional molar ratio in this type of reaction in the art, for example, (10-200):1, for example, (50-100):1.

[0181] In certain preferred embodiments of the present invention, when the reducing agent is zinc powder / hydrochloric acid, the molar ratio of the hydrochloric acid to the zinc powder can be a conventional molar ratio in this type of reaction in the art, such as (2-10):1, for example 6.5:1.

[0182] In certain preferred embodiments of the present invention, the temperature of the reduction reaction may be a conventional temperature for such reactions in the art, such as 10°C to 100°C; or 20°C to 70°C.

[0183] In certain preferred embodiments of the present invention, the multi-substituted alkylarylazo compound represented by Formula I or Formula II is prepared by the preparation method described above.

[0184] The progress of the reduction reaction can be monitored by conventional monitoring methods in the art (e.g., TLC, HPLC, NMR, or GC). The reaction endpoint is generally when the polysubstituted alkylarylazo compound represented by Formula I or Formula II disappears or ceases to react. The reaction time can be 5 to 48 hours.

[0185] In the present invention, when the polysubstituted alkylarylazo compound represented by Formula I or Formula II has one or more chiral carbon atoms, optically pure isomers, such as pure enantiomers, racemates, or mixed isomers, can be isolated. Pure single isomers can be obtained by separation methods known in the art, such as chiral crystallization to form salts or separation using chiral preparative columns.

[0186] In the present invention, if stereoisomers exist in the polysubstituted alkylarylazo compound as shown in Formula I or Formula II, they may exist in the form of a single stereoisomer or a mixture thereof (e.g., a racemate). The term "stereoisomer" refers to cis-trans isomers or optical isomers. These stereoisomers can be separated, purified, and enriched by chiral separation methods (including but not limited to thin layer chromatography, rotary chromatography, column chromatography, gas chromatography, high pressure liquid chromatography, etc.), and can also be obtained by chiral separation by bonding with other chiral compounds (chemical bonding, etc.) or forming salts (physical bonding, etc.). The term "single stereoisomer" means that the mass content of one stereoisomer of the compound of the present invention relative to all stereoisomers of the compound is not less than 95%.

[0187] Definitions and General Terms

[0188] Unless otherwise specified, all technical terms used in the present invention have the same meaning as commonly understood by those skilled in the art to which the present invention belongs. All patents and publications related to the present invention are incorporated herein by reference in their entirety.

[0189] Unless otherwise indicated, the following definitions used herein shall apply. For purposes of the present invention, the chemical elements are referred to in accordance with the Periodic Table of the Elements, CAS version, and Handbook of Chemistry and Physics, 75th edition, 1994. In addition, general principles of organic chemistry may be found in "Organic Chemistry," Thomas Sorrell, University Science Books, Sausalito: 1999, and "March's Advanced Organic Chemistry" by Michael B. Smith and Jerry March, John Wiley & Sons, New York: 2007, the entire contents of which are incorporated herein by reference.

[0190] In this specification, groups and substituents thereof can be selected by those skilled in the art to provide stable structural moieties and compounds. When substituents are described by conventional chemical formulas written from left to right, the substituents also include chemically equivalent substituents obtained when the structural formula is written from right to left.

[0191] Certain chemical groups defined herein are preceded by a shorthand notation to indicate the total number of carbon atoms present in the group. For example, a C1-C6 alkyl group refers to an alkyl group as defined below having a total of 1, 2, 3, 4, 5, or 6 carbon atoms. The total number of carbon atoms in the shorthand notation does not include carbons that may be present in substituents of the group.

[0192] As used herein, numerical ranges defined in substituents, such as 0 to 4, 1-4, 1 to 3, etc., indicate integers within the range, such as 1-6, which represents 1, 2, 3, 4, 5, or 6.

[0193] In addition to the foregoing, when used in the specification and claims of this application, the following terms have the meanings indicated below unless otherwise specifically stated.

[0194] The term "comprising" is an open expression, that is, including the contents specified in the present invention, but not excluding other contents.

[0195] Stereochemical definitions and conventions used herein generally follow SP Parker, Ed., McGraw-Hill Dictionary of Chemical Terms (1984) McGraw-Hill Book Company, New York; and Eliel, E. and Wilen, S., “Stereochemistry of Organic Compounds”, John Wiley & Sons, Inc., New York, 1994.

[0196] Any asymmetric atom (e.g., carbon, etc.) of the compounds disclosed herein can exist in a racemic or enantiomerically enriched form, such as in the (R)-, (S)-, or (R,S)-configuration. In certain embodiments, each asymmetric atom has at least 0% enantiomeric excess, at least 60% enantiomeric excess, at least 70% enantiomeric excess, at least 80% enantiomeric excess, at least 90% enantiomeric excess, at least 95% enantiomeric excess, or at least 99% enantiomeric excess in terms of the (R)- or (S)-configuration.

[0197] Any resulting mixture of stereoisomers can be separated into the pure or substantially pure geometric isomers, enantiomers, and diastereomers on the basis of the differences in the constituent physicochemical properties, for example, by chromatography and / or fractional crystallization.

[0198] The term "substituted" means that any one or more hydrogen atoms on a particular atom are replaced by a substituent, including deuterium and hydrogen variants, as long as the valence of the particular atom is normal and the substituted compound is stable.

[0199] In general, the term "substituted" means that one or more hydrogen atoms in a given structure are replaced by a specified substituent. Furthermore, when a group is substituted with one or more of the substituents, the substituents are independent of each other, i.e., the one or more substituents may be different or the same. Unless otherwise indicated, a substituent group may be substituted at every substitutable position of the substituted group. When more than one position in a given structure is substitutable by one or more substituents selected from the specified group, the substituents may be the same or different at each position.

[0200] The term "one or more" or "one or more than two" means 1, 2, 3, 4, 5, 6, 7, 8, 9 or more; for example, 1, 2, 3, 4 or 5.

[0201] Those skilled in the art will understand that according to the conventions used in the art, the structural formulas used in this application to describe groups It means that the corresponding group is connected to other fragments and groups in the compound through this site.

[0202] In various parts of this specification, the substituents of the compounds disclosed in the present invention are disclosed according to group types or ranges. It is specifically pointed out that the present invention includes every independent subcombination of the individual members of these group types and ranges. For example, the term "C1-C6 alkyl" or "C 1-6 The term "alkyl" may be in the form of a straight chain or a branched chain, and specifically refers to the independently disclosed methyl, ethyl, C3 alkyl, C4 alkyl, C5 alkyl and C6 alkyl; the term "C1-4 alkyl" specifically refers to the independently disclosed methyl, ethyl, C3 alkyl (i.e., propyl, including n-propyl and isopropyl), C4 alkyl (i.e., butyl, including n-butyl, isobutyl, sec-butyl and tert-butyl).

[0203] In various parts of the present invention, linking substituents are described. When the structure clearly requires a linking group, the Markush variable listed for that group should be understood to be a linking group. For example, if the structure requires a linking group and the Markush group definition for that variable lists "alkyl" or "aryl", it should be understood that the "alkyl" or "aryl" represents a linking alkylene group or arylene group, respectively.

[0204] In some specific structures, when an alkyl group is clearly indicated as a linking group, the alkyl group represents a linked alkylene group, for example, the C1-C6 alkyl in the group "halo-C1-C6 alkyl" should be understood as a C1-C6 alkylene.

[0205] The term "alkyl" as used herein refers to a saturated, linear or branched, monovalent hydrocarbon group containing 1 to 20 carbon atoms. Examples of alkyl groups include, but are not limited to, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, 2-pentyl, 3-pentyl, 2-methyl-2-butyl, 3-methyl-2-butyl, 3-methyl-1-butyl, 2-methyl-1-butyl, n-hexyl, 2-hexyl, 3-hexyl, 2-methyl-2-pentyl, 3-methyl-2-pentyl, 4-methyl-2-pentyl, 3-methyl-3-pentyl, 2-methyl-3-pentyl, 2,3-dimethyl-2-butyl, 3,3-dimethyl-2-butyl, n-heptyl, n-octyl, and the like.

[0206] In some specific structures, when an alkyl group is clearly indicated as a linking group, the alkyl group represents a linked alkylene group, for example, the C1-C6 alkyl in the group "halo-C1-C6 alkyl" should be understood as a C1-C6 alkylene.

[0207] The term "alkylene" refers to a saturated divalent hydrocarbon group obtained by removing two hydrogen atoms from a saturated straight or branched hydrocarbon group. Examples of alkylene groups include methylene (-CH2-), ethylene (including -CH2CH2- or -CH(CH3)-), isopropylene (including -CH(CH3)CH2- or -C(CH3)2-), and the like.

[0208] The term "alkenyl" refers to a linear or branched monovalent hydrocarbon radical containing 2 to 12 carbon atoms, wherein there is at least one site of unsaturation, i.e., a carbon-carbon sp 2 Double bonds, including "cis" and "tans" orientations, or "E" and "Z" orientations. Examples of alkenyl groups include, but are not limited to, vinyl (-CH=CH2), allyl (-CH2CH=CH2), and the like.

[0209] The term "alkoxy" or "alkyl-O-" refers to an alkyl group attached to the remainder of the molecule through an oxygen atom, wherein the alkyl group has the meaning as defined herein. Examples of alkoxy groups include, but are not limited to, methoxy, ethoxy, 1-propoxy, 2-propoxy, 1-butoxy, and the like.

[0210] The term "haloalkyl", "haloalkoxy" or "haloalkyl-O-" means an alkyl or alkoxy group substituted with one or more halogen atoms. Examples include, but are not limited to, trifluoromethyl, trifluoromethoxy and the like.

[0211] The term "cycloalkyl" refers to a monovalent or polyvalent saturated monocyclic or bicyclic ring system containing 3-12 ring carbon atoms. Examples of cycloalkyl groups include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, and the like; wherein the C3-C6 cycloalkyl group includes cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl.

[0212] The term "halogen" or "halo" refers to fluorine (F), chlorine (Cl), bromine (Br), or iodine (I).

[0213] The term "aryl" refers to monocyclic, bicyclic and tricyclic carbon ring systems containing 6 to 14 ring atoms, or 6 to 10 ring atoms. Examples of aryl groups may include phenyl, naphthyl and anthracenyl. Unless otherwise specified, the group "C6-C 10 "Aryl" means an aromatic group containing 6 to 10 ring carbon atoms.

[0214] The term "heteroaryl" refers to monocyclic, bicyclic, and tricyclic ring systems containing 5-6 ring atoms, or 5-10 ring atoms, or 5-12 ring atoms, wherein at least one ring contains one or more ring heteroatoms selected from nitrogen, oxygen, and sulfur. Unless otherwise specified, the heteroaryl group can be attached to the rest of the molecule (e.g., the main structure in the general formula) through any reasonable position (which can be C in CH or N in NH). Examples include, but are not limited to, furanyl, imidazolyl, isoxazolyl, oxazolyl, pyrrolyl, pyrazolyl, pyridyl, pyrimidinyl, pyridazinyl, pyrazinyl, thienyl, thiazolyl, and the like; and also include, but are not limited to, the following bicyclic rings: benzimidazolyl, benzofuranyl, benzothienyl, indolyl, oxoindolyl, imidazopyridinyl, pyrazolopyridinyl, pyrazolopyrimidinyl, quinolinyl, isoquinolinyl, quinazolinyl, and the like.

[0215] The "sequence rule" for substituents used in this article refers to the one officially adopted by the International Union of Pure and Applied Chemistry (IU-PAC) in 1970. It is the basic basis for main chain numbering, substituent listing order, determination of Z and E forms of olefin structures, and determination of R and S configurations of chiral compounds in the nomenclature of organic compounds.

[0216] As used herein, the terms "moiety," "moiety," "chemical moiety," "group," and "chemical group" refer to specific segments or functional groups in a molecule. A chemical moiety is generally considered to be a chemical entity embedded in or attached to a molecule.

[0217] When a substituent is listed without indicating the atom via which it is bonded to a compound included in the general chemical formula but not specifically mentioned, such substituent may be bonded via any atom thereof. Combinations of substituents and / or variations thereof are permissible only if such combinations result in stable compounds.

[0218] When a group is listed without specifying whether it has a substituent, such group refers only to the group being unsubstituted. For example, when "C1-C4 alkyl" is not preceded by the phrase "substituted or unsubstituted", it refers only to "C1-C4 alkyl" itself or "unsubstituted C1-C4 alkyl".

[0219] Additionally, it should be noted that, unless explicitly stated otherwise, the term "independently" used in the present invention should be broadly interpreted to mean that the individual entities described are independent of each other and can independently represent the same or different specific groups. More specifically, the term "independently" can mean that the specific options represented by the same symbol in different groups do not affect each other, or that the specific options represented by the same symbol in the same group do not affect each other.

[0220] Unless otherwise indicated, the abbreviations of any protecting groups, amino acids and other compounds used in the present invention are based on their commonly used and recognized abbreviations or refer to the IUPAC-IUB Commissionon Biochemical Nomenclature (see Biochem. 1972, 11: 942-944).

[0221] Unless otherwise specified, all technical and scientific terms used herein have the standard meanings in the art to which the claimed subject matter belongs. If there are multiple definitions for a term, the definition herein shall prevail.

[0222] It should be understood that the singular forms used in the present invention, such as "a", include plural references unless otherwise specified. In addition, the term "comprising" is an open limitation rather than a closed limitation, that is, it includes the content specified in the present invention, but does not exclude other aspects of the content.

[0223] Unless otherwise stated, the present invention adopts conventional methods of mass spectrometry and elemental analysis, and each step and condition can refer to conventional operating steps and conditions in the art.

[0224] Unless otherwise indicated, the present invention employs standard nomenclature and standard laboratory procedures and techniques for analytical chemistry, synthetic organic chemistry, and optics. In some cases, standard techniques are used for chemical synthesis, chemical analysis, and light-emitting device performance testing.

[0225] Without violating the common sense in the art, the above-mentioned preferred conditions can be arbitrarily combined to obtain preferred embodiments of the present invention.

[0226] The reagents and raw materials used in the present invention are commercially available.

[0227] The positive advances of the present invention are that the method provided by the present invention is very simple and efficient. By using different nitrogen heterocyclic carbene (NHC) ligands, allene products and propargyl-substituted products can be prepared with high selectivity. All of the prepared products contain azo functional groups. The prepared alkylarylazo compounds can be used to efficiently prepare α-quaternary amines, etc. The polysubstituted alkylarylazo compounds prepared by the present invention provide a technical solution that is completely different from the existing technology to prepare allene or propargyl-substituted alkyl α-quaternary amine compounds, and achieve good yield and selectivity. BRIEF DESCRIPTION OF THE DRAWINGS

[0228] Figure 1 This is the X-ray diffraction structure diagram of the single crystal of product 19 in Example 5.

[0229] Figure 2 This is the X-ray diffraction structure diagram of the single crystal of product 21 in Example 5. DETAILED DESCRIPTION

[0230] The present invention is further illustrated by way of examples below, but the present invention is not limited to the scope of the examples. Experimental methods in the following examples where specific conditions are not specified were performed according to conventional methods and conditions, or selected according to the product specifications.

[0231] The following abbreviations are used throughout this invention:

[0232] LDA (lithium diisopropylamide), DMF (N,N-dimethylformamide), DMA (N,N-dimethylacetamide), DCM (dichloromethane), DME (ethylene glycol dimethyl ether), PE (petroleum ether), EA (ethyl acetate), THF (tetrahydrofuran), Ac (acetyl), MeOH (methanol), Boc (tert-butoxycarbonyl), rt (room temperature), eq means equivalent, Rf: specific gravity, g (gram), mg (milligram), mol (mole), mmol (millimol), h (hour), min (minute), mL (milliliter).

[0233] Overnight refers to 8 hours to 15 hours, for example, 12 hours; room temperature refers to 10° C. to 30° C.; and solvent ratio, for example, PE / EA, refers to volume ratio.

[0234] In the examples described below, all temperatures are set forth in degrees Celsius unless otherwise indicated.

[0235] Note: Solid / dashed lines indicate absolute configuration R or S.

[0236] In the present invention, according to common knowledge in the art, the dr value represents the molar ratio between diastereomers. For example, if the diastereomers are cis-trans isomers, and the molar amount of the trans-configured compound is greater than the cis-configured compound in the diastereomer, then the dr value = anti / syn * 100%, that is, the dr value is the molar ratio of the trans-configured compound to the cis-configured compound in the diastereomer; and vice versa.

[0237] Example 1: Palladium-catalyzed reaction of hydrazone with propargyl reagent to prepare allene product with high selectivity

[0238]

[0239] Hydrazone (0.4 mmol) and toluene (2.0 mL) were added to a 10 mL dry reaction tube. LiHMDS (1.0 Min THF, 0.4 mL, 0.4 mmol) was added under ice bath. After the addition, the mixture was stirred at room temperature for 30 min. [Pd(η 3 -C3H5)Cl]2 (1.83 mg, 0.005 mmol), L (4.3 mg, 0.01 mmol) and toluene (1.0 mL) were added at room temperature. t-BuOK (1.0 M in THF, 25 uL, 0.025 mmol) was added. After the addition was completed, the mixture was stirred at room temperature for 30 min and then added to the above 10 mL reaction tube. Then, propargyl reagent (32.2 mg, 0.2 mmol) and toluene (1.0 mL) were added. The reaction was allowed to proceed overnight at the corresponding temperature. After the reaction was completed, water (0.5 mL) was added to quench the reaction. The mixture was passed through a short silica gel column, washed with ethyl acetate (50 mL), concentrated, and mesitylene was added as an internal standard. The regioselectivity and diastereoselectivity of the reaction were 1 The yield of the allene product was determined by crude H NMR spectroscopy and preparative plate separation (PE / EA=50 / 1).

[0240] The following compounds were prepared by selecting corresponding raw materials:

[0241] and / or its enantiomers

[0242] Bright yellow liquid (55.0 mg, 82%, 87 / 7 / 6, >20 / 1dr) (wherein, "87 / 7 / 6" represents the ratio of 16aa / 17aa / 17ab. "dr" represents the diastereoisomer ratio of the allene product. The following examples are the corresponding product ratios.). 1HNMR(400MHz, CDCl3) δ7.91(d,J=7.6Hz,2H),7.57(dd,J=10.5,8.2Hz,5H),7.43(t,J=7.5Hz,2H) ,7.35(d,J=7.2Hz,1H),5.16(q,J=6.9Hz,1H),1.79(d,J=6.9Hz,3H),1.76(s,3H),-0.00(s,9H). 13 C NMR (101MHz, CDCl3) δ207.54,151.93,145.94,130.46,129.02,128.00,126.93,126.58,122.62,103.43,82.71,79.09, 27.78,13.77,0.43.IR(film):ν2594,2893,1939,1687,1598,1491,1444,1365,1244,1070,1027,835,758,688.ESI-MS m / z(rel):367.0(M+CH3OH+H) + ;HRMS(ESI)Calcd.for C 21 H 27 N2Si(M+H) + :335.1938;Found:335.1932.

[0243] and / or its enantiomers

[0244] Bright yellow liquid (56.6 mg, 80%, 86 / 8 / 6, >20 / 1 dr). 1 H NMR(400MHz, CDCl3) δ7.90(d,J=7.6Hz,2H),7.56(ddd,J=12.1,11.1,6.2Hz,5H),7.12( t,J=8.6Hz,2H),5.15(q,J=6.9Hz,1H),1.78(d,J=6.9Hz,3H),1.74(s,3H),0.00(s,9H). 13 C NMR(101MHz, CDCl3)δ207.52,161.64(d,J=245.1Hz),151.83,141.73,141.70,130.59,129.05, 128.57(d,J=7.8Hz),122.60,114.74(d,J=21.1Hz),103.50,82.86,78.57,27.85,13.71,0.43. 19F NMR(376MHz, CDCl3)δ-116.61.IR(film):ν2955,2893,1939,1688,1598,1503,1366,1244,1228,1158,1089,1015,964,832,757,688.ESI-MS m / z(rel):385.0(M+CH3OH+H) + ;HRMS(ESI)Calcd.for C 21 H 26 FN2Si(M+H) + :353.1844; Found:353.1836.

[0245] and / or its enantiomers

[0246] Bright yellow liquid (53.0 mg, 71%, 84 / 11 / 5, >20 / 1 dr). 1 H NMR(400MHz, CDCl3) δ7.89(d,J=7.5Hz,2H),7.65–7.54(m,3H),7.51(d,J=8.2Hz,2H),7.4 0(d,J=8.3Hz,2H),5.16(q,J=6.9Hz,1H),1.78(d,J=6.9Hz,3H),1.73(s,3H),0.00(s,9H). 13 C NMR (101MHz, CDCl3) δ207.60,151.79,144.62,132.40,130.65,129.06,128.41,128.13,122.61,103.28,82.96,78.59, 27.80,13.71,0.45.IR(film):ν2954,2922,1939,1594,1488,1453,1397,1365,1245,1093,1013,835,759,687.ESI-MS m / z(rel):368.9(M+H) + ;HRMS(ESI)Calcd.forC 21 H 26 N2ClSi(M+H) + :369.1548; Found:369.1547

[0247] and / or its enantiomers

[0248] Bright yellow liquid (56.4 mg, 77%, 86 / 8 / 6, >20 / 1 dr). 1H NMR (400MHz, CDCl3) δ7.88(d,J=7.8Hz,2H),7.55(dt,J=13.6,6.9Hz,3H),7.46(d,J=8.4Hz,2H),6.96( d,J=8.3Hz,2H),5.12(q,J=6.8Hz,1H),3.88(s,3H),1.77(d,J=6.9Hz,3H),1.73(s,3H),-0.00(s,9H). 13 CNMR(101MHz, CDCl3)δ207.43,158.24,151.94,137.94,130.39,129.00,128.07,122.59,113.32,103.64,82.61,78.67,55.18,2 7.71,13.78,0.48.IR(film):ν3064,2953,2859,1939,1657,1606,1507,1453,1365,1244,1176,1033,964,830,757,688.ESI-MS m / z(rel):397.0(M+CH3OH+H) + ;HRMS(ESI)Calcd.for C 22 H 29 N2OSi(M+H) + :365.2044;Found:365.2039.

[0249] and / or its enantiomers

[0250] Bright yellow liquid (62.4 mg, 80%, 87 / 9 / 4, >20 / 1 dr). 1 H NMR (400MHz, CDCl3) δ8.14(d,J=8.1Hz,2H),7.93(d,J=7.5Hz,2H),7.68(d,J=8.1Hz,2H),7.66–7 .54(m,3H),5.20(q,J=6.9Hz,1H),4.02(s,3H),1.81(d,J=6.9Hz,3H),1.77(s,3H),0.00(s,9H). 13C NMR (101MHz, CDCl3) δ207.66,167.08,151.78,151.48,130.71,129.36,129.07,128.41,126.98,122.61,103.12,83.07,78.98,52.0 1,27.71,13.67,0.40.IR(film):ν2951,2893,1939,1721,1608,1435,1366,1274,1245,1183,1109,1018,965,835,759,689.ESI-MS m / z(rel):425.0(M+CH3OH+H) + ;HRMS(ESI)Calcd.for C 23 H 29 N2O2Si(M+H) + :393.1993;Found:393.1987.

[0251] and / or its enantiomers

[0252] Bright yellow liquid (55.5 mg, 77%, 79 / 20 / 1, >20 / 1 dr). 1 H NMR(400MHz, CDCl3)δ7.80(d,J=6.7Hz,2H),7.62(q,J=8.5Hz,4H),7.56–7.45( m,3H),5.09(q,J=7.0Hz,1H),1.69(d,J=7.0Hz,3H),1.63(s,3H),-0.12(s,9H). 13 C NMR (101MHz, CDCl3) δ207.80,151.76,151.60,131.89,130.97,129.14,127.78,122.64,119.07,110.41,102.89,83.36,78.76 ,27.72,13.64,0.39.IR(film):ν2963,2894,2223,1952,1603,1500,1451,1401,1259,1157,1094,1016,833,799,685.ESI-MS m / z(rel):360.0(M+H) + ;HRMS(ESI)Calcd.for C 22 H 26 N3Si(M+H) + :360.1891;Found:360.1891

[0253] and / or its enantiomers

[0254] Bright yellow liquid (50.0 mg, 72%, 87 / 9 / 4, >20 / 1 dr). 1 H NMR (400MHz, CDCl3) δ7.97–7.86(m,2H),7.65–7.46(m,3H),7.34(dd,J=16.0,8.8Hz,3H),7.15(d, J=7.1Hz,1H),5.16(q,J=6.9Hz,1H),2.45(s,3H),1.78(d,J=6.9Hz,3H),1.75(s,3H),0.00(s,9H). 13 C NMR (101MHz, CDCl3) δ207.54,151.99,145.87,137.44,130.41,129.02,127.89,127.68,127.33,124.03,122.63,103.43,82.67,79 .11,27.85,21.72,13.79,0.47.IR(film):ν3061,2954,2893,1938,1605,1479,1452,1365,1244,1071,1020,835,757,688.ESI-MS m / z(rel):381.0(M+CH3OH+H) + ;HRMS(ESI)Calcd.for C 22 H 29 N2Si(M+H) + :349.2095;Found:349.2099.

[0255] and / or its enantiomers

[0256] Bright yellow liquid (60.0 mg, 82%, 90 / 6 / 4, >20 / 1 dr). 1 H NMR (400MHz, CDCl3) δ7.89 (d, J = 7.7Hz, 2H), 7.55 (dt, J = 20.4, 7.1Hz, 3H), 7.33 (dd, J = 13.9, 6.0Hz, 1H), 7.14 (d, J = 8. 2Hz,2H),6.88(d,J=8.2Hz,1H),5.15(q,J=6.9Hz,1H),3.88(s,3H),1.78(d,J=6.9Hz,3H),1.74(s,3H),-0.00(s,9H). 13C NMR (101MHz, CDCl3) δ207.55,159.35,151.93,147.70,130.48,129.02,128.95,122.62,119.47,113.34,111.47,103.36,82.74,79.0 0,55.17,27.81,13.77,0.45.IR(film):ν3065,2953,2859,1938,1598,1581,1482,1452,1365,1287,1245,1046,835,758,688.ESI-MS m / z(rel):397.0(M+CH3OH+H) + ;HRMS(ESI)Calcd.forC 22 H 29 N2OSi(M+H) + :365.2044;Found:365.2039.

[0257] and / or its enantiomers

[0258] Bright yellow liquid (56.0 mg, 80%, 81 / 16 / 3, >20 / 1 dr). 1 H NMR (400MHz, CDCl3) δ7.81–7.73(m,2H),7.54–7.41(m,4H),7.26(ddd,J=6.8,6.1,1.8Hz,1H),7.12(td,J= 7.7,1.2Hz,1H),7.06–6.93(m,1H),4.95(q,J=6.9Hz,1H),1.75(s,3H),1.64(d,J=7.0Hz,3H),0.00(s,9H). 13 C NMR (101MHz, CDCl3) δ207.59, 160.56 (d, J = 249.7Hz), 151.96, 132.90 (d, J = 11.2Hz), 130.41, 128.96, 128.82 (d, J = 4.7Hz), 128 .61(d,J=8.6Hz),123.28(d,J=3.4Hz),122.55,116.15(d,J=22.9Hz),103.04,82.81,77.62(d,J=4.0Hz),25.33,13.52,0.51. 19F NMR(61MHz, CDCl3)δ99.55.IR(film):ν2954,2893,1940,1580,1486,1445,1365,1245,1210,1066,964,906,836,752,688.ESI-MS m / z(rel):353.0(M+H) + ;HRMS(ESI)Calcd.for C 21 H 26 FN2Si(M+H) + :353.1844;Found:353.1834.

[0259] and / or its enantiomers

[0260] Bright yellow liquid (39.0 mg, 53%, 67 / 33 / 0, >20 / 1 dr). 1 H NMR (400MHz, CDCl3) δ7.72(d,J=8.0Hz,2H),7.51–7.39(m,4H),7.27(t,J=7.7Hz,1H),6.96(t,J=7.5Hz,1H) ,6.87(d,J=8.1Hz,1H),4.86(q,J=6.8Hz,1H),3.65(s,3H),1.72(s,3H),1.62(d,J=6.9Hz,3H),0.02(s,9H). 13 C NMR (101MHz, CDCl3) δ207.29,157.08,152.33,134.12,129.90,128.85,128.38,128.11,122.36,119.80,111.71,103.88,82.14,78.4 6,55.25,25.16,13.66,0.65.IR(film):ν2953,2893,2833,1939,1597,1582,1487,1434,1364,1284,1242,1028,835,750,688.ESI-MS m / z(rel):365.0(M+H) + ;HRMS(ESI)Calcd.for C 22 H 29 N2OSi(M+H) + :365.2044;Found:365.2046.

[0261] and / or its enantiomers

[0262] Bright yellow liquid (62.0 mg, 81%, 86 / 9 / 5, >20 / 1 dr). 1 H NMR (400MHz, CDCl3) δ7.99 (s, 1H), 7.92 (dd, J = 13.8, 7.7Hz, 5H), 7.72 (d, J = 8.5Hz, 1H), 7.59 (t, J = 7.3Hz, 2H), 7.53 (dd, J=7.3, 4.7Hz, 3H), 5.19 (q, J=6.8Hz, 1H), 1.84 (s, 3H), 1.79 (d, J=6.9Hz, 3H), -0.00 (s, 9H). 13 C NMR (101MHz, CDCl3) δ207.79,152.02,143.50,133.24,132.39,130.58,129.11,128.27,127.67,127.58,125.88,125.70,125.38,122.71,103 .53,82.87,79.29,27.84,13.83,0.57.IR(film):ν3057,2954,2892,1934,1598,1504,1452,1365,1244,1127,1068,966,835,745,687.ESI-MS m / z(rel):417.0(M+CH3OH+H) + ;HRMS(ESI)Calcd.for C 25 H 29 N2Si(M+H) + :385.2095; Found:385.2088

[0263] and / or its enantiomers

[0264] Bright yellow liquid (56.0 mg, 74%, 84 / 8 / 8, >20 / 1 dr). 1 H NMR(400MHz, CDCl3) δ7.79(d,J=7.5Hz,2H),7.56–7.40(m,3H),7.00(s,1H),6.92(d,J=8.2Hz,1H),6.78 (d,J=8.1Hz,1H),5.95(s,2H),5.04(q,J=6.9Hz,1H),1.68(d,J=6.9Hz,3H),1.62(s,3H),-0.08(s,9H). 13CNMR(101MHz, CDCl3)δ207.45,151.84,147.33,146.06,139.96,130.46,128.98,122.59,120.11,107.89,107.69,103.55,100.87,8 2.68,78.78,27.83,13.71,0.43.IR(film):ν2957,2893,1937,1755,1674,1597,1483,1365,1242,1104,1034,838,753,691.ESI-MS m / z(rel):379.0(M+H) + ;HRMS(ESI)Calcd.for C 22 H 27 N2O2Si(M+H) + :379.1836;Found:379.1836.

[0265] and / or its enantiomers

[0266] Bright yellow liquid (57.0 mg, 88%, 88 / 8 / 4, >20 / 1 dr). 1 H NMR (400MHz, CDCl3) δ7.71 (d, J = 7.5Hz, 2H), 7.48–7.36 (m, 4H), 6.33 (s, 1H), 6.2 7(s,1H),4.96(q,J=6.9Hz,1H),1.72(s,3H),1.64(d,J=7.0Hz,3H),0.00(s,9H). 13 C NMR (101MHz, CDCl3) δ207.96,157.17,151.86,141.74,130.49,128.93,122.56,110 .10,106.96,102.03,82.91,75.68,24.29,13.64,0.26.IR(film):ν2955,2894,193 8,1596,1499,1453,1365,1245,1157,1069,1008,919,836,732,687.IR(film):ν30 67,2953,2893,1937,1666,1597,1496,1452,1365,1244,1020,835,758,687.ESI-MS m / z(rel):357.0(M+CH3OH+H) + ;HRMS(ESI)Calcd.for C 19 H 25N2OSi(M+H) + :325.1731;Found:325.173.

[0267] and / or its enantiomers

[0268] Bright yellow liquid (54.0 mg, 80%, 85 / 10 / 5, >20 / 1 dr). 1 H NMR (400MHz, CDCl3) δ7.81–7.74(m,2H),7.52–7.42(m,3H),7.26–7.20(m,1H),7.01– 6.94(m,2H),5.04(q,J=7.0Hz,1H),1.75(s,3H),1.69(d,J=7.0Hz,3H),-0.05(s,9H). 13 C NMR (101MHz, CDCl3) δ207.45,151.68,150.34,130.64,129.01,126.34,124.50,123.90,122.66,104.13,83.23,83.14,77 .27,28.44,13.68,0.34.IR(film):ν3067,2953,2893,1937,1597,1496,1452,1365,1244,1097,960,835,758,687.ESI-MS m / z(rel):341.0(M+H) + ;HRMS(ESI)Calcd.forC 19 H 25 N2SSi(M+H) + :341.1502;Found:341.1499.

[0269] and / or its enantiomers

[0270] Bright yellow liquid (63.0 mg, 84%, 88 / 8 / 4, >20 / 1 dr). 1 H NMR (400MHz, CDCl3) δ7.79(d,J=7.9Hz,2H),7.58(d,J=7.2Hz,1H),7.54–7.44(m,4H),7.31–7. 21(m,2H),6.73(s,1H),5.06(q,J=6.9Hz,1H),1.85(s,3H),1.71(d,J=7.0Hz,3H),0.06(s,9H). 13C NMR (101MHz, CDCl3) δ208.29,160.38,154.86,151.77,130.70,128.98,128.92,128.43,123.64 ,122.64,122.48,122.37,120.85,111.19,103.77,101.69,83.22,76.05,24.36,13.61,0.41.I R(film):ν3065,2954,2894,1935,1579,1522,1453,1365,1248,1164,907,836,737,687.IR(fi lm):ν3065,2983,2897,2167,1581,1420,1299,1249,1208,1095,925,838,805,737,687.ESI-MS m / z(rel):375.0(M+H) + ;HRMS(ESI)Calcd.for C 23 H 27 N2OSi(M+H) + :375.1887; Found:375.1883.

[0271] and / or its enantiomers

[0272] Bright yellow liquid (53.2 mg, 69%, 88 / 8 / 4, >20 / 1 dr). 1 H NMR (400MHz, CDCl3) δ7.93–7.69(m,3H),7.48(dt,J=21.3,7.0Hz,3H),7.32(d,J=8.2Hz,1H),7.24(dd,J=12.6,5.3Hz,1H) ,7.10(t,J=7.5Hz,1H),7.02(s,1H),5.02(q,J=6.9Hz,1H),3.78(s,3H),1.88(s,3H),1.73(d,J=6.9Hz,3H),-0.04(s,9H). 13C NMR (101MHz, CDCl3) δ207.38,152.05,137.58,130.21,128.95,126.62,122.59,121.80,121.28,119.18,118.70,109.11,103.59,82.46,76. 30,32.77,26.07,13.76,0.62.IR(film):ν3057,2952,2891,1936,1653,1542,1468,1365,1327,1243,1218,1095,1016,835,736,688.ESI-MS m / z(rel):388.0(M+H) + ;HRMS(ESI)Calcd.for C 24 H 30 N3Si(M+H) + :388.2204;Found:388.2203.

[0273] and / or its enantiomers

[0274] Bright yellow liquid (48.3 mg, 70%, 90 / 6 / 4, >20 / 1 dr). 1 H NMR (400MHz, CDCl3) δ7.99(d,J=7.4Hz,2H),7.76(d,J=7.6Hz,2H),7.65(dt,J=21.9,7.1Hz,3H),7.53(t,J=7.6Hz,2H),7.4 3(t,J=7.2Hz,1H),5.23(q,J=6.9Hz,1H),2.35(q,J=7.3Hz,2H),1.89(d,J=6.9Hz,3H),0.89(t,J=7.3Hz,3H),0.00(s,9H). 13 C NMR (101MHz, CDCl3) δ207.79,152.66,145.43,131.03,129.63,128.43,128.31,127.09,123.07,103.03,82.92,82.18,35 .21,14.37,9.67,0.95.IR(film):ν3060,2966,1935,1689,1597,1490,1445,1365,1244,1070,915,836,757,688.ESI-MS m / z(rel):349.0(M+H) + ;HRMS(ESI)Calcd.for C 22 H 29N2Si(M+H) + :349.2095;Found:349.2093.

[0275] and / or its enantiomers

[0276] Bright yellow liquid (64.0 mg, 85%, 95 / 4 / 1, >20 / 1 dr). 1 H NMR (400MHz, CDCl3) δ8.07(d,J=7.6Hz,2H),7.91(d,J=7.8Hz,2H),7.71(dt,J=23 .5,7.1Hz,3H),7.59(t,J=7.6Hz,2H),7.48(t,J=7.2Hz,1H),5.29(q,J=6.9Hz,1H ),2.38(dd,J=14.0,5.2Hz,1H),2.24(dd,J=14.0,6.0Hz,1H),1.96(d,J=6.9Hz,3 H),1.87–1.73(m,1H),0.90(d,J=6.7Hz,3H),0.82(d,J=6.6Hz,3H),-0.00(s,9H). 13 C NMR (101MHz, CDCl3) δ206.67,151.93,145.29,130.48,129.08,127.88,127.70,126.51,122.58,103.48,82.58,81.86,51.84, 24.62,24.47,24.36,13.92,0.33.IR(film):ν3060,2952,2866,1934,1598,1490,1466,1365,1244,1070,835,758,688.ESI-MS m / z(rel):377.0(M+H) + ;HRMS(ESI)Calcd.for C 24 H 33 N2Si(M+H) + :377.2408;Found:3772405

[0277] and / or its enantiomers

[0278] Bright yellow liquid (60.0 mg, 96%, 98 / 1 / 1, >20 / 1 dr). 1H NMR (400MHz, CDCl3) δ7.76–7.64(m,2H),7.53–7.36(m,3H),4.91(q,J=6.9Hz,1H),2.22–2.09(m ,2H),1.89(ddd,J=12.8,8.4,4.1Hz,2H),1.67(d,J=6.9Hz,3H),1.62–1.44(m,6H),0.05(s,9H); 13 C NMR (101MHz, CDCl3) δ208.13,152.16,129.99,128.87,122.11,102.10,81.88,75.69,35.53,35.38,25.92,22.80,2 2.77,13.77,1.09; IR(film):ν2930,2856,1930,1478,1449,1365,1245,1136,1068,1020,917,834,758,687; ESI-MS m / z(rel):313.0(M+H) + ;HRMS(ESI)Calcd.forC 19 H 29 N2Si(M+H) + :313.2095;Found:313.2094.

[0279] and / or its enantiomers

[0280] Bright yellow liquid (78.3 mg, 91%, 98 / 1 / 1, >20 / 1 dr). 1 H NMR (400MHz, CDCl3) δ7.78–7.67(m,2H),7.58–7.47(m,3H),7.25–7.12(m,8H),7.12–7.04(m,2H),5.01(q,J=7.0Hz,1 H),3.52(d,J=13.4Hz,1H),3.43(d,J=13.1Hz,1H),3.22(dd,J=13.3,3.5Hz,2H),1.72(d,J=7.0Hz,3H),-0.20(s,9H); 13C NMR (101MHz, CDCl3) δ207.57,151.23,137.77,137.73,131.60,131.55,130.59,129.11,127.47,127.40,125.93,125.90,122.53,102.38 ,82.63,80.96,46.87,46.57,12.87,-0.07.IR(film):ν3028,2950,1933,1703,1598,1495,1453,1368,1247,1001,915,834,693.ESI-MS m / z(rel):425.0(M+H) + ;HRMS(ESI)Calcd.forC 28 H 33 N2Si(M+H) + :425.2408;Found:425.241.

[0281] and / or its enantiomers

[0282] Bright yellow liquid (81.2 mg, 98%, 98 / 1 / 1, >20 / 1 dr). 1 H NMR (400MHz, CDCl3) δ7.60(d,J=7.1Hz,2H),7.32(dt,J=14.2,6.9Hz,3H),6.96(d,J=8.5Hz,2H),6.68(d,J=8.5Hz,2H),4. 87(q,J=6.9Hz,1H),3.63(s,3H),2.49–2.30(m,2H),2.11–1.93(m,2H),1.57(d,J=6.9Hz,3H),1.33(s,3H),-0.00(s,9H). 13 C NMR (101MHz, CDCl3) δ207.71,158.14,152.34,135.47,130.78,129.70,129.47,122.89,114.25,103.91,82.65,77.27,55.70,43.23 ,30.45,25.48,14.32,1.40.IR(film):ν2950,2860,2833,1931,1611,1510,1453,1441,1364,1243,1176,1036,835,761,689.ESI-MS m / z(rel):393.0(M+H) + ;HRMS(ESI)Calcd.for C 24 H 33N2OSi(M+H) + :393.2357; Found:393.2356.

[0283] and / or its enantiomers

[0284] Bright yellow liquid (77.0 mg, 83%, 88 / 7 / 5, 14 / 1 dr). 1 H NMR (400MHz, CDCl3) δ7.89–7.80(m,2H),7.52(t,J=3.2Hz,1H),7.48(dd,J=6.7,5.5Hz,4H),7.36(dd,J=10.1,5.3Hz,2H),7.27( dd,J=11.6,4.8Hz,1H),5.30(td,J=6.4,1.1Hz,1H),4.26(d,J=6.5Hz,2H),1.70(s,3H),0.93(s,9H),0.11(s,6H),-0.07(s,9H); 13 C NMR (101MHz, CDCl3) δ200.12,146.45,140.25,125.18,123.65,122.69,12 1.54,121.50,121.31,117.29,99.89,83.89,73.64,56.32,22.59,20.66, 20.60,13.01,-4.94,-10.44,-10.49.IR(film):ν2953,2928,2893,2855, 1940,1598,1492,1467,1444,1361,1248,1072,1006,833,759,691.ESI-MS m / z(rel):465.0(M+H) + ;HRMS(ESI)Calcd.for C 27 H 41 ON2Si2(M+H) + :465.2752;Found:465.2751.

[0285] and / or its enantiomers

[0286] Bright yellow liquid (63.8 mg, 77%, 91 / 4 / 5,>20 / 1 dr). 1H NMR(400MHz, CDCl3) δ7.92(d,J=7.1Hz,2H),7.68–7.50(m,5H),7.44(t,J=7.3Hz,2H),7. 41–7.28(m,6H),5.40(t,J=6.8Hz,1H),3.50(d,J=6.8Hz,2H),1.78(s,3H),0.00(s,9H). 13 C NMR (101MHz, CDCl3) δ206.71,151.85,145.69,140.71,130.52,129.03,128.69,128.31,128.03,126.98,126.65,126.05,122.67,10 4.69,88.11,79.09,35.25,27.64,0.47.IR(film):ν3060,2954,1939,1599,1492,1452,1378,1244,1069,1027,838,759,688.ESI-MS m / z(rel):443.0(M+CH3OH+H) + ;HRMS(ESI)Calcd.for C 27 H 31 N2Si(M+H) + :411.2251;Found:411.2241.

[0287] and / or its enantiomers

[0288] Bright yellow liquid (35.0 mg, 48%, 77 / 19 / 4, >20 / 1 dr). 1 H NMR (400MHz, CDCl3) δ7.93(d,J=7.3Hz,2H),7.61(dd,J=15.9,7.8Hz,5H),7.46(t,J=7.5Hz,2H),7.37(dd,J=9.4, 4.9Hz,1H),5.28(d,J=5.5Hz,1H),2.46(dq,J=13.0,6.5Hz,1H),1.77(s,3H),1.15(d,J=6.7Hz,6H),0.00(s,9H). 13C NMR (101MHz, CDCl3) δ205.06,151.88,146.02,130.44,128.99,127.97,126.94,126.53,122.60,105.08,96.01,78.92,27 .89,27.65,22.77,0.40.IR(film):ν2957,2895,1938,1599,1490,1444,1363,1244,1150,1070,963,835,757,688.ESI-MS m / z(rel):363.0(M+H) + ;HRMS(ESI)Calcd.for C 23 H 31 N2Si(M+H) + :363.2251;Found:363.224.

[0289] and / or its enantiomers

[0290] Bright yellow liquid (35.0 mg, 49%, 87 / 8 / 5, >20 / 1 dr). 1 H NMR (400MHz, CDCl3) δ7.84–7.79(m,2H),7.55–7.45(m,5H),7.35(dd,J=10.3,4.8Hz,2H),7.26(t,J=7.3Hz,1H),5.88(ddt,J= 16.7,10.1,6.4Hz,1H),5.15(d,J=6.7Hz,1H),5.12–4.96(m,2H),2.80(t,J=6.6Hz,2H),1.67(s,3H),-0.10(d,J=3.3Hz,9H). 13 C NMR (101MHz, CDCl3) δ206.66,151.86,145.80,136.88,130.47,128.99,127.99,126.91,126.58,122.58,114.99,104.45,86.42,78. 94,32.92,27.81,0.40.IR(film):ν3060,2954,1938,1759,1687,1598,1492,1444,1365,1244,1069,1027,912,836,759,689.ESI-MS m / z(rel):361.0(M+H) + ;HRMS(ESI)Calcd.for C 23 H 29 N2Si(M+H)+ :361.2095;Found:361.209.

[0291] and / or its enantiomers

[0292] Bright yellow liquid (25.1 mg, 36%, 51 / 46 / 3, >20 / 1 dr). 1 H NMR(400MHz, CDCl3)δ7.76(d,J=7.1Hz,2H),7.52–7.40(m,5H),7.35(t,J=7.6Hz,2 H),7.25(dd,J=9.5,5.0Hz,1H),5.34(tt,J=6.5,3.2Hz,1H),2.00(dd,J=14.6,6.8 Hz,2H),1.93–1.74(m,2H),1.59(s,3H),1.43(dt,J=14.6,7.3Hz,2H),1.34–1.27( m,2H),1.18(dt,J=14.4,7.2Hz,2H),0.93(t,J=7.4Hz,3H),0.77(t,J=7.3Hz,3H). 13 C NMR (101MHz, CDCl3) δ202.13,152.29,145.25,130.31,128.91,128.10,127.14,126.54,122.38,109.97,94.92,77.88,31.45,30.35,28.37, 26.12,22.45,22.34,14.02,13.94.IR(film):ν3060,2956,2928,2869,1956,1598,1491,1445,1365,1181,1104,1026,918,760,690.ESI-MS m / z(rel):345.0(M+H) + ;HRMS(ESI)Calcd.for C 24 H 29 N2(M+H) + :345.2325;Found:345.2326.

[0293] and / or its enantiomers

[0294] Yellow solid (40.0 mg, 58%, 72 / 24 / 4, >20 / 1 dr). mp: 111.5-112.2°C. 1H NMR (400MHz, CDCl3) δ7.79(d,J=7.3Hz,2H),7.56–7.42(m,5H),7.35(t,J=7.6Hz,2H),7.26(t,J=7.2Hz,1H),5.34(q,J=6 .8Hz,1H),1.89–1.77(m,1H),1.70(d,J=6.8Hz,3H),1.67(s,1H),1.60(s,3H),1.55(d,J=13.3Hz,4H),1.18–0.93(m,5H); 13 C NMR (101MHz, CDCl3) δ203.44,152.28,145.11,130.36,129.00,127.97,127.25,126.62,122.45,115.75,90.05,78.23,38.20,35.08,33.94,26 .77,26.74,26.14,25.63,14.91.IR(film):ν2988,2922,2846,1953,1597,1487,1441,1365,1303,1176,1100,1068,989,888,759,688.ESI-MS m / z(rel):345.0(M+H) + ;HRMS(ESI)Calcd.for C 24 H 29 N2(M+H) + :345.2325;Found:345.2325.

[0295] and / or its enantiomers

[0296] Bright yellow liquid (50.0 mg, 67%, 89 / 8 / 3, >20 / 1 dr). 1 H NMR (400MHz, CDCl3) δ7.82(d,J=7.9Hz,2H),7.49(tdd,J=6.9,4.5,2.3Hz,3H),7.40(d,J=8.0Hz,2H),7.34(t,J=7.6Hz,2H),7. 25(dd,J=9.0,5.3Hz,1H),5.08(q,J=7.0Hz,1H),1.70(d,J=7.0Hz,3H),1.63(s,3H),0.77(s,9H),-0.09(s,3H),-0.21(s,3H). 13C NMR (101MHz, CDCl3) δ208.78,151.83,146.09,130.42,128.93,127.99,126.88,126.51,122.67,100.63,82.98,78.94,27.8 1,27.18,18.00,13.86,-3.58.IR(film):ν2955,2927,2854,1938,1598,1491,1443,1364,1246,1070,821,761,689.ESI-MS m / z(rel):377.3(M+H) + ;HRMS(ESI)Calcd.for C 24 H 33 N2Si(M+H) + :377.2408;Found:377.2403.

[0297] and / or its enantiomers

[0298] Bright yellow liquid (50.5 mg, 80%, 92 / 6 / 2). 1 H NMR (400MHz, CDCl3) δ7.74–7.66(m,2H),7.46–7.31(m,5H),7.28(t,J=7.6Hz,2H),7.19(d,J=7.3Hz,1H),4.89–4.79(m, 2H),1.88–1.65(m,2H),1.54(s,3H),1.28(tq,J=13.7,6.8Hz,2H),1.10(dd,J=11.9,8.5Hz,4H),0.71(t,J=6.9Hz,3H); 13 C NMR (101MHz, CDCl3) δ206.73,152.28,144.96,130.50,128.98,128.24,127.13,126.75,122.48,109.56,78.86,77.23,31.53, 28.03,27.65,26.25,22.55,14.10.IR(film):ν2961,2955,1711,1682,1597,1493,1258,1072,1018,866,896,754,691.ESI-MS m / z(rel):319.0(M+H) + ;HRMS(ESI)Calcd.for C 22 H 27 N2(M+H) +:319.2169; Found:319.2167.

[0299] Example 2: Palladium-catalyzed reaction of hydrazone with propargyl reagent to prepare propargyl substituted products with high selectivity

[0300]

[0301] Hydrazone (0.4 mmol) and toluene (2.0 mL) were added to a 10 mL dry reaction tube. LiHMDS (1.0 Min THF, 0.4 mL, 0.4 mmol) was added under ice bath. After the addition, the mixture was stirred at room temperature for 30 min. [Pd(η 3 -C3H5)Cl]2 (1.83 mg, 0.005 mmol), L (4.3 mg, 0.01 mmol) and toluene (1.0 mL) were added at room temperature. t-BuOK (1.0 M in THF, 25 uL, 0.025 mmol) was added. After the addition was completed, the mixture was stirred at room temperature for 30 min and then added to the above 10 mL reaction tube. Then, propargyl reagent (0.2 mmol, 32.2 mg) and toluene (1.0 mL) were added. The reaction was allowed to proceed overnight at the corresponding temperature. After the reaction was completed, water (0.5 mL) was added to quench the reaction. The mixture was passed through a short silica gel column, washed with ethyl acetate (50 mL), concentrated, and mesitylene was added as an internal standard. The regioselectivity and diastereoselectivity of the reaction were 1 The yield of the propargyl substituted product was determined by crude H NMR spectroscopy and preparative plate separation (PE / EA=50 / 1).

[0302] The following compounds were prepared by selecting corresponding raw materials:

[0303] and / or its enantiomers

[0304] Bright yellow liquid 17aa (59.4 mg, 89%, 0 / 94 / 6, >20 / 1dr) (wherein, "87 / 7 / 6" represents the ratio of 16aa / 17aa / 17ab. "dr" represents the diastereoisomer ratio of the propargyl product. The following examples are the corresponding product ratios.). 1 H NMR (400MHz, CDCl3) δ7.77(d,J=7.3Hz,2H),7.54–7.43(m,5H),7.36(t,J=7.5Hz,2H),7. 31–7.23(m,1H),3.63(q,J=6.9Hz,1H),1.74(s,3H),1.21(d,J=7.0Hz,3H),0.07(s,9H). 13C NMR (101MHz, CDCl3) δ152.18,144.02,130.38,128.91,127.90,127.15,126.81,122.35,108.74,86.97,76.55,38.15, 19.43,16.28,0.01.IR(film):ν3060,2958,2897,2167,1599,1494,1450,1369,1248,1069,926,837,757,689.ESI-MS m / z(rel):335.0(M+H) + ;HRMS(ESI)Calcd.for C 21 H 27 N2Si(M+H) + :335.1938;Found:335.1935.

[0305] and / or its enantiomers

[0306] Bright yellow liquid 17ba (55.0 mg, 79%, 0 / 92 / 8, >20 / 1 dr). 1 H NMR (400MHz, CDCl3) δ7.81–7.68(m,2H),7.48(dt,J=15.7,5.1Hz,5H),7.04(t,J=8 .7Hz,2H),3.58(q,J=7.0Hz,1H),1.70(s,3H),1.17(d,J=7.0Hz,3H),0.07(s,9H). 13 C NMR (101MHz, CDCl3) δ161.74(d,J=245.5Hz),152.03,139.75,139.71,130.53,128.90(d,J =8.6Hz),122.32,114.58(d,J=21.1Hz),108.44,87.14,76.15,38.12,18.96,16.14,-0.03. 19 F NMR(376MHz, CDCl3)δ-116.23.IR(film):ν3065,2982,2959,2897,2168,1600,1508,1452,1370,1248,1231,1163,1078,838,759,688,642; ESI-MS m / z(rel):353.0(M+H) + ; (M+H) + ;HRMS(ESI)Calcd.forC 21 H 26FN2Si(M+H) + :353.1844;Found:353.1842.

[0307] and / or its enantiomers

[0308] Bright yellow liquid (56.0 mg, 76%, 0 / 93 / 7, >20 / 1 dr). 1 H NMR (400MHz, CDCl3) δ7.74(d,J=7.6Hz,2H),7.48(dd,J=15.2,7.4Hz,5H),7.33(d,J =8.6Hz,2H),3.57(q,J=6.9Hz,1H),1.70(s,3H),1.18(d,J=7.0Hz,3H),0.08(s,9H). 13 C NMR (101MHz, CDCl3) δ152.01,142.53,132.76,130.60,128.96,128.70,127.96,122.34,108.28,87.30,76.17,38.05,18 .94,16.16,-0.02.IR(film):ν3064,2958,2167,1594,1491,1452,1370,1428,1094,1012,926,838,758,688,641; ESI-MS m / z(rel):369.0(M+H) + ;HRMS(ESI)Calcd.for C 21 H 26 ClN2Si(M+H) + :369.1548;Found:369.1546.

[0309] and / or its enantiomers

[0310] Bright yellow liquid (56.0 mg, 77%, 0 / 91 / 9, >20 / 1 dr). 1 H NMR(400MHz, CDCl3)δ7.74(d,J=7.0Hz,2H),7.51–7.39(m,5H),6.89(d,J=8.8Hz,2H) ,3.81(s,3H),3.58(q,J=6.9Hz,1H),1.70(s,3H),1.18(d,J=7.0Hz,3H),0.07(s,9H). 13C NMR (101MHz, CDCl3) δ158.34,152.18,136.10,130.32,128.89,128.29,122.31,113.24,108.96,86.85,76.16,55.23,55.20,38.0 9,19.31,16.26,0.03.IR(film):ν3064,2956,2897,2167,1609,1510,1453,1298,1248,1181,1033,927,838,759,689,643; ESI-MS m / z(rel):365.0(M+H) + ;HRMS(ESI)Calcd.for C 22 H 29 N2OSi(M+H) + :365.2044;Found:365.2036.

[0311] and / or its enantiomers

[0312] Bright yellow liquid (70.7 mg, 90%, 0 / 95 / 5, 12.5 / 1 dr). 1 H NMR (400MHz, CDCl3) δ8.03(d,J=8.4Hz,2H),7.75(d,J=7.0Hz,2H),7.59(d,J=8.4Hz,2H),7.47(d, J=7.7Hz,3H),3.91(s,3H),3.60(q,J=6.9Hz,1H),1.72(s,3H),1.18(d,J=7.0Hz,3H),0.05(s,9H). 13 C NMR (101MHz, CDCl3) δ166.99,151.99,149.25,130.64,129.12,128.96,1 28.60,127.30,122.36,108.04,87.43,76.57,52.04,52.02,38.07,19.07 ,16.18,-0.04.IR(film):ν2979,2955,2168,1720,1608,1435,1371,1275 ,1248,1189,1109,1016,931,837,761,688.ESI-MSm / z(rel):393.0(M+H) + ;HRMS(ESI)Calcd.for C 23 H 29 N2O2Si(M+H) +:393.1993;Found:393.1987.

[0313] and / or its enantiomers

[0314] Bright yellow liquid (64.9 mg, 90%, 0 / 98 / 2, >20 / 1 dr). 1 H NMR (400MHz, CDCl3) δ7.77–7.71(m,2H),7.64(s,4H),7.48(d,J=7.3Hz,3H),3.58(q,J=7.0Hz,1H),1.70(s,3H),1.16(d,J=7.0Hz,3H),0.05(s,9H). 13 C NMR (101MHz, CDCl3) δ151.78,149.48,131.60,130.94,129.05,128.19,122.39,118.95,110.71,107.52,87.75,76.48,37.98,18 .38,16.04,-0.05.IR(film):ν2958,2228,2168,1607,1503,1451,1404,1372,1248,1100,1050,1017,911,838,759,688.ESI-MS m / z(rel):360.0(M+H) + ;HRMS(ESI)Calcd.for C 22 H 26 N3Si(M+H) + :360.1891;Found:360.1893.

[0315] and / or its enantiomers

[0316] Bright yellow liquid (59.1 mg, 85%, 0 / 94 / 6, >20 / 1 dr). 1 H NMR (400MHz, CDCl3) δ7.83–7.72(m,2H),7.55–7.43(m,3H),7.35–7.23(m,3H),7.11(d,J=7.1Hz,1 H),3.63(q,J=6.9Hz,1H),2.40(s,3H),1.73(s,3H),1.23(d,J=7.0Hz,3H),0.09(d,J=1.4Hz,9H). 13C NMR (101MHz, CDCl3) δ152.22,143.98,137.28,130.34,128.91,127.81,127.56,124.23,122.36,108.88,86.91,77.05,38. 16,21.79,19.61,16.34,0.05.IR(film):ν3063,2958,2167,1605,1479,1452,1370,1248,1082,928,838,758,688; ESI-MS m / z(rel):349.0(M+H) + ;HRMS(ESI)Calcd.for C 22 H 29 N2Si(M+H) + :349.2095;Found:349.2091.

[0317] and / or its enantiomers

[0318] Bright yellow liquid (60.9 mg, 84%, 0 / 93 / 7, >20 / 1 dr). 1 H NMR(400MHz, CDCl3) δ7.76(d,J=7.6Hz,2H),7.53–7.41(m,3H),7.28(t,J=8.3Hz,1H),7.09(s,2H),6. 93–6.76(m,1H),3.82(s,3H),3.60(q,J=6.9Hz,1H),1.72(s,3H),1.22(d,J=7.0Hz,3H),0.07(s,9H). 13 C NMR (101MHz, CDCl3) δ159.22,152.16,145.70,130.39,128.91,128.84,122.37,119.60,113.76,111.58,108.68,87.02,76.4 3,55.17,55.14,38.22,19.67,16.33,0.02.IR(film):ν2957,2833,2166,1600,1486,1432,1248,1043,838,759,689.ESI-MS m / z(rel):365.0(M+H) + ;HRMS(ESI)Calcd.for C 22 H 29 N2OSi(M+H) + :365.2044;Found:365.2042.

[0319] and / or its enantiomers

[0320] Bright yellow liquid (63.0 mg, 89%, 0 / 95 / 5, >20 / 1 dr). 1 H NMR (400MHz, CDCl3) δ7.84–7.69(m,2H),7.60–7.41(m,3H),7.28(dt,J=7.8,6.2Hz,2H),7 .18–7.00(m,2H),3.83(q,J=7.0Hz,1H),1.73(s,3H),1.45(d,J=7.0Hz,3H),0.03(s,9H). 13 C NMR (101MHz, CDCl3) δ160.15 (d, J = 248.1Hz), 152.25, 131.36 (d, J = 11.9Hz), 130.40, 129.48 (d, J = 5.3Hz), 128.88, 128.78 (d, J = 8.8Hz), 123 .53(d,J=3.2Hz),122.36,116.17(d,J=23.7Hz),108.43,86.99,75.81(d,J=5.4Hz),36.04(d,J=4.7Hz),19.77(d,J=2.2Hz),16.65,-0.04. 19 F NMR(376MHz, CDCl3)δ-108.62.IR(film):ν2958,2168,1578,1486,1448,1370,1248,1211,1148,1091,1034,929,838,754,688.ESI-MS m / z(rel):353.0(M+H) + ;HRMS(ESI)Calcd.for C 21 H 26 FN2Si(M+H) + :353.1844; Found:353.1848.

[0321] and / or its enantiomers

[0322] Bright yellow liquid (42.0 mg, 58%, 0 / 99 / 1, >20 / 1 dr). 1H NMR (400MHz, CDCl3) δ7.73(d,J=7.9Hz,2H),7.54–7.38(m,3H),7.26(t,J=7.7Hz,1H),7.10(d,J=7.9Hz,1H ),6.96–6.85(m,2H),4.09(q,J=7.0Hz,1H),3.77(s,3H),1.69(s,3H),1.44(d,J=7.0Hz,3H),-0.00(s,9H). 13 C NMR (101MHz, CDCl3) δ156.51,152.61,132.60,129.94,128.88,128.79,128.14,122.27,120.27,111.47,109.56,86.55,76.26,55 .30,34.94,20.04,17.00,0.03.IR(film):ν2957,2897,2165,1598,1582,1489,1434,1366,1241,1129,1026,838,751,689.ESI-MS m / z(rel):365.0(M+H) + ;HRMS(ESI)Calcd.for C 22 H 29 N2OSi(M+H) + :365.2044; Found:365.2045

[0323] and / or its enantiomers

[0324] Bright yellow liquid (70.7 mg, 92%, 0 / 94 / 6, >20 / 1 dr). 1 H NMR (400MHz, CDCl3) δ7.95(s,1H),7.84(dd,J=13.3,8.0Hz,5H),7.70(d,J=8.6Hz,1H),7.51( dt,J=7.8,6.4Hz,5H),3.76(q,J=6.6Hz,1H),1.86(s,3H),1.28(d,J=6.8Hz,3H),0.05(s,9H). 13C NMR (101MHz, CDCl3) δ152.24,141.52,133.06,132.36,130.47,128.97,128.31,127.49,127.43,126.16,125.84,125.37,122.42,108.7 1,87.22,76.74,38.10,19.69,16.41,-0.00.IR(film):ν3058,2958,2166,1598,1505,1452,1371,1248,1094,949,839,731,688.ESI-MS m / z(rel):385.0(M+H) + ;HRMS(ESI)Calcd.for C 25 H 29 N2Si(M+H) + :385.2095;Found:385.2092.

[0325] and / or its enantiomers

[0326] Bright yellow liquid (60.0 mg, 80%, 0 / 94 / 6, >20 / 1 dr). 1 H NMR (400MHz, CDCl3) δ7.74(d,J=7.0Hz,2H),7.55–7.34(m,3H),7.05(s,1H),6.95(d,J=8.2Hz,1H),6.79(d, J=8.2Hz,1H),5.94(d,J=5.6Hz,2H),3.53(q,J=6.9Hz,1H),1.67(s,3H),1.17(d,J=7.0Hz,3H),0.07(s,9H). 13 C NMR (101MHz, CDCl3) δ152.08,147.25,146.24,137.94,130.43,128.90,122.33,120.48,108.75,108.16,107.57,100.88,87.01,76.3 0,38.23,19.34,16.23,0.01.IR(film):ν2957,2893,2166,1608,1503,1485,1433,1345,1240,1090,1069,934,838,759,689.ESI-MS m / z(rel):379.0(M+H) + ;HRMS(ESI)Calcd.for C 22 H 27 N2O2Si(M+H)+ :379.1836; Found:379.1838.

[0327] and / or its enantiomers

[0328] Bright yellow liquid (58.1 mg, 90%, 0 / 97 / 3, >20 / 1 dr). 1 H NMR (400MHz, CDCl3) δ7.70 (d, J=6.5Hz, 2H), 7.43 (dd, J=11.9, 5.8Hz, 4H), 6.35 (s,2H),3.77(q,J=7.0Hz,1H),1.72(s,3H),1.23(d,J=7.0Hz,3H),0.08(s,9H). 13 C NMR (101MHz, CDCl3) δ155.72,152.01,141.90,130.52,128.87,122.36,109.96,108.32,107.60,86.57,74.89,3 5.36,17.53,15.59,0.04.IR(film):ν2983,2897,2168,1524,1453,1368,1248,1086,1007,838,759,688.ESI-MS m / z(rel):325.0(M+H) + ;HRMS(ESI)Calcd.for C 19 H 25 N2OSi(M+H) + :325.1731;Found:325.1729.

[0329] and / or its enantiomers

[0330] Bright yellow liquid (42.3 mg, 62%, 0 / 97 / 3, >20 / 1 dr). 1 H NMR(400MHz, CDCl3) δ7.76(d,J=6.9Hz,2H),7.56–7.40(m,3H),7.35–7.21(m,1H),7.10(d,J=3.1H z,1H),7.06–6.94(m,1H),3.52(q,J=7.0Hz,1H),1.79(s,3H),1.17(d,J=7.0Hz,3H),0.10(s,9H). 13C NMR (101MHz, CDCl3) δ151.85,147.44,130.61,128.93,126.00,124.82,124.35,122.49,108.20,87.29,76.07,39.1 6,19.89,16.05,0.02.IR(film):ν2958,2896,2167,1478,1451,1371,1295,1247,1093,1019,838,759,689.ESI-MS m / z(rel):341.0(M+H) + ;HRMS(ESI)Calcd.for C 19 H 25 N2SSi(M+H) + :341.1502;Found:341.151.

[0331] and / or its enantiomers

[0332] Bright yellow liquid (63.0 mg, 84%, 0 / 95 / 5, >20 / 1 dr). 1 H NMR(400MHz, CDCl3) δ7.76(d,J=6.6Hz,2H),7.57(d,J=7.4Hz,1H),7.52–7.44(m,4H),7.25(dt,J=20 .3,7.0Hz,2H),6.74(s,1H),3.85(q,J=7.0Hz,1H),1.83(s,3H),1.33(d,J=7.0Hz,3H),0.04(s,9H). 13 C NMR (101MHz, CDCl3) δ158.75,154.82,151.99,130.75,128.95,128.28,123.77,122.55,122.49,120.87,111.20,107.95,104.64,104.60,8 7.13,75.19,35.59,18.09,15.85,-0.03.IR(film):ν3065,2983,2167,1581,1475,1453,1370,1249,1208,1136,1009,838,737,687.ESI-MS m / z(rel):375.0(M+H) + ;HRMS(ESI)Calcd.for C 23 H 27 N2OSi(M+H) + :375.1887; Found:375.1891.

[0333] and / or its enantiomers

[0334] Bright yellow liquid (56.0 mg, 90%, 0 / 98 / 2). 1 H NMR (400MHz, CDCl3) δ7.73–7.64(m,2H),7.52–7.39(m,3H),2.94(q,J=7.0Hz,1H),2.37(d,J=13.4Hz,1H),2.22(d,J=13.5Hz,1H),1.96(dd,J =17.1,8.2Hz,1H),1.90–1.77(m,1H),1.58(ddd,J=27.5,21.3,8.2Hz,4H),1.26(dt,J=24.2,11.9Hz,2H),1.08(d,J=7.0Hz,3H),0.16(s,9H). 13 C NMR (101MHz, CDCl3) δ152.39,130.04,128.85,121.90,109.38,86.45,72.68,36.07,33.14,29.69,25.91,22 .22,22.10,14.85,0.19.IR(film):ν3064,2933,2854,2165,1450,1248,1019,893,837,759,688,640; ESI-MS m / z(rel):313.0(M+H) + ;HRMS(ESI)Calcd.for C 19 H 29 N2Si(M+H) + :313.2095;Found:313.209.

[0335] and / or its enantiomers

[0336] Bright yellow liquid (60.0 mg, 86%, 0 / 95 / 5, >20 / 1 dr). 1H NMR (400MHz, CDCl3) δ7.80(d,J=7.6Hz,2H),7.51(t,J=7.3Hz,2H),7.49–7.42(m,3H),7.40(t,J=7.6Hz,2H),7.30(t,J=7.1Hz,1H),3.35 (q,J=7.1Hz,1H),2.50(dd,J=14.2,7.2Hz,1H),2.12(dd,J=14.3,7.3Hz,1H),1.19(d,J=7.1Hz,3H),0.68(t,J=7.3Hz,3H),0.05(s,9H). 13 C NMR (101MHz, CDCl3) δ152.27,141.14,130.26,128.87,128.02,127.89,126.65,122.31,108.39,87.46,78.77,37.43,28.14,1 6.62,8.52,-0.03.IR(film):ν3060,2961,2879,2166,1600,1494,1478,1446,1248,1149,949,886,838,757,697,688; ESI-MS m / z(rel):349.0(M+H) + ;HRMS(ESI)Calcd.for C 22 H 29 N2Si(M+H) + :349.2095;Found:349.209.

[0337] and / or its enantiomers

[0338] Bright yellow liquid (60.0 mg, 80%, 0 / 95 / 5, 8 / 1 dr). 1 H NMR(400MHz, CDCl3) δ7.83(d,J=7.6Hz,2H),7.49(ddd,J=30.1,15.3,5.5Hz,7H),7.40–7.29(m,1H),3.33(q,J=7.0Hz,1H),2.44(dd,J =14.3,6.8Hz,1H),2.06(dd,J=14.3,4.8Hz,1H),1.62–1.44(m,1H),1.15(d,J=7.1Hz,3H),0.68(dd,J=11.7,6.7Hz,6H),0.06(s,9H). 13C NMR (101MHz, CDCl3) δ152.08,141.46,130.30,128.91,128.16,127.78,126.64,122.37,108.57,87.49,78.54,45.0 0,38.52,24.49,16.56,-0.03.IR(film):ν3061,2954,2899,2167,1600,1447,1248,912,838,729,689,642; ESI-MS m / z(rel):377.0(M+H) + ;HRMS(ESI)Calcd.for C 24 H 33 N2Si(M+H) + :377.2408;Found:377.2405.

[0339] and / or its enantiomers

[0340] Bright yellow liquid (74.0 mg, 90%, 0 / 95 / 5, >20 / 1 dr). 1 H NMR (400MHz, CDCl3) δ7.88(d,J=7.8Hz,2H),7.61–7.48(m,3H),7.31(d,J=5.5Hz,3H),7.14(d,J=5.7Hz,3H),7.07–6.95(m,2 H),6.95–6.75(m,2H),3.72(d,J=13.6Hz,1H),3.55(q,J=6.7Hz,1H),3.39(d,J=13.6Hz,1H),1.49–1.36(m,3H),0.15(s,9H). 13 C NMR (101MHz, CDCl3) δ152.10,139.72,137.66,131.07,130.46,128.97,128.00,127.81,127.48,126.89,125.93,122.52,108.52,8 8.80,79.41,43.23,34.63,16.55,0.06.IR(film):ν3060,2958,2166,1602,1478,1452,1248,1002,909,838,758,698,647; ESI-MS m / z(rel):411.0(M+H) + ;HRMS(ESI)Calcd.forC 27 H 31 N2Si(M+H) +:411.2251; Found:411.2248.

[0341] and / or its enantiomers

[0342] Bright yellow liquid (81.0 mg, 95%, 0 / 100 / 0). 1 H NMR (400MHz, CDCl3) δ7.95 (s, 2H), 7.75 (s, 3H), 7.67–7.48 (m, 5H), 7.44 (s, 5H), 3.81 (d, J = 13.7 Hz,1H),3.64(d,J=13.5Hz,2H),3.51(s,1H),3.21(d,J=13.6Hz,1H),1.43(s,3H),0.59(s,9H). 13 C NMR (101MHz, CDCl3) δ151.81,138.36,137.35,131.92,130.83,129.36,128.16,127.83,126.50,126.44,122.67,110.69,88.53,77.28,4 2.06,39.04,32.71,15.52,0.64.IR(film):ν3061,2956,2897,2162,1601,1494,1453,1435,1248,1081,1031,924,838,751,689.ESI-MS m / z(rel):425.0(M+H) + ;HRMS(ESI)Calcd.for C 28 H 33 N2Si(M+H) + :425.2408;Found:425.2408.

[0343] and / or its enantiomers

[0344] Bright yellow liquid (41.5 mg, 53%, 0 / 100 / 0, 1.5 / 1 dr). 1H NMR(400MHz,CDCl3)(taken asmixture of diastereoisomers)(major diastereoisomer)δ7.70(d,J=7.5Hz,2H),7.52–7.42(m,3H),7.11(dd,J=15.2,8.4Hz,2H),6.83(t,J=8.6Hz,2H),3.78(s,3H), 3.44(q,J=6.9Hz,1H),2.57–2.50(m,2H),2.40–2.31(m,1H),2.19–2.09(m,1H),1.37(s,3H),1.12(d,J=7.0Hz,3H),0.20(s,9H); 13 C NMR(101MHz,CDCl3)(taken as mixture ofdiastereoisomers)δ157.73,157.67,152.15,134.78,134.75,130.24,130.09,129.19,128 .94,128.86,122.07,113.80,113.76,109.16,109.11,86.51,86.26,74.20,73.82,55.25,41. 53,38.30,35.78,34.42,29.30,28.80,19.07,17.42,15.51,0.21,0.13.IR(film):ν2953,283 3,2165,1611,1510,1453,1371,1244,1176,1037,838,758,688.ESI-MSm / z(rel):393.0(M+H) + ;HRMS(ESI)Calcd.for C 24 H 33 N2OSi(M+H) + :393.2357;Found:393.2353.

[0345] and / or its enantiomers

[0346] Bright yellow liquid (65.1 mg, 80%, 0 / 99 / 1, >20 / 1 dr). 1H NMR (400MHz, CDCl3) δ7.85(d,J=7.8Hz,2H),7.59–7.46(m,5H),7.40(t,J=7.4Hz,2H),7.31(s,5H),7.25(d,J= 4.3Hz,1H),3.75(d,J=11.0Hz,1H),2.93(d,J=13.0Hz,1H),2.77(t,J=12.1Hz,1H),1.88(s,3H),0.06(s,9H). 13 C NMR (101MHz, CDCl3) δ152.15,143.89,140.32,130.58,129.37,129.02,128.09,128.05,127.06,126.97,126.18,122.47,106.63,89.33,7 6.82,47.03,36.84,20.33,-0.08.IR(film):ν3060,3025,2960,2168,1598,1493,1450,1367,1247,1072,1047,998,841,755,689.ESI-MS m / z(rel):411.0(M+H) + ;HRMS(ESI)Calcd.for C 27 H 31 N2Si(M+H) + :411.2251; Found:411.2248.

[0347] and / or its enantiomers

[0348] Bright yellow liquid (66.6 mg, 92%, 0 / 100 / 0, >20 / 1 dr). 1 H NMR (400MHz, CDCl3) δ7.81 (d, J = 7.4Hz, 2H), 7.57–7.42 (m, 5H), 7.37 (t, J = 7.5Hz, 2H), 7.32–7. 24(m,1H),3.40(s,1H),1.95(d,J=6.3Hz,1H),1.76(s,3H),0.98(t,J=7.3Hz,6H),0.07(s,9H). 13C NMR (101MHz, CDCl3) δ152.06,144.97,130.31,128.91,128.10,126.73,126.68,122.53,104.76,90.12,77.55,52.11,52 .08,27.82,24.14,22.84,19.82,0.04.IR(film):ν3060,2958,2168,1599,1493,1445,1248,1012,838,758,687.ESI-MS m / z(rel):363.0(M+H) + ;HRMS(ESI)Calcd.for C 23 H 31 N2Si(M+H) + :363.2251;Found:363.225.

[0349] and / or its enantiomers

[0350] Bright yellow liquid (58.3 mg, 81%, 0 / 92 / 8, >20 / 1 dr). 1 H NMR (00MHz, CDCl3) δ7.81–7.74(m,2H),7.54–7.43(m,5H),7.37(dd,J=14.4,7.2Hz,2H),7.30–7.23(m,1H),6.03– 5.84(m,1H),5.12–5.01(m,2H),3.54(t,J=7.3Hz,1H),2.28(t,J=7.3Hz,2H),1.77(s,3H),0.08(d,J=3.4Hz,9H). 13 C NMR (101MHz, CDCl3) δ152.08,143.95,136.55,130.46,128.92,127.99,127.02,126.86,122.40,116.15,106.65,88.56,76. 59,44.48,34.79,20.12,-0.01.IR(film):ν3063,2957,2169,1641,1599,1494,1444,1371,1248,1027,837,758,689.ESI-MS m / z(rel):360.9(M+H) + ;HRMS(ESI)Calcd.for C 23 H 29 N2Si(M+H) + :361.2095;Found:361.2089.

[0351] and / or its enantiomers

[0352] Bright yellow liquid (60.0 mg, 83%, 0 / 95 / 5, >20 / 1 dr). 1 H NMR (400MHz, CDCl3) δ7.77(d,J=6.8Hz,2H),7.55–7.43(m,5H),7.36(t,J=7.5Hz,2H),7.31–7.24(m,1H),3. 51(d,J=11.0Hz,1H),1.75(s,3H),1.72–1.65(m,1H),1.54–1.34(m,3H),0.93(t,J=6.9Hz,3H),0.07(s,9H). 13 C NMR (101MHz, CDCl3) δ152.16,144.29,130.36,128.91,127.90,127.10,126.74,122.37,107.57,87.88,76.76,44.32,3 2.09,21.41,19.92,13.94,0.05.IR(film):ν3060,2957,2168,1599,1493,1445,1371,1248,1066,837,758,689.ESI-MS m / z(rel):363.0(M+H) + ;HRMS(ESI)Calcd.for C 23 H 31 N2Si(M+H) + :363.2251;Found:363.2258.

[0353] and / or its enantiomers

[0354] Bright yellow liquid (60.0 mg, 87%, 0 / 97 / 3, >20 / 1 dr). 1 H NMR (400MHz, CDCl3) δ7.75(d,J=7.1Hz,2H),7.57–7.41(m,5H),7.35(t,J=7.6Hz,2H),7.26(d,J=6.8Hz,1H),3.48(d,J=8 .9Hz,1H),2.15–1.96(m,2H),1.72(s,3H),1.66(s,1H),1.48–1.22(m,7H),0.91(t,J=7.0Hz,3H),0.84(t,J=7.1Hz,3H). 13C NMR (101MHz, CDCl3) δ152.20,144.69,130.25,128.89,127.89,127.02,126.60,122.33,83.63,80.26,77.07,43.31,32.52,31.05,21.75,2 1.48,19.85,18.40,13.93,13.59.IR(film):ν3060,2955,2930,2869,2320,1598,1493,1449,1371,1152,1099,1069,1026,760,691.ESI-MS m / z(rel):347.1(M+H) + ;HRMS(ESI)Calcd.for C 24 H 31 N2(M+H) + :347.2482; Found:347.2479.

[0355] and / or its enantiomers

[0356] Yellow solid (50.0 mg, 73%, 0 / 95 / 5, >20 / 1 dr). mp: 108.7-109.2 ° C; 1 H NMR(400MHz, CDCl3)δ7.77(d,J=7.8Hz,2H),7.58–7.42(m,5H),7.36(t,J=7.3Hz,2H),7.31–7.23(m,1H), 3.63(q,J=6.8Hz,1H),2.31(s,1H),1.74(s,3H),1.64(d,J=22.5Hz,4H),1.42(s,1H),1.39–1.15(m,8H). 13 C NMR (101MHz, CDCl3) δ152.23,144.48,130.29,128.90,127.89,127.14,126.68,122.35,87.08,81.70,76.92,37.20,32.79,28.8 5,26.01,24.51,19.38,16.83.IR(film):ν2979,2926,2850,1598,1521,1446,1370,1300,1233,1101,1067,923,761,688.ESI-MS m / z(rel):345.0(M+H) + ;HRMS(ESI)Calcd.for C 24 H 29 N2(M+H)+ :345.2325;Found:345.2327.

[0357] and / or its enantiomers

[0358] Bright yellow liquid (47.0 mg, 62%, 0 / 90 / 10, >20 / 1 dr). 1 H NMR (400MHz, CDCl3) δ7.74(d,J=7.3Hz,2H),7.51–7.44(m,5H),7.34(t,J=7.6Hz,2H),7.26(d,J= 7.6Hz,1H),3.64(q,J=7.1Hz,1H),1.72(s,3H),1.21(d,J=7.0Hz,3H),0.81(s,9H),-0.01(s,6H). 13 C NMR (101MHz, CDCl3) δ152.04,143.92,130.38,128.86,127.96,127.08,126.79,122.41,109.00,84.97,38.06,25.98,19. 50,16.45,-4.60.IR(film):ν2951,2928,2854,2166,1599,1494,1449,1371,1249,1097,1005,923,835,762,686.ESI-MS m / z(rel):377.3(M+H) + ;HRMS(ESI)Calcd.for C 24 H 33 N2Si(M+H) + :377.2408;Found:377.2409.

[0359] Example 3

[0360]

[0361] Hydrazone (0.4 mmol) and toluene (2.0 mL) were added to a 10 mL dry reaction tube. LiHMDS (1.0 Min THF, 0.4 mL, 0.4 mmol) was added under ice bath. After the addition, the mixture was stirred at room temperature for 30 min. [Pd(η 3-C3H5)Cl]2 (1.83 mg, 0.005 mmol), L (0.01 mmol) and toluene (1.0 mL) were added at room temperature. t-BuOK (1.0 M inTHF, 25 uL, 0.025 mmol) was added. After the addition was completed, the mixture was stirred at room temperature for 30 min and then added to the above 10 mL reaction tube. Then, propargyl reagent (32.2 mg, 0.2 mmol) and toluene (1.0 mL) were added. The reaction was allowed to proceed overnight at the corresponding temperature. After the reaction was completed, water (0.5 mL) was added to quench the reaction. The mixture was passed through a short silica gel column, washed with ethyl acetate (50 mL), concentrated, and mesitylene was added as an internal standard. The regioselectivity and diastereoselectivity of the reaction were 1 The crude H NMR spectrum was confirmed.

[0362] When When it is a ligand, the reaction yield (16aa+17aa) is 83%, 16aa / 17aa / 17ab=83 / 12 / 5, for product 16aa, anti / syn>20 / 1, for product 17aa, anti / syn=1 / 1;

[0363] When When it is a ligand, the reaction yield (16aa+17aa) is 98%, 16aa / 17aa / 17ab=39 / 58 / 3, for the product 16aa, anti / syn>20 / 1, for the product 17aa, anti / syn=6 / 1;

[0364] When When it is a ligand, the reaction yield (16aa+17aa) is 98%, 16aa / 17aa / 17ab=14 / 83 / 3, for the product 16aa, anti / syn>20 / 1, for the product 17aa, anti / syn=6 / 1;

[0365] When When it is a ligand, the reaction yield (16aa+17aa) is 28%, 16aa / 17aa / 17ab=60 / 20 / 20, for the product 16aa, anti / syn>20 / 1, for the product 17aa, anti / syn=1 / 1;

[0366] When When it is a ligand, the reaction yield (16aa+17aa) is 9%, 16aa / 17aa / 17ab=0 / 100 / 0, and for the product 17aa, anti / syn=1 / 1;

[0367] When When it is a ligand, the reaction yield (16aa+17aa) is 85%, 16aa / 17aa / 17ab=0 / 84 / 16, and for the product 17aa, anti / syn>20 / 1;

[0368] When When it is the ligand, the reaction yield (16aa+17aa) is <5%;

[0369] When PPh3 was used as the ligand, the reaction yield (16aa+17aa) was 16%, 16aa / 17aa / 17ab=0 / 15 / 85, and for the product 17aa, anti / syn=1.2 / 1;

[0370] When (R)-BINAP was used as the ligand, the reaction yield (16aa+17aa) was 25%, 16aa / 17aa / 17ab=0 / 25 / 75, and for the product 17aa, anti / syn=2.6 / 1;

[0371] Example 4 (Chirality transfer experiment)

[0372]

[0373] Hydrazone (0.4 mmol) and toluene (2.0 mL) were added to a 10 mL dry reaction tube. LiHMDS (1.0 Min THF, 0.4 mL, 0.4 mmol) was added under ice bath. After the addition, the mixture was stirred at room temperature for 30 min. [Pd(η 3 -C3H5)Cl]2 (1.83 mg, 0.005 mmol), L (4.3 mg, 0.01 mmol) and toluene (1.0 mL) were added at room temperature. t-BuOK (1.0 M in THF, 25 uL, 0.025 mmol) was added. After the addition was completed, the mixture was stirred at room temperature for 30 min and then added to the above 10 mL reaction tube. Then, propargyl reagent (S)-15a (32.2 mg, 0.2 mmol) and toluene (1.0 mL) were added. The reaction was allowed to proceed overnight at the corresponding temperature. After the reaction was completed, water (0.5 mL) was added to quench the reaction. The mixture was passed through a short silica gel column, rinsed with ethyl acetate (50 mL), concentrated, and mesitylene was added as an internal standard. The regioselectivity and diastereoselectivity of the reaction were 1 The yield of the propargyl substituted product was determined by crude H NMR spectroscopy and preparative plate separation (PE / EA=50 / 1).

[0374]

[0375] Bright yellow liquid (49 mg, 73%, 84 / 5 / 11, >20 / 1dr, 97% ee). [α] D25 =60.9 (c 1.0, CHCl3); HPLC (PC-3 (Phenomenex Cellulose-3), CH3CN:H2O = 80:20, 0.7mL / min, 214nm, Column Temperature: 25): t minor =7.47min,t major =9.22min.

[0376]

[0377] Hydrazone (0.4 mmol) and toluene (2.0 mL) were added to a 10 mL dry reaction tube. LiHMDS (1.0 Min THF, 0.4 mL, 0.4 mmol) was added under ice bath. After the addition, the mixture was stirred at room temperature for 30 min. [Pd(η 3 -C3H5)Cl]2 (1.83 mg, 0.005 mmol), L (4.3 mg, 0.01 mmol) and toluene (1.0 mL) were added at room temperature. t-BuOK (1.0 M in THF, 25 uL, 0.025 mmol) was added. After the addition was completed, the mixture was stirred at room temperature for 30 min and then added to the above 10 mL reaction tube. Then, propargyl reagent (0.2 mmol, 32.2 mg) and toluene (1.0 mL) were added. The reaction was allowed to proceed overnight at the corresponding temperature. After the reaction was completed, water (0.5 mL) was added to quench the reaction. The mixture was passed through a short silica gel column, washed with ethyl acetate (50 mL), concentrated, and mesitylene was added as an internal standard. The regioselectivity and diastereoselectivity of the reaction were 1 The yield of the propargyl substituted product was determined by crude H NMR spectroscopy and preparative plate separation (PE / EA=50 / 1).

[0378]

[0379] Bright yellow liquid (55 mg, 82%, 84 / 5 / 11, >20 / 1dr, 90% ee). [α] D 25 =-14.0 (c 1.0, CHCl3); Yellow oil; HPLC (PC-3 (Phenomenex Cellulose-3), CH3CN:H2O=80:20, 0.7mL / min, 214nm, Column Temperature: 25): t minor =7.74min,t major =9.36min.

[0380] When (R)-15a was used, the reaction also afforded (R,R)-16aa and (S,R)-17aa with excellent enantioselectivity.

[0381] Example 5

[0382]

[0383] To a 50 mL reflux reaction flask were added 16aa (0.15 mmol, 50 mg), zinc powder (13.7 mmol, 0.9 g), and methanol (6.0 mL). Concentrated hydrochloric acid (90 mmol, 6.0 M × 15.0 mL) was then added. The mixture was heated to 75°C for 4 h, and then sodium hydroxide solution was added to adjust the solution pH to >12. The solution was extracted three times with ethyl acetate. The organic phases were combined, washed with saturated sodium chloride solution (50 mL), dried over anhydrous sodium sulfate, and the solvent was removed under reduced pressure. Separation on a preparative plate (PE / Et2O = 90 / 8) gave 18 (21.3 mg, 58% yield) as a light yellow liquid. 1 H NMR (400MHz, CDCl3) δ7.45(d,J=7.5Hz,2H),7.29(t,J=7.6Hz,2H),7.19(t,J=7.2Hz,1H ),5.04(q,J=6.7Hz,1H),1.85(s,2H),1.72(d,J=6.8Hz,3H),1.60(s,3H),-0.11(s,9H). 13 C NMR(101MHz, CDCl3)δ205.56,148.42,127.94,126.33,125.79,83.16,57.72,31.88,14.01,0.31; HRMS(ESI)Calcd.for C 15 H 24 NSi(M+H) + :246.16725;Found:246.16681.

[0384] To a 10 mL reaction tube, add 4-bromophenylmethanesulfonyl chloride (0.044 mmol, 11 mg) and dichloromethane (0.5 mL), followed by triethylamine (0.044 mmol, 7.0 uL). Stir for 2 min, then add amine 18 (0.044 mmol, 10 mg) and dichloromethane (0.5 mL). Slowly warm the mixture to room temperature. TLC indicates the reaction is complete. Concentrate the mixture and separate it on a preparative plate (PE / EA = 10 / 1) to obtain 19 (14 mg, 70% yield), a colorless solid. 97% ee; [α] D 20 =61.9 (c 1.0, CHCl3); 1H NMR (400MHz, CDCl3) δ7.26(t,J=6.9Hz,2H),7.08(t,J=7.5Hz,5H),6.99(t,J=7.4Hz,2H ),5.53(s,1H),5.30(q,J=6.8Hz,1H),1.94(s,3H),1.78(d,J=6.9Hz,3H),-0.24(s,9H). 13 C NMR (101MHz, CDCl3) δ202.30,141.49,140.23,131.37,128.04,128.00,127.53,127.32,1 25.99,106.88,87.54,60.88,27.28,14.06,-0.02.IR(film):ν3296,2992,2894,1948,15 75,1472,1380,1321,1281,1160,1115,1090,969,838,744,964; MS(EI)m / z(ref):340(10 0),338(95),221(25),219(22),157(28),156(24),155(38),73(46); HRMS(EI)Calcd.for C 21 H 26 NO2SiSBr(M + ):463.0637; Found:463.0634.HPLC(IC,Hexane:iPrOH=82:18,0.7mL / min,214nm):t minor =9.24min,t major =10.05min.

[0385] The single crystal data of product 19 are as follows:

[0386]

[0387]

[0388] In a 50 mL reflux reaction flask, 17aa (0.2 mmol, 65 mg), zinc powder (18.3 mmol, 1.2 g), and methanol (8.0 mL) were added, followed by concentrated hydrochloric acid (120 mmol, 6.0 M × 20.0 mL). The mixture was heated to 75°C for 4 h, and then sodium hydroxide solution was added to adjust the solution pH to >12. The solution was extracted three times with ethyl acetate. The organic phases were combined, washed with saturated sodium chloride solution (50 mL), dried over anhydrous sodium sulfate, and the solvent was removed under reduced pressure. The mixture was separated on a preparative plate (PE / EA = 4 / 1) to give 20 (20 mg, 65% yield) as a light yellow liquid. 1HNMR (400MHz, CDCl3) δ7.42(d,J=7.8Hz,2H),7.31(t,J=7.6Hz,2H),7.22(dd,J=13.3,6.0Hz,1H ),2.90(q,J=7.1Hz,1H),2.22(s,2H),2.16(d,J=0.8Hz,1H),1.58(s,3H),0.90(d,J=7.0Hz,3H). 13 C NMR(101MHz, CDCl3)δ145.66,128.14,126.47,125.36,86.22,71.04,56.92,38.52,30.42,15.76.HRMS(ESI)Calcd.for C 12 H 15 N(M) + :173.1199;Found:173.1197.

[0389] To a 10 mL reaction tube, add 4-bromobenzoyl chloride (0.06 mmol, 15 mg) and dichloromethane (0.5 mL). Then, add triethylamine (0.06 mmol, 9.0 uL). Stir for 2 min, then add amine 20 (0.06 mmol, 15 mg) and dichloromethane (0.5 mL). Slowly warm the mixture to room temperature. TLC indicates the reaction is complete. Concentrate the mixture and separate it on a preparative plate (PE / EA = 10 / 1) to obtain a colorless solid 21 (18 mg, 80% yield). 92% ee; [α] D 20 =-30.8 (c 1.0, CHCl3); 1 H NMR (400MHz, CDCl3) δ7.69(d,J=8.6Hz,2H),7.59(d,J=8.6Hz,2H),7.41(d,J=7.2Hz,2H),7.33(t,J=7.5Hz,2H),7.27 (d,J=6.7Hz,1H),6.81(s,1H),3.14(qd,J=7.0,2.4Hz,1H),2.31(d,J=2.5Hz,1H),2.03(s,3H),1.00(d,J=7.1Hz,3H). 13C NMR (101MHz, CDCl3) δ163.01,147.74,138.78,131.61,129.27,125.91,125.48,124.55,123.51,82.25,70.17,57.99,35.30,21 .58,13.62.IR(film):ν3359,3270,2920,2851,1643,1572,1457,1418,1324,1280,1153,1080,1010,970,876,770,695.ESI-MS m / z(rel):391.9(M) + ;HRMS(ESI)Calcd.for C 18 H 17 O2NBrS(MH) + :390.0163; Found:390.0174.HPLC(IE3,Hexane:iPrOH=95:5,0.7mL / min,214nm):t minor =31.74min,t major =29.72min.

[0390] The single crystal data of product 21 are as follows:

[0391]

[0392]

[0393] Single crystals of products 19 and 21 confirm that when the propargyl reagent is chiral, the target compound with corresponding chiral shift and absolute configuration can be obtained. This provides a new method for further preparation of chiral compounds, especially compounds with absolute configuration.

[0394] Comparative Example 1

[0395] When an imine with the following structure is used instead of a hydrazone, the reaction can only obtain a propargyl-substituted product with a low yield and an extremely poor dr value, and an allene product cannot be obtained through ligand regulation.

[0396]

[0397] Hydrazone (0.4 mmol) and toluene (2.0 mL) were added to a 10 mL dry reaction tube. LiHMDS (1.0 Min THF, 0.4 mL, 0.4 mmol) was added under ice bath. After the addition, the mixture was stirred at room temperature for 30 min. [Pd(η 3-C3H5)Cl]2 (1.83 mg, 0.005 mmol), L (4.3 mg, 0.01 mmol) and toluene (1.0 mL) were added at room temperature. t-BuOK (1.0 M in THF, 25 uL, 0.025 mmol) was added. After the addition was completed, the mixture was stirred at room temperature for 30 min and then added to the above 10 mL reaction tube. Then, propargyl reagent (32.2 mg, 0.2 mmol) and toluene (1.0 mL) were added. The reaction was allowed to proceed overnight at the corresponding temperature. After the reaction was completed, water (0.5 mL) was added to quench the reaction. The mixture was passed through a short silica gel column, washed with ethyl acetate (50 mL), concentrated, and mesitylene was added as an internal standard. The regioselectivity and diastereoselectivity of the reaction were 1 The crude H NMR spectrum was confirmed.

[0398] When X is OBoc, the reaction yield (16aa+17aa) at room temperature is 11%, 16aa / 17aa / 18aa=13 / 4 / 83, and for product 16aa, anti / syn>20 / 1;

[0399] When X is OPiv, the reaction cannot occur at room temperature;

[0400] When X is Br, the reaction yield (16aa + 17aa) at room temperature is 49%, 16aa / 17aa / 18aa = 9 / 55 / 36. For product 16aa, the anti / syn ratio is > 20 / 1, and for product 17aa, the anti / syn ratio is 1 / 1.

[0401] Comparative Example 3

[0402] When the allenyl reagent 22 with the following structure is used instead of the propargyl reagent 15, no allene product and propargyl substitution product are observed in the reaction.

[0403]

[0404] The present invention provides a technical solution that is completely different from the prior art concept to prepare polysubstituted alkyl α-quaternary carbon amine compounds substituted with allene or propynyl groups; and the technical solution provided by the present invention achieves good yield and selectivity.

[0405] Specifically, in the reaction of the present invention, the hydrazone is a nucleophile and the propargyl reagent is an electrophile, and it can be seen that the hydrazone portion undergoes dipole flipping. The method of the present invention can obtain two consecutive tertiary carbon and quaternary carbon products with large steric hindrance in high yield and high diastereoselectivity. By using nitrogen heterocyclic carbene ligands (NHCs) of different structures, allene products and propargyl substituted products can be obtained with high regioselectivity and high diastereoselectivity, respectively. The method effectively solves the selectivity problem in the addition reaction of allene metal reagents and propargyl metal reagents to imines.

[0406] All documents mentioned in this application are incorporated herein by reference, just as if each document were incorporated herein by reference individually. It should also be understood that after reading the above teachings of the present invention, those skilled in the art may make various changes or modifications to the present invention, and that such equivalents also fall within the scope of the claims appended hereto.

Claims

1. A method for preparing a polysubstituted alkylaryl azo compound as shown in Formula I and / or Formula II, characterized in that: It includes the following steps: Step 1: In a solvent, a hydrazone as shown in Formula IV is subjected to a hydrogen extraction reaction with a strong base to obtain a mixture A; Step 2: In the presence of an nitrogen heterocyclic carbene-palladium catalyst system and a base, the mixture A and a propargyl reagent represented by Formula III are subjected to a coupling reaction as shown below to obtain a polysubstituted alkylaryl azo compound represented by Formula I and / or Formula II; The nitrogen heterocyclic carbene is as shown in Formula V; Wherein, X is a halogen; R 8a and R 8a’ are independently H or phenyl; Or, R 8a and R 8a’ connected to it Together they form a benzene ring; R 8b and R 8b’ Independently C5-C 10 The polycyclic cycloalkyl group or one or more R 10a Substituted C5-C 10 When there are multiple substituents, they may be the same or different; n1 is independently 0, 1, 2 or 3; R 9a 、R 9b and R 9c are independently halogen, C1-C6 alkyl, 10c Substituted C1-C6 alkyl, C3-C7 cycloalkyl, one or more R 10b Substituted C3-C7 cycloalkyl; when there are multiple substituents, they may be the same or different; R 9d are independently H, C1-C6 alkyl or one or more R 10d Substituted C1-C6 alkyl; when there are multiple substituents, they may be the same or different; R 9e Independently C6-C 14 The aryl group or one or more R 10e Substituted C6-C 14 When there are multiple substituents, they may be the same or different; R 10a 、R 10b 、R 10c 、R 10d and R 10e are independently C1-C6 alkyl or phenyl; represents a single bond or a double bond; Among them, R 1 are independently H, C1-C 10 Alkyl, one or more R 1a Substituted C1-C 10 Alkyl, C2-C 10 Alkenyl, one or more R 1b Substituted C2-C 10 Alkenyl, C6-C 14 The aryl group, one or more R 1c Substituted C6-C 14 aryl, 5-10 membered heteroaryl or one or more R 1d substituted 5-10 membered heteroaryl; when there are multiple substituents, they are the same or different; the 5-10 membered heteroaryl and the one or more R 1d In the 5-10 membered heteroaryl group of the substituted 5-10 membered heteroaryl group, the heteroatom is selected from one or more of N, O and S, and the number of the heteroatoms is 1, 2, 3 or 4; R 2 Independently C1-C 10 Alkyl, one or more R 2a Substituted C1-C 10 Alkyl, C3-C 10 Cycloalkyl, one or more R 2b Substituted C3-C 10 Cycloalkyl or When there are multiple substituents, they may be the same or different; R 3 and R 4 Independently C1-C 10 Alkyl, one or more R 3a Substituted C1-C 10 Alkyl, C2-C 10 Alkenyl, one or more R 3b Substituted C2-C 10 Alkenyl, C6-C 14 The aryl group, one or more R 3c Substituted C6-C 14 aryl, 5-10 membered heteroaryl or one or more R 3d Substituted 5-10 membered heteroaryl; when there are multiple substituents, they are the same or different; the 5-10 membered heteroaryl may be replaced by one or more R 3d In the 5-10 membered heteroaryl group of the substituted 5-10 membered heteroaryl group, the heteroatom is selected from one or more of N, O and S, and the number of the heteroatoms is 1, 2, 3 or 4; Or, R 3 and R 4 connected, independently forming with the carbon to which it is connected: C3-C 10 The cycloalkyl group or one or more R 4a Substituted C3-C 10 When there are multiple substituents, they may be the same or different; R 5 Independently C6-C 14 The aryl group, one or more R 5a Substituted C6-C 14 aryl, 5-10 membered heteroaryl or one or more R 5b substituted 5-10 membered heteroaryl; when there are multiple substituents, they are the same or different; the 5-10 membered heteroaryl and the one or more R 5b In the 5-10 membered heteroaryl group of the substituted 5-10 membered heteroaryl group, the heteroatom is selected from one or more of N, O and S, and the number of the heteroatoms is 1, 2, 3 or 4; R 1a 、R 1b 、R 1c 、R 1d 、R 2a 、R 2b 、R 3a 、R 3b 、R 3c 、R 3d 、R 4a 、R 5a and R 5b are independently CN, halogen, C1-C6 alkyl, C1-C6 alkyl-O-, C1-C6 alkyl-OC(=O)-, -O-(C1-C4 alkylene)-O-, phenyl or The C1-C6 alkyl, C1-C6 alkyl-O-, C1-C6 alkyl-OC(=O)-, -O-(C1-C4 alkylene)-O- and phenyl groups are optionally substituted by one or more substituents R 7a Replacement, R 7a are independently CN, halogen, C1-C6 alkyl or C1-C6 alkyl-O-; when there are multiple substituents, they are the same or different; R 2c 、R 2d 、R 2e 、R 6a 、R 6b and R 6c are independently C1-C6 alkyl; The carbon atom marked with "*" indicates that when it is a chiral carbon atom, it is in S configuration, R configuration or a mixture thereof.

2. The method for preparing the multi-substituted alkylaryl azo compound of formula I and / or formula II according to claim 1, characterized in that: When R 1 Independently C1-C 10 The alkyl group or one or more R 1a Substituted C1-C 10 When the alkyl group is C1-C 10 The alkyl group and one or more R 1a Substituted C1-C 10 The C1-C 10 The alkyl group is methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl or tert-butyl; and / or, when R 1 Independently C2-C 10 The alkenyl group or one or more R 1b Substituted C2-C 10 When the alkenyl group, the C2-C 10 The alkenyl group and one or more R 1b Substituted C2-C 10 The C2-C 10 The alkenyl group is vinyl, 1-propenyl, 2-propenyl, 2-butenyl, 1-butenyl or butadienyl; and / or, when R 1 Independently C6-C 14 The aryl group or one or more R 1c Substituted C6-C 14 When the aryl group is 14 The aryl group and one or more R 1c Substituted C6-C 14 The C6-C 14 The aryl group is phenyl or naphthyl; and / or, when R 1 is independently a 5-10 membered heteroaryl or is replaced by one or more R 1d When the 5-10 membered heteroaryl is substituted, the 5-10 membered heteroaryl may be replaced by one or more R 1d In the 5-10 membered heteroaryl group of the substituted 5-10 membered heteroaryl group, the heteroatom is selected from one or more of N, O and S, and the number of heteroatoms is 1, 2 or 3; and / or, when R 2 Independently C1-C 10 The alkyl group or one or more R 2a Substituted C1-C 10 When the alkyl group is C1-C 10 The alkyl group and one or more R 2a Substituted C1-C 10 The C1-C 10 The alkyl group is methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl or tert-butyl; and / or, when R 2 Independently C3-C 10 The cycloalkyl group or one or more R 2b Substituted C3-C 10 When the cycloalkyl group is 10 The cycloalkyl group and one or more R 2b Substituted C3-C 10 The C3-C 10 The cycloalkyl group is cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl; and / or, when R 3 and R 4 Independently C1-C 10 The alkyl group or one or more R 3a Substituted C1-C 10 When the alkyl group is C1-C 10 The alkyl group and one or more R 3a Substituted C1-C 10 The C1-C 10 The alkyl group is methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl or tert-butyl; and / or, when R 3 and R 4 Independently C2-C 10 The alkenyl group or one or more R 3b Substituted C2-C 10 When the alkenyl group, the C2-C 10 The alkenyl group and one or more R 3b Substituted C2-C 10 The C2-C 10 The alkenyl group is vinyl, 1-propenyl, 2-propenyl, 2-butenyl, 1-butenyl or butadienyl; and / or, when R 3 and R 4 Independently C6-C 14 The aryl group or one or more R 3c Substituted C6-C 14 When the aryl group is 14 The aryl group and one or more R 3c Substituted C6-C 14 The C6-C 14 The aryl group is phenyl or naphthyl; and / or, when R 3 and R 4 is independently a 5-10 membered heteroaryl or is replaced by one or more R 3d When the 5-10 membered heteroaryl is substituted, the 5-10 membered heteroaryl and one or more R 3d In the 5-10 membered heteroaryl group of the substituted 5-10 membered heteroaryl group, the heteroatom is selected from one or more of N, O and S, and the number of heteroatoms is 1, 2 or 3; and / or, when R 3 and R 4 connected, independently forming with the carbon to which it is connected: C3-C 10 The cycloalkyl group or one or more R 4a Substituted C3-C 10 When the cycloalkyl group is 10 The cycloalkyl group and one or more R 4a Substituted C3-C 10 The C3-C 10 The cycloalkyl group is cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl; and / or, when R 5 Independently C6-C 14 The aryl group or one or more R 5a Substituted C6-C 14 When the aryl group is C6-C 14 The aryl group and one or more R 5a Substituted C6-C 14 The C6-C 14 The aryl group is phenyl or naphthyl; and / or, when R 5 is independently a 5-10 membered heteroaryl or is replaced by one or more R 5b When the 5-10 membered heteroaryl is substituted, the 5-10 membered heteroaryl and one or more R 5b In the 5-10 membered heteroaryl group of the substituted 5-10 membered heteroaryl group, the heteroatom is selected from one or more of N, O and S, and the number of heteroatoms is 1, 2 or 3; and / or, when R 1a 、R 1b 、R 1c 、R 1d 、R 2a 、R 2b 、R 3a 、R 3b 、R 3c 、R 3d 、R 4a 、R 5a and R 5b When they are independently C1-C6 alkyl, C1-C6 alkyl-O- or C1-C6 alkyl-OC(=O)-, the C1-C6 alkyl in the C1-C6 alkyl, C1-C6 alkyl-O- and C1-C6 alkyl-OC(=O)- is methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl or tert-butyl; and / or, R 2c 、R 2d 、R 2e 、R 6a 、R 6b and R 6c When they are independently C1-C6 alkyl, the C1-C6 alkyl is methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl or tert-butyl; and / or, when R 1a 、R 1b 、R 1c 、R 1d 、R 2a 、R 2b 、R 3a 、R 3b 、R 3c 、R 3d 、R 4a 、R 5a 、R 5b and R 7a When independently halogen, the halogen is fluorine, chlorine, bromine or iodine; and / or, when R 1a 、R 1b 、R 1c 、R 1d 、R 2a 、R 2b 、R 3a 、R 3b 、R 3c 、R 3d 、R 4a 、R 5a and R 5b When they are independently -O-(C1-C4 alkylene)-O-, the C1-C4 alkylene is methylene, -CH2CH2-, -CH(CH3)-, -CH(CH3)CH2- or -C(CH3)2-; and / or, when R 7a When they are independently C1-C6 alkyl or C1-C6 alkyl-O-, the C1-C6 alkyl in the C1-C6 alkyl and C1-C6 alkyl-O- is methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl or tert-butyl; and / or, when R 1 Independently by one or more R 1a Substituted C1-C 10 When the alkyl group is 1a Phenyl or and / or, when R 2 Independently hour, is trimethylsilyl; and / or, when R 3 and R 4 Independently by one or more R 3a Substituted C1-C 10 When the alkyl group is 3a is phenyl or R 7a substituted phenyl; and / or, when R 3 and R 4 Independently by one or more R 3c Substituted C6-C 14 When the aryl group is 3c is CN, halogen, C1-C6 alkyl, C1-C6 alkyl-O-, C1-C6 alkyl-OC(=O)-, or -O-(C1-C4 alkylene)-O-; and / or, R 1 are independently H, C1-C 10 Alkyl, one or more R 1a Substituted C1-C 10 Alkyl, C2-C 10 The alkenyl group or one or more R 1b Substituted C2-C 10 alkenyl; and / or, R 2 Independently C1-C 10 Alkyl, one or more R 2a Substituted C1-C 10 Alkyl, C3-C 10 Cycloalkyl or and / or, R 3 and R 4 Independently C1-C 10 Alkyl, one or more R 3a Substituted C1-C 10 Alkyl, C6-C 14 The aryl group, one or more R 3c Substituted C6-C 14 aryl, 5-10 membered heteroaryl or one or more R 3d substituted 5-10 membered heteroaryl; and / or, R 5 Independently C6-C 14 The aryl group, one or more R 5a Substituted C6-C 14 aromatic groups; And / or, in the polysubstituted alkylarylazo compound as shown in formula I, when the carbon atoms with "*" at positions 1 and 2 are both chiral carbon atoms, and according to the "sequence rule" of the substituents, R 4 Prioritizes R 3 When , it is as shown below: and / or its enantiomers; And / or, in the multi-substituted alkylarylazo compound as shown in formula II, when the carbon atoms with "*" at positions 1 and 2 are both chiral carbon atoms, and according to the "sequence rule" of the substituents, R 4 Prioritizes R 3 When , it is as shown below: and / or its enantiomers.

3. The method for preparing the multi-substituted alkylaryl azo compound of formula I and / or formula II according to claim 2, characterized in that: When R 1 Independently C1-C 10 The alkyl group or one or more R 1a Substituted C1-C 10 When the alkyl group is C1-C 10 The alkyl group and one or more R 1a Substituted C1-C 10 The C1-C 10 The alkyl group is methyl, n-propyl or isopropyl; and / or, when R 1 Independently C2-C 10 The alkenyl group or one or more R 1b Substituted C2-C 10 When the alkenyl group, the C2-C 10 The alkenyl group and one or more R 1b Substituted C2-C 10 The C2-C 10 The alkenyl group is -CH2CH=CH2; and / or, when R 1 Independently C6-C 14 The aryl group or one or more R 1c Substituted C6-C 14 When the aryl group is 14 The aryl group and one or more R 1c Substituted C6-C 14 The C6-C 14 The aryl group is phenyl, and / or, when R 1 is independently a 5-10 membered heteroaryl or is replaced by one or more R 1d When the 5-10 membered heteroaryl is substituted, the 5-10 membered heteroaryl may be replaced by one or more R 1d The 5-10 membered heteroaryl in the substituted 5-10 membered heteroaryl is furyl, thienyl, benzofuranyl or indolyl; and / or, when R 2 Independently C1-C 10 The alkyl group or one or more R 2a Substituted C1-C 10 When the alkyl group is C1-C 10 The alkyl group and one or more R 2a Substituted C1-C 10 The C1-C 10 The alkyl group is n-butyl; and / or, when R 2 Independently C3-C 10 The cycloalkyl group or one or more R 2b Substituted C3-C 10 When the cycloalkyl group is 10 The cycloalkyl group and one or more R 2b Substituted C3-C 10 The C3-C 10 The cycloalkyl group is cyclopentyl or cyclohexyl; and / or, when R 3 and R 4 Independently C1-C 10 The alkyl group or one or more R 3a Substituted C1-C 10 When the alkyl group is C1-C 10 The alkyl group and one or more R 3a Substituted C1-C 10 The C1-C 10 The alkyl group is methyl, ethyl or isobutyl; and / or, when R 3 and R 4 Independently C2-C 10 The alkenyl group or one or more R 3b Substituted C2-C 10 When the alkenyl group, the C2-C 10 The alkenyl group and one or more R 3b Substituted C2-C 10 The C2-C 10 The alkenyl group is -CH2CH=CH2; and / or, when R 3 and R 4 Independently C6-C 14 The aryl group or one or more R 3c Substituted C6-C 14 When the aryl group is 14 The aryl group and one or more R 3c Substituted C6-C 14 The C6-C 14 The aryl group is phenyl, and / or, when R 3 and R 4 is independently a 5-10 membered heteroaryl or is replaced by one or more R 3d When the 5-10 membered heteroaryl is substituted, the 5-10 membered heteroaryl and one or more R 3d The 5-10 membered heteroaryl in the substituted 5-10 membered heteroaryl is furyl, thienyl, benzofuranyl or indolyl; and / or, when R 3 and R 4 connected, independently forming with the carbon to which it is connected: C3-C 10 The cycloalkyl group or one or more R 4a Substituted C3-C 10 When the cycloalkyl group is 10 The cycloalkyl group and one or more R 4a Substituted C3-C 10 The C3-C 10 The cycloalkyl group is cyclohexyl; and / or, when R 5 Independently C6-C 14 The aryl group or one or more R 5a Substituted C6-C 14 When the aryl group is 14 The aryl group and one or more R 5a Substituted C6-C 14 The C6-C 14 The aryl group is phenyl, and / or, when R 5 is independently a 5-10 membered heteroaryl or is replaced by one or more R 5b When the 5-10 membered heteroaryl is substituted, the 5-10 membered heteroaryl and one or more R 5b The 5-10 membered heteroaryl in the substituted 5-10 membered heteroaryl is furyl, thienyl, benzofuranyl or indolyl; and / or, when R 1a 、R 1b 、R 1c 、R 1d 、R 2a 、R 2b 、R 3a 、R 3b 、R 3c 、R 3d 、R 4a 、R 5a and R 5b When they are independently C1-C6 alkyl, C1-C6 alkyl-O- or C1-C6 alkyl-OC(=O)-, the C1-C6 alkyl in the C1-C6 alkyl, C1-C6 alkyl-O- and C1-C6 alkyl-OC(=O)- is methyl or tert-butyl; and / or, R 2c 、R 2d 、R 2e 、R 6a 、R 6b and R 6c When they are independently C1-C6 alkyl, the C1-C6 alkyl is methyl or tert-butyl; and / or, when R 1a 、R 1b 、R 1c 、R 1d 、R 2a 、R 2b 、R 3a 、R 3b 、R 3c 、R 3d 、R 4a 、R 5a 、R 5b and R 7a When independently halogen, the halogen is fluorine or chlorine; and / or, when R 1a 、R 1b 、R 1c 、R 1d 、R 2a 、R 2b 、R 3a 、R 3b 、R 3c 、R 3d 、R 4a 、R 5a and R 5b When they are independently -O-(C1-C4 alkylene)-O-, the C1-C4 alkylene is methylene or -CH2CH2-; and / or, when R 7a When they are independently C1-C6 alkyl or C1-C6 alkyl-O-, the C1-C6 alkyl in the C1-C6 alkyl and C1-C6 alkyl-O- is methyl; and / or, when R 1 Independently by one or more R 1a Substituted C1-C 10 When the alkyl group is 1a is phenyl or tert-butyldimethylsilyloxy; and / or, when R 3 and R 4 Independently by one or more R 3a Substituted C1-C 10 When the alkyl group is 3a is phenyl or R 7a Substituted phenyl, R 7a is a C1-C6 alkyl-O-; and / or, when R 3 and R 4 Independently by one or more R 3c Substituted C6-C 14 When the aryl group is 3c is CN, fluorine, chlorine, methyl, methoxy, methyl-OC(=O)- or -O-(CH2)-O-; and / or, R 1 are independently H, C1-C 10 Alkyl, one or more R 1a Substituted C1-C 10 Alkyl or C2-C 10 alkenyl; and / or, R 3 and R 4 One of them is independently C1-C 10 Alkyl, one or more R 3a Substituted C1-C 10 Alkyl; and / or, R 3 and R 4 One of them is independently one or more R 3a Substituted C1-C 10 Alkyl, C6-C 14 The aryl group, one or more R 3c Substituted C6-C 14 aryl, 5-10 membered heteroaryl or one or more R 3d substituted 5-10 membered heteroaryl; and / or, R 5 Independently C6-C 14 of aromatic groups.

4. The method for preparing the multi-substituted alkylaryl azo compound of formula I and / or formula II according to claim 1, characterized in that: R 1 are independently H, methyl, n-propyl, isopropyl, allyl, tert-butyldimethylsilyloxy-substituted methyl or benzyl; and / or, R 2 are independently trimethylsilyl, n-butyl, cyclopentyl or cyclohexyl; and / or, R 3 and R 4 are independently methyl, ethyl, isobutyl, benzyl, phenyl, 4-fluorophenyl, 4-chlorophenyl, 4-methoxyphenyl, 4-methoxyacylphenyl, 4-cyano-phenyl, 3-methylphenyl, 3-methoxyphenyl, 2-fluoro-phenyl, 2-methoxyphenyl, and / or, when R 3 and R 4 When connected to form a C3-C7 cycloalkyl group together with the connected group, the C3-C7 cycloalkyl group is independently a cyclohexyl group; and / or, R 5 are independently phenyl.

5. The method for preparing the multi-substituted alkylaryl azo compound of formula I and / or formula II according to claim 1, characterized in that: The polysubstituted alkylarylazo compound as shown in formula I is selected from the following group or its enantiomers: And / or, the polysubstituted alkylarylazo compound as shown in Formula II is selected from the following group or its enantiomers:

6. The method for preparing the multi-substituted alkylaryl azo compound of formula I and / or formula II according to claim 1, wherein: The solvent is one or a combination of two or more of an aromatic hydrocarbon solvent, an ether solvent, a halogenated hydrocarbon solvent and a cycloalkane solvent; And / or, the mass volume ratio of the propargyl reagent represented by Formula III to the solvent is 1 g / L-50 g / L; and / or, the molar volume ratio of the hydrazone represented by Formula IV to the solvent is 0.01 mol / L-10 mol / L; And / or, in step 1, the strong base is LiHMDS, NaHMDS, KHMDS, LDA, n BuLi and One or a combination of two or more of the following: And / or, in step 2, the base is t BuOK, t BuOLi, t BuONa, LDA, and n One or a combination of two or more of BuLi; and / or, the molar ratio of the hydrazone of formula IV to the propargyl reagent of formula III is 2:(1-2); And / or, in step 1, the molar ratio of the hydrazone represented by formula IV to the strong base is 1:1; And / or, in step 1, the reaction temperature is -10°C to 80°C; And / or, in step 2, the reaction temperature is 0°C to 80°C; And / or, the preparation method further comprises post-processing, wherein the post-processing comprises the following steps: after the coupling reaction is completed, quenching, and separation by thin layer chromatography and / or column chromatography; And / or, X is chlorine or bromine; And / or, the nitrogen heterocyclic carbene-palladium catalytic system is a mixture of a metal palladium precursor and a nitrogen heterocyclic carbene ligand precursor as shown in formula V'; wherein Y is independently Cl, OTf or BF4; and / or, n1 is independently 0 or 1; and / or, when R 9a 、R 9b and R 9c is independently a C1-C6 alkyl group or is replaced by one or more R 10c When the C1-C6 alkyl group is substituted, the C1-C6 alkyl group is replaced by one or more R 10c The C1-C6 alkyl group in the substituted C1-C6 alkyl group is methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl or tert-butyl; and / or, when R 9a 、R 9b and R 9c When independently halogen, the halogen is chlorine or fluorine; and / or, when R 9a 、R 9b and R 9c is independently a C3-C7 cycloalkyl group or is replaced by one or more R 10b When the C3-C7 cycloalkyl group is substituted, the C3-C7 cycloalkyl group and one or more R 10b The C3-C7 cycloalkyl in the substituted C3-C7 cycloalkyl is cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl; and / or, when R 9d is independently a C1-C6 alkyl group or is replaced by one or more R 10d When the C1-C6 alkyl group is substituted, the C1-C6 alkyl group is replaced by one or more R 10d The C1-C6 alkyl group in the substituted C1-C6 alkyl group is methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl or tert-butyl; and / or, when R 9e Independently C6-C 14 The aryl group or one or more R 10e Substituted C6-C 14 When the aryl group is 14 The aryl group and one or more R 10e Substituted C6-C 14 The C6-C 14 The aryl group is phenyl or naphthyl; and / or, when R 10a 、R 10c 、R 10d and R 10e When they are independently C1-C6 alkyl, the C1-C6 alkyl is methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl or tert-butyl; and / or, R 8b and R 8b’ Independently C5-C 10 The polycyclic cycloalkyl group or one or more R 10a Substituted C5-C 10 of a polycyclic cycloalkyl group.

7. The method for preparing the multi-substituted alkylaryl azo compound of formula I and / or formula II according to claim 1, wherein: When R 8b and R 8b’ At least one of which is independently When the above steps are repeated, a polysubstituted alkylarylazo compound as shown in Formula I and / or Formula II can be obtained.

8. The method for preparing the multi-substituted alkylaryl azo compound of formula I and / or formula II according to claim 1, wherein: When R 8b and R 8b’ Independently C5-C 10 The polycyclic cycloalkyl group or one or more R 10a Substituted C5-C 10 The polycyclic cycloalkyl group of R 9a and R 9b When it is a methyl group, a multi-substituted alkylarylazo compound as shown in Formula II can be obtained.

9. The method for preparing a polysubstituted alkylaryl azo compound of formula I and / or formula II according to claim 6, wherein: R 8b and R 8b’ Independently C5-C 10 The polycyclic cycloalkyl group or one or more R 10a Substituted C5-C 10 When the polycyclic cycloalkyl group is C5-C 10 The polycyclic cycloalkyl group and one or more R 10a Substituted C5-C 10 The C5-C 10 The polycyclic cycloalkyl group of is adamantyl or bicyclo[3.1.1]heptanyl.

10. The method for preparing the multi-substituted alkylaryl azo compound of formula I and / or formula II according to claim 6, wherein: When the solvent is an aromatic hydrocarbon solvent, the aromatic hydrocarbon solvent is one or a combination of two or more of toluene, xylene and mesitylene; and / or, when the solvent is an ether solvent, the ether solvent is one or a combination of two or more of tetrahydrofuran, diethyl ether and dioxane; And / or, when the solvent is a halogenated hydrocarbon solvent, the halogenated hydrocarbon solvent is dichloromethane and / or chloroform; and / or, when the solvent is a cycloalkane solvent, the cycloalkane solvent is cyclohexane; And / or, the mass volume ratio of the propargyl reagent represented by Formula III to the solvent is 5 g / L-20 g / L; and / or, the molar volume ratio of the hydrazone represented by Formula IV to the solvent is 0.05 mol / L-0.2 mol / L; And / or, in step 1, the strong base is LiHMDS; And / or, in step 2, the base is t BuOK; And / or, in step 1, the reaction temperature is 0-30°C; And / or, in step 2, the reaction temperature is 10-30°C; And / or, X is chlorine; And / or, when the nitrogen heterocyclic carbene-palladium catalytic system is a mixture of a metal palladium precursor and a nitrogen heterocyclic carbene ligand precursor as shown in formula V', the metal palladium precursor is selected from the following group: one or a combination of two or more of Pd(OAc)2, Pd2(dba)3, Pd(dba)2, Pd2(dba)3·CHCl3, [Pd(C3H5)Cl]2, [Pd(cinnammyl)Cl]2 and Pd(PPh3)4; And / or, when the nitrogen heterocyclic carbene-palladium catalytic system is a mixture of a metal palladium precursor and a nitrogen heterocyclic carbene ligand precursor as shown in formula V', Y is independently Cl or BF4; And / or, when the nitrogen heterocyclic carbene-palladium catalyst system is a mixture of a metal palladium precursor and a nitrogen heterocyclic carbene ligand precursor as shown in formula V', the nitrogen heterocyclic carbene-palladium catalyst system is a complex of the metal palladium precursor and the nitrogen heterocyclic carbene ligand precursor as shown in formula V'; And / or, when the nitrogen heterocyclic carbene-palladium catalytic system is a mixture of a metal palladium precursor and a nitrogen heterocyclic carbene ligand precursor as shown in formula V', the molar ratio of the hydrazone shown in formula IV to the metal palladium precursor is 2:(0.01-0.5); And / or, when the nitrogen heterocyclic carbene-palladium catalytic system is a mixture of a metal palladium precursor and a nitrogen heterocyclic carbene ligand precursor as shown in formula V', the molar ratio of the nitrogen heterocyclic carbene ligand precursor as shown in formula V' to the metal palladium precursor is (1-3):1; And / or, when the nitrogen heterocyclic carbene-palladium catalytic system is a mixture of a metallic palladium precursor and a nitrogen heterocyclic carbene ligand precursor as shown in Formula V', in step 2, the molar ratio of the nitrogen heterocyclic carbene ligand precursor to the base is 1:(1-5); and / or, R 8b and R 8b’ Independently C5-C 10 The polycyclic cycloalkyl group or one or more R 10a Substituted C5-C 10 When the polycyclic cycloalkyl group is C5-C 10 The polycyclic cycloalkyl group and one or more R 10a Substituted C5-C 10 The C5-C 10 The polycyclic cycloalkyl group is and / or, when R 9a 、R 9b and R 9c is independently a C1-C6 alkyl group or is replaced by one or more R 10c When the C1-C6 alkyl group is substituted, the C1-C6 alkyl group is replaced by one or more R 10c The C1-C6 alkyl group in the substituted C1-C6 alkyl group is methyl or isopropyl; and / or, when R 9a 、R 9b and R 9c When independently halogen, the halogen is fluorine; and / or, when R 9a 、R 9b and R 9c is independently a C3-C7 cycloalkyl group or is replaced by one or more R 10b When the C3-C7 cycloalkyl group is substituted, the C3-C7 cycloalkyl group and one or more R 10b The C3-C7 cycloalkyl group in the substituted C3-C7 cycloalkyl group is cyclohexyl; and / or, when R 9d is independently a C1-C6 alkyl group or is replaced by one or more R 10d When the C1-C6 alkyl group is substituted, the C1-C6 alkyl group is replaced by one or more R 10d The C1-C6 alkyl group in the substituted C1-C6 alkyl group is a methyl group or a tert-butyl group; and / or, when R 9e Independently C6-C 14 The aryl group or one or more R 10e Substituted C6-C 14 When the aryl group is 14 The aryl group and one or more R 10e Substituted C6-C 14 The C6-C 14 The aryl group is phenyl, and / or, when R 10a 、R 10b 、R 10c 、R 10d and R 10e When they are independently C1-C6 alkyl, the C1-C6 alkyl is methyl or isopropyl; and / or, R 9a 、R 9b and R 9c is independently fluoro, methyl, isopropyl, benzhydryl or cyclohexyl; and / or, R 9d are independently H, methyl or tert-butyl; and / or, R 9e are independently phenyl, 2-methylphenyl or naphthyl.

11. The method for preparing the multi-substituted alkylaryl azo compound of formula I and / or formula II according to claim 1, wherein: When R 8b and R 8b’ Independently When R 9a and R 9b When it is a secondary carbon group or a tertiary carbon group, the molar ratio of the polysubstituted alkyl aryl azo compound as shown in Formula I to the polysubstituted alkyl aryl azo compound as shown in Formula II is greater than 1:

1.

12. The method for preparing the multi-substituted alkylarylazo compound of formula I and / or formula II according to claim 1, wherein: When R 8b and R 8b’ Independently C5-C 10 The polycyclic cycloalkyl group or one or more R 10a Substituted C5-C 10 When the polycyclic cycloalkyl group is a polycyclic cycloalkyl group, the molar ratio of the polysubstituted alkylaryl azo compound as shown in Formula II to the polysubstituted alkylaryl azo compound as shown in Formula I is greater than 98:

1.

13. The method for preparing the multi-substituted alkylarylazo compound of formula I and / or formula II according to claim 10, characterized in that: When the nitrogen heterocyclic carbene-palladium catalytic system is a mixture of a metal palladium precursor and a nitrogen heterocyclic carbene ligand precursor as shown in formula V', the metal palladium precursor is [Pd(η 3 -C3H5)Cl]2; And / or, when the nitrogen heterocyclic carbene-palladium catalytic system is a mixture of a metal palladium precursor and a nitrogen heterocyclic carbene ligand precursor as shown in formula V', the molar ratio of the nitrogen heterocyclic carbene ligand precursor as shown in formula V' to the metal palladium precursor is 2:1; And / or, when the nitrogen heterocyclic carbene-palladium catalytic system is a mixture of a metal palladium precursor and a nitrogen heterocyclic carbene ligand precursor as shown in formula V', in step 2, the molar ratio of the nitrogen heterocyclic carbene ligand precursor to the base is 1:2.5; And / or, when the propargyl reagent as shown in formula III is in the following configuration, and according to the "sequence rule" of the substituents, R 4 Prioritizes R 3 When the polysubstituted alkylarylazo compound shown in Formula I or Formula II is obtained, the polysubstituted alkylarylazo compound shown in Formula I or Formula II is obtained. Alternatively, when the propargyl reagent as shown in formula III is in the following configuration, and according to the "order rule" of substituents, R 4 Prioritizes R 3 When the polysubstituted alkylarylazo compound shown in Formula I or Formula II is obtained, the polysubstituted alkylarylazo compound shown in Formula I or Formula II is obtained. And / or, the ligand precursor of the nitrogen heterocyclic carbene as shown in formula V is: or a combination thereof.

14. The method for preparing the multi-substituted alkylarylazo compound of formula I and / or formula II according to claim 13, wherein: The ligand precursor of the nitrogen heterocyclic carbene as shown in Formula V is:

15. Use of a polysubstituted alkylarylazo compound as shown in Formula I or Formula II in the preparation of an α-quaternary carbon amine compound; characterized in that: It includes the following steps: In a solvent, in the presence of a reducing agent, a multi-substituted alkylaryl azo compound as shown in Formula I or Formula II is subjected to a reduction reaction as shown below to obtain an α-quaternary carbon amine compound as shown in Formula VI or Formula VII; Among them, R 1 、R 2 、R 3 、R 4 、R 5 and "*" as defined in any one of claims 1-5; The multi-substituted alkylarylazo compound represented by Formula I or Formula II is prepared by the preparation method described in any one of claims 1 to 14.

16. The use according to claim 15, characterized in that The reducing agent is Zn / HCl or SnCl2 / HCl; and / or, the solvent is an alcohol solvent; And / or, when the reducing agent is zinc powder / hydrochloric acid, the molar ratio of the zinc powder to the polysubstituted alkylaryl azo compound of Formula I or the polysubstituted alkylaryl azo compound of Formula II is (10-200):1; And / or, when the reducing agent is zinc powder / hydrochloric acid, the molar ratio of the hydrochloric acid to the zinc powder is (2-10):1; And / or, the reduction reaction temperature is 10°C to 100°C.

17. The use according to claim 16, characterized in that The reducing agent is zinc powder / hydrochloric acid; and / or, the solvent is methanol; And / or, when the reducing agent is zinc powder / hydrochloric acid, the molar ratio of the zinc powder to the polysubstituted alkylaryl azo compound of Formula I or the polysubstituted alkylaryl azo compound of Formula II is (50-100):1; and / or, when the reducing agent is zinc powder / hydrochloric acid, the molar ratio of the hydrochloric acid to the zinc powder is 6.5:1; And / or, the temperature of the reduction reaction is 20°C to 70°C.

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