Chiral imide carboxylic acid double-rhodium complex as well as preparation method and application thereof

Abstract

The invention discloses a chiral imide carboxylic acid double-rhodium complex as well as a preparation method and application thereof. The chiral imide carboxylic acid double-rhodium complex has a structure as shown in a formula (5) and is mainly characterized in that four imide carboxylic acid anions are coordinated to two rhodium atoms. The complex can catalyze an asymmetric (2 + 3) cyclization reaction of alkenyl amide and enol diazoacetate to obtain an aza-quaternary carbon chiral center functionalized five-membered ring. The synthesis route is simple, various binuclear rhodium complexes with different electrical properties and steric hindrances can be rapidly prepared, and a technical means is provided for establishment of a chiral binuclear rhodium compound library. # imgabs0 #

Description

Technical Field

[0001] The present invention relates to a preparation method and application of a chiral carboxylic acid bis-rhodium complex, and specifically to a preparation method of a chiral imide carboxylic acid bis-rhodium complex and its application in asymmetric catalytic (2+3) cyclization reaction of enamide and enol diazoacetate. The present invention belongs to the technical field of organic synthesis. Background Art

[0002] Binuclear rhodium metal complexes are a class of homonuclear bimetallic compounds with unique structures. They are widely used to catalyze a series of important chemical transformations, especially in the decomposition of diazo compounds to form rhodium carbenes, and to achieve carbene CH bond insertion, cyclopropanation and dipolar cycloaddition reactions (Davies, HM L et al. Coord. Chem. Rev. 2008, 252, 545; Ghanem, A. et al. Curr. Org. Chem. 2012, 16, 1808; Doyle, MP et al. Curr. Org. Chem. 2016, 20, 61; Davies, HM L et al. Nat. Rev. Chem. 2019, 3, 347). Structurally, binuclear rhodium metal complexes have three significant characteristics [Formula (1)]. First, they contain a rhodium-rhodium metal single bond, which is prone to the transition of d electrons from π* to σ*. The excitation wavelength is in the visible light region, which is why most binuclear rhodium appears green. Second, the bridging ligand and the di-rhodium form a unique axle-shaped coordination structure, and its catalytic activity is significantly affected by the structure and electrical properties of the bridging ligand. For example, as the electron-withdrawing ability of the bridging ligand increases, the electrophilicity of rhodium also increases. Third, in the axial position, it contains an empty orbital, which can easily coordinate with neutral ligands, anionic ligands, etc.

[0003]

[0004] In the past few decades, the catalytic technology of binuclear rhodium complexes has been deeply studied and has made important progress. Since the 1980s, the emergence of binuclear rhodium complexes coordinated by chiral ligands has provided new options for the study of catalytic asymmetric transformations in which they participate. Among these chiral binuclear rhodium complexes, the most studied are chiral carboxylic acid di-rhodium complexes and chiral amide di-rhodium complexes. Among the chiral carboxylic acid di-rhodium complexes, there is a class of chiral imide-carboxylic acid coordinated di-rhodium complexes, which have attracted extensive attention from many scientific researchers due to their high asymmetric induction and catalytic activity. At present, the known imide-carboxylic acid type di-rhodium complexes can be divided into the following three types. The first type was first reported by Ikegami and Hashimoto et al. of Teikyo University in Japan in 1990, using phthalimide-carboxylic acid as a bidentate ligand for rhodium-catalyzed intramolecular carbon-hydrogen bond insertion reaction [Formula (2)] (Ikegami, K. et al. Tetrahedron Lett. 1990, 31, 5173; Ikegami, K.; Hashimoto, S. et al. Tetrahedron Lett. 1993, 34, 5109). Subsequently, the Davies group and the Ghanem group, etc., constructed a series of phthalimide-carboxylic acid binuclear rhodium complex analogs by changing the steric hindrance and electrical properties of the aromatic structural unit substituents, providing more possibilities for the diversity of catalytic reactions and enantioselectivity (Davies, HML et al. Org. Lett. 2006, 8, 3437; Davies, HML et al. Nature 2018, 564, 395; Ghanem, A. Chem. Eur. J. 2016, 22, 3447). The second type is an amide-carboxylic acid binuclear rhodium complex with a bridged ring structural unit developed by the Ghanem group, and applied to a variety of cyclopropanation reactions [Formula (3)] (Ghanem, A. Chem. Eur. J. 2016, 22, 3447). The third type is the 1,8-naphthalene diimide-carboxylic acid binuclear rhodium complex developed by the Müller group, which exhibits relatively excellent reactivity and enantioselectivity in the cyclopropanation reaction of olefins with phenyl iodide derived from Michaelis acid [Formula (4)] (Müller, P. et al. Tetrahedron Asymmetry 2003, 14, 779). Although many imide-carboxylic acid binuclear rhodium complexes have been synthesized, no catalyst can be perfectly applied to many different types of catalytic reactions. Further synthesis of binuclear rhodium catalysts with different electrical properties and active cavities, in order to achieve diverse catalytic reactions and reveal their catalytic reaction process, still has important practical significance.

[0005] Summary of the invention

[0006] The purpose of the present invention is to provide a chiral imide carboxylic acid di-rhodium complex and a preparation method and application thereof.

[0007] In order to achieve the above object, the present invention adopts the following technical means:

[0008] The present invention discloses a chiral imide carboxylic acid bis-rhodium complex or its enantiomer or racemate, wherein the chiral imide carboxylic acid bis-rhodium complex has a structure shown in formula (5):

[0009]

[0010] Wherein, n and m represent the number of atoms participating in the ring formation, n=5-10, m=5-8; the ring is a saturated or unsaturated ring;

[0011] X and Y are independently selected from hydrogen, alkyl, chloroalkyl, phenyl, substituted phenyl, naphthyl, furyl, thienyl, benzyl or R'CH=; the substituent on the phenyl is hydroxyl, cyano, nitro, halogen, trifluoromethyl, benzyloxy, benzylsulfonyl, p-toluenesulfonyl, mesyl, aryl or heteroaryl, C3-C9 cycloalkyl, C1-C4 alkyloxy C1-C4 alkyl, unsubstituted, singly substituted or polysubstituted straight or branched C1-C 18 Alkyl, unsubstituted, singly substituted or polysubstituted, straight or branched chain C1-C 18 Alkoxy, unsubstituted, singly or polysubstituted, straight-chain or branched C1-C 18 Alkyl-substituted amino, the number of substituents is 1 to 5; R' is selected from C1-C6 straight chain or branched alkyl or phenyl; X and Y can be the same or different; or X and Y form a saturated or unsaturated five- to ten-membered carbon ring or heterocycle through a chemical bond or a saturated or unsaturated five- to ten-membered carbon ring or heterocycle substituted with a substituent;

[0012] Wherein, R is a C1-C6 alkyl group, 1-adamantyl group, 3-hydroxy-1-adamantyl group, benzyl group or phenyl group;

[0013] in, It means that X and Y may or may not be connected by a chemical bond.

[0014] Wherein, preferably, the chiral imide carboxylic acid di-rhodium complex has a structure shown in formula (5'):

[0015]

[0016] Wherein, the X and Y are independently selected from hydrogen, methyl, phenyl or substituted phenyl, 2-thienyl, CH3CH=, CH3(CH2)2CH=, PhCH=, (CH3)2C=; the substituent on the phenyl is tert-butyl, phenyl, benzyl, fluorine or chlorine, and the number of substituents is 1 to 3; or X and Y form a saturated or unsaturated five- to ten-membered carbon ring or heterocycle or a saturated or unsaturated five- to ten-membered carbon ring or heterocycle substituted by a substituent through a chemical bond; the saturated or unsaturated five- to ten-membered carbon ring or heterocycle or a saturated or unsaturated five- to ten-membered carbon ring or heterocycle substituted by a substituent includes cyclohexane, cycloheptane, cyclooctane, dibenzocyclohexane A nitrogen-containing six-membered unsaturated heterocyclic ring substituted with cyclooctene or pivaloyl; wherein R is tert-butyl, 1-adamantyl, 3-hydroxy-1-adamantyl, benzyl or phenyl.

[0017] Wherein, preferably, the chiral imide carboxylic acid di-rhodium complex is selected from the following compounds:

[0018]

[0019] Furthermore, the present invention also provides a method for preparing the chiral imide carboxylic acid double rhodium complex or its enantiomer or racemate: in the presence of an organic solvent and a base, a compound having a structure represented by formula (6) and a compound having a structure represented by formula (7) are reacted in a reactor for 2 to 12 hours to prepare a compound having a structure represented by formula (8); the compound having a structure represented by formula (8) is reacted with dimerized rhodium acetate to exchange and replace acetate to obtain a compound represented by formula (5):

[0020]

[0021] Among them, n, m, X, Y, R and The meaning is as described above.

[0022] Among them, preferably, the base is triethylamine, diisopropylethylamine, 1,8-diazacyclo[5.4.0]undecene-7 or triethylenediamine; the organic solvent is one of toluene, xylene, mesitylene, 1,4-dioxane, tetrahydrofuran, methyl tert-butyl ether, N,N-dimethylformamide, chlorobenzene or a mixed solvent of several thereof.

[0023] Furthermore, the present invention also proposes the use of the chiral imide carboxylic acid bis-rhodium complex or its enantiomer in the preparation of a catalyst for catalyzing the asymmetric (2+3) cyclization reaction of enamide and enol diazoacetate.

[0024] Among them, preferably, in an organic solvent, the chiral imide carboxylic acid bis-rhodium complex or its enantiomer is used as a chiral catalyst to catalyze the asymmetric (2+3) cyclization reaction of enamide and enol diazoacetate to obtain a nitrogen-containing quaternary carbon chiral center functionalized five-membered ring.

[0025] Preferably, in an acetone solvent, the chiral imide carboxylic acid bis-rhodium complex or its enantiomer is used as a chiral catalyst, the enamide shown in formula (9) is used as a substrate, and the diazo compound shown in formula (10) is added dropwise to the reaction system to obtain a highly enantioselective compound shown in formula (11), and the reaction formula for the asymmetric catalytic (2+3) cyclization reaction of the enamide and the enol diazoacetate is:

[0026]

[0027] Among them, R 1 ,R 2 ,R 3 and R 4 are the same or different and are each independently selected from: hydrogen, hydroxy, cyano, nitro, halogen, trifluoromethyl, benzyl, alkyl, alkoxy, aryl or heteroaryl; or

[0028] R 1 ,R 2 ,R 3 and R 4 Adjacent groups form a full carbon ring or a heterocyclic ring, wherein the full carbon ring or the heterocyclic ring is selected from the following structures:

[0029]

[0030] Preferably, the concentration of the enamide substrate is 0.1 M; the molar ratio of the enamide substrate to the catalyst is (1000:1 to 50:1); and the reaction temperature is 25°C.

[0031] Compared with the prior art, the present invention has the following beneficial effects:

[0032] The present invention designs and synthesizes a new type of imide-carboxylic acid binuclear rhodium complex, and some of the complexes show excellent reactivity and enantioselectivity in the asymmetric (2+3) cyclization reaction of enamide and enol diazoacetate catalyzed by the complex. The imide-carboxylic acid binuclear rhodium complex of the present invention has a simple synthesis route, and can quickly prepare a variety of binuclear rhodium complexes with different electrical properties and steric hindrances, providing a technical means for the establishment of a chiral binuclear rhodium compound library. DETAILED DESCRIPTION

[0033] The present invention is further described below by specific examples, but the present invention is not limited to the scope of the examples. The experimental methods without specific conditions in the following examples are selected according to conventional methods and conditions, or according to the product specifications.

[0034] General Notes:

[0035] The abbreviations used in the implementation examples have the following meanings:

[0036] Me is a methyl group, t Bu is tert-butyl, Ph is phenyl, Bn is benzyl, Piv is pivaloyl, HO-Ad is 3-hydroxy-1-adamantyl, DMF is N,N-dimethylformamide, TLC is thin layer chromatography, and NMR is nuclear magnetic resonance.

[0037] Experimental materials:

[0038] 6a, 6l-6o, 7a-7e were purchased from Bede Pharmaceuticals with a purity of 95%;

[0039] 6b-6j were prepared by referring to the prior art literature (Chem. Eur. J. 2010, 16, 11993);

[0040] 6k was obtained by self-production with reference to the prior art literature (Org.Lett.2015,17,4122);

[0041] 6r was obtained by self-production with reference to the prior art literature (Chem. Commun., 2018, 54, 2086);

[0042] 6p, 6q, 6s, and 6t were obtained by self-production according to the prior art literature (Angew. Chem. Int. Ed. 2015, 54, 1527);

[0043] 6u-6v was obtained by self-production with reference to the prior art literature (Adv. Synth. Catal. 2012, 354, 2859).

[0044] Example 1: Preparation of a compound of formula (8) from compounds of formula (6) and formula (7)

[0045]

[0046] The molecular formula of the compound represented by formula (6) is as follows:

[0047]

[0048] Compounds with the structure shown in formula (7) include: L-alanine (7a), L-valine (7b), L-phenylalanine (7c), L-tert-leucine (7d), and 3-hydroxy-1-adamantyl-D-glycine (7e).

[0049] The molecular formula of the compound of formula (8) obtained is as follows:

[0050]

[0051] Example 1-1: Preparation of Compound 8aa from Compound 6a and Compound 7a

[0052] Compound 6a (1.0 g, 4.0 mmol) was dissolved in 50 mL DMF, and compound 7a (0.36 g, 4.0 mmol) was added, and the temperature was raised to 150°C and stirred for 3 h. After TLC monitoring, the raw material completely disappeared, and the mixture was cooled to room temperature, 100 mL of water and 100 mL of ethyl acetate were added in sequence, and the organic phase was separated. The aqueous phase was extracted with ethyl acetate, and the organic phases were combined and washed with saturated brine and dried over anhydrous sodium sulfate. After concentration under reduced pressure, a light yellow solid 8aa was obtained.

[0053] Example 1-2: Preparation of Compounds 8ab-8ae, 8bd-8xd, 8oe and 8ve from Compounds 6b-6x and Compounds 7b-7e

[0054] The preparation process is similar to that of Example 1-1, except that the raw material used is replaced by compound 6b-6x instead of 6a, and the raw material used is replaced by compound 7b-7e instead of 7a.

[0055] The yields and related analytical data of compounds 8aa-8ae, 8bd-8xd, 8oe and 8ve obtained in the above stages are shown below:

[0056] 8aa(yellow solid, 99% yield, 1 H NMR (600MHz, CDCl3) δ=7.50-7.45(m,4H),7.40-7.31(m,6H),5.02-4.94(m,1H),1.75-1.68(m,3H)ppm. 13 C NMR (151MHz, CDCl3) δ = 175.4, 169.7, 136.3, 129.95, 129.91, 128.5, 128.4, 47.6, 15.0ppm.

[0057] 8ab (yellow solid, 92% yield, 1H NMR (600MHz, CDCl3) δ = 7.53-7.44 (m, 4H), 7.41-7.31 (m, 6H), 4.60 (d, J = 12.0 Hz,1H),2.78-2.68(m,1H),1.16(d,J=6.0Hz,3H),.0.98(d,J=6.0Hz,3H)ppm. 13 C NMR (151MHz, CDCl3) δ = 174.5, 170.1, 136.1, 130.0, 129.9, 128.5, 128.3, 58.0, 28.5, 20.8, 19.6ppm.

[0058] 8ac (yellow solid, 93% yield, 1 H NMR (600MHz, CDCl3) δ = 7.41-7.15 (m, 15H), 5.17 (dd, J = 12.0, 6.0Hz, 1H), 3.60-3.48 (m, 2H) ppm. 13 C NMR (151MHz, CDCl3) δ = 174.1, 169.8, 136.6, 136.1, 129.9, 129.8, 128.9, 128.6, 128.5, 128.3, 126.9, 53.5, 34.5ppm.

[0059] 8ae (yellow solid, 59% yield, 1 H NMR(600MHz, CDCl3)δ=7.54-7.47(m,4H),7.41-7.32(m,6H),5.39(brs,2H),4.62(s, 1H),2.27-2.20(m,2H),2.03-1.89(m,3H),1.79-1.64(m,7H),1.60-1.50(m,2H)ppm. 13 C NMR (151MHz, CDCl3) δ=171.5,170.4,136.1,130.0,128.5,128.3,69.4,60.0,46.7,44.1,43.8,40.7,38.1,37.9,35.0,30.5,30.2ppm.

[0060] 8bd (yellow solid, 68% yield, 1 H NMR (400MHz, CDCl3) δ = 7.84-7.15 (m, 14H), 4.84 (s, 1H), 1.31 (s, 9H) ppm. 13C NMR (151MHz, CDCl3) δ = 172.9, 170.3, 140.1, 133.4, 130.4, 128.4, 126.4, 126.1, 125.1, 60.8, 35.7, 28.1ppm.

[0061] 8cd (yellow solid, 87% yield, 1 H NMR (600MHz, CDCl3) δ = 7.42-7.26 (m, 8H), 4.69 (s, 1H), 1.21 (s, 9H), 1.17 (s, 18H) ppm. 13 C NMR (151MHz, CDCl3) δ = 173.7, 170.5, 151.2, 136.7, 128.3, 128.2, 127.1, 127.0, 126.9, 60.4, 35.5, 34.6, 31.0, 28.0ppm.

[0062] 8dd (yellow solid, 90% yield, 1 H NMR (600MHz, CDCl3) δ = 7.40-7.23 (m, 12H), 7.13 (s, 2H), 7.10 (d, J = 6.0Hz, 2H), 7.00 (dd, J = 12.0, 6.0Hz, 2H), 4.93 (s, 4H), 4.69 (s, 1H), 1.21 (s, 9H) ppm. 13 C NMR (151MHz, CDCl3) δ = 170.1, 158.7, 136.6, 136.0, 129.6, 129.5, 128.6, 128.0, 127.5, 122.7, 117.2, 115.9, 70.1, 60.4, 35.6, 27.9ppm.

[0063] 8ed (yellow solid, 81% yield, 1 H NMR (400MHz, CDCl3) δ = 7.68-7.56 (m, 12H), 7.48-7.32 (m, 6H), 4.73 (s, 1H), 1.24 (s, 9H) ppm. 13 C NMR (101MHz, CDCl3) δ = 173.7, 170.4, 142.7, 140.0, 135.4, 130.5, 128.9, 127.9, 127.3, 127.2, 127.0, 60.4, 35.6, 28.0ppm.

[0064] 8fd (yellow solid, 92% yield, 1 H NMR (400MHz, CDCl3) δ = 7.37 (s, 2H), 7.22 (s, 6H), 4.67 (s, 1H), 1.20 (s, 27H) ppm. 13 C NMR (101MHz, CDCl3) δ = 173.2, 170.9, 150.7, 137.5, 128.1, 124.1, 123.7, 60.7, 34.7, 31.2, 28.1ppm.

[0065] 8gd (yellow solid, 91% yield, 1 H NMR (400MHz, CDCl3) δ = 7.22-7.09 (m, 4H), 4.66 (s, 1H), 1.19 (s, 9H) ppm. 13 C NMR (151MHz, CDCl3) δ = 173.3, 168.6, 152.3 (dd, J = 10.6, 4.5Hz, 2C), 150.6 (dd, J = 10.6, 4.5Hz, 2C), 142.1 (t, J = 15.1Hz, 1C) ,140.4(t,J=15.1Hz,1C),134.1,123.1-122.9(m,2C) 114.6(d,J=4.5Hz,2C),114.5(d,J=4.5Hz,2C),60.7,35.5,27.9ppm.

[0066] 8hd (yellow solid, 96% yield, 1 H NMR (400MHz, CDCl3) δ = 7.52 (s, 4H), 7.24 (s, 2H), 4.64 (s, 1H), 1.17 (s, 9H) ppm. 13 C NMR (101MHz, CDCl3) δ = 173.3, 168.5, 135.1, 134.3, 134.0, 129.5, 127.1, 60.7, 35.5, 27.9ppm.

[0067] 8id(yellow solid, 95%yield, 1 H NMR (400MHz, CDCl3) δ = 7.47 (d, J = 8.0Hz, 3H), 7.35 (d, J = 8.0Hz, 3H), 4.64 (s, 1H), 1.31 (s, 36H), 1.17 (s, 9H) ppm. 13C NMR (101MHz, CDCl3) δ = 173.2, 170.8, 153.1, 135.1, 129.7, 125.7, 125.5, 60.4, 35.5, 34.8, 31.1, 27.9ppm.

[0068] 8jd (yellow solid, 74% yield, 1 H NMR (400MHz, CDCl3) δ = 7.85 (d, J = 2.8Hz, 2H), 7.58 (d, J = 4.0Hz, 2H), 7.13 (dd, J = 4.0Hz, 2.8Hz, 2H), 4.67 (s, 1H), 1.19 (s, 9H) ppm. 13 C NMR (151MHz, CDCl3) δ = 173.3, 169.7, 131.6, 131.1, 129.4, 127.5, 127.5, 60.5, 35.5, 27.9ppm.

[0069] 8kd (yellow solid, 97% yield, 1 H NMR (600MHz, CDCl3) δ=7.62-7.57(m,2H),7.50-7.42(m,3H),4.61(s,1H),2.23(s,3H),1.17(s,9H)ppm. 13 C NMR (151MHz, CDCl3) δ = 173.9, 171.5, 170.5, 137.2, 136.6, 129.7, 129.6, 128.7, 128.5, 60.1, 35.4, 27.9, 10.1ppm.

[0070] 8md (yellow solid, 87% yield, 1 H NMR (400MHz, CDCl3) δ=7.96-7.91(m,2H),7.50-7.42(m,3H),6.79(s,1H),4.61(s,1H),1.17(s,9H)ppm. 13 C NMR (101MHz, CDCl3) δ = 173.7, 170.2, 169.9, 143.7, 131.3, 128.9, 128.7, 128.5, 123.9, 59.9, 35.5, 27.9ppm.

[0071] 8nd (white solid, 68% yield, 1H NMR (600MHz, CDCl3) δ = 6.40 (q, J = 1.8Hz, 1H), 4.51 (s, 1H), 2.11 (s, 3H), 1.28 (s, 9H) ppm. 13 C NMR (151MHz, CDCl3) δ = 173.93, 173.90, 171.3, 170.3, 145.7, 127.5, 59.9, 35.3, 27.8, 11.1ppm.

[0072] 8od(white solid, 99%yield, 1 H NMR (600MHz, CDCl3) δ = 4.50 (s, 1H), 2.35 (s, 4H), 1.78 (s, 4H), 1.13 (s, 9H) ppm. 13 C NMR (101MHz, CDCl3) δ = 174.0, 170.6, 141.7, 59.6, 35.3, 27.8, 21.2, 20.0ppm.

[0073] 8oe(white solid, 70%yield, 1 H NMR (600MHz, CDCl3) δ=5.54(brs,2H),4.41(s,1H),2.34(s,4H),2.20(brs,2H),1.91-1.81(m,3H),1.77(s,4H),1.65(s,5H),1.62-1.47(m,4H)ppm. 13 C NMR (151MHz, CDCl3) δ = 171.7, 170.8, 141.8, 69.2, 59.5, 46.7, 44.2, 43.9, 40.6, 38.0, 37.9, 35.0, 30.5, 30.2, 21.2, 20.1.

[0074] 8pd(white solid, 80%yield, 1 H NMR (600MHz, CDCl3) δ = 4.49 (s, 1H), 2.54 (t, J = 6.0Hz, 4H), 1.83-1.77 (m, 2H), 1.72-1.6 (m, 4H), 1.12 (s, 9H) ppm. 13 C NMR (151MHz, CDCl3) δ = 173.7, 171.5, 142.5, 60.3, 35.4, 30.0, 27.8, 26.5, 24.8ppm.

[0075] 8qd(white solid, 32% yield, 1 H NMR (600MHz, CDCl3) δ = 4.52 (s, 1H), 2.60 (t, 6.0Hz, 4H), 1.78 (brs, 4H), 1.58-1.52 (m, 4H), 1.13 (s, 9H) ppm. 13 C NMR (151MHz, CDCl3) δ = 173.6, 171.6, 141.2, 60.2, 35.4, 27.9, 27.8, 26.4, 25.6, 22.2ppm.

[0076] 8rd (yellow solid, 86% yield, 1 H NMR (600MHz, CDCl3) δ = 9.12 (brs, 2H), 8.72 (brs, 2H), 7.78 (d, J = 12.0Hz, 4H), 4.81 (s, 1H), 1.25 (s, 9H) ppm. 13 C NMR (151MHz, CDCl3) δ = 172.1, 169.6, 133.5, 129.6, 128.5, 127.2, 126.4, 125.4, 123.2, 59.8, 35.7, 28.0ppm.

[0077] 8st(white solid, 41% yield, 1 H NMR(600MHz, CDCl3)δ=7.03-6.98(m,2H),4.62(s,1H),4.59(s,1H),3.53-3.45(m,2H),2.48-2.2 5(m,6H),1.85-1.68(m,8H),1.56-1.47(m,2H),1.42-1.30(m,4H),1.12(s,9H),1.11(s,9H)ppm. 13 C NMR (151MHz, CDCl3) δ = 177.8, 177.7, 172.6, 172.6, 172.5, 172.5, 169.5, 169.4, 139.5, 139.5, 129.8, 129.7, 60 .08,60.06,42.8,42.7,35.7,35.6,33.3,33.2,27.92,27.88,27.6,26.04,26.02,25.14,25.12,23.8,23.7ppm.

[0078] 8td (white solid, 27% yield, 1H NMR(600MHz, CDCl3)δ=8.03-7.99(m,2H),4.61-4.54(m,2H),4.47-4.41(m,2H),3.34-3.27(m, 2H),3.20-3.12(m,2H),2.57-2.48(m,2H),1.62-1.47(m,2H),1.36(s,18H),1.10(s,18H)ppm. 13 CNMR(151MHz, CDCl3)δ=177.4,174.8,174.7,172.1,172.1,168.3,168.2,131.7,131.6,106.5 ,106.4,59.9,59.8,43.4,43.4,40.0,39.1,39.0,35.6,35.5,28.4,27.9,27.8,27.0,21.7ppm.

[0079] 8ud(white solid, 66% yield, 1 H NMR (600MHz, CDCl3) δ = 7.01-6.87 (m, 1H), 4.67 (s, 1H), 3.30 (s, 2H), 1.89 (d, J = 12.0Hz, 3H), 1.14 (s, 9H) ppm. 13 C NMR (151MHz, CDCl3) δ = 173.8, 171.8, 169.5, 135.2, 125.9, 60.4, 35.7, 31.7, 27.9, 15.5ppm.

[0080] 8vd(white solid, 67% yield, 1 H NMR (600MHz, CDCl3) δ = 6.86 (tt, J = 12.0, 6.0Hz, 1H), 4.64 (s, 1H), 3.28 (s, 2H), 2 .18(q,J=12.0Hz,2H),1.58-1.51(m,2H),1.13(s,9H),0.97(t,J=6.0Hz,3H)ppm. 13 C NMR (151MHz, CDCl3) δ = 173.9, 172.7, 169.5, 140.1, 124.9, 60.2, 35.6, 31.9, 31.8, 27.9, 21.4, 13.8ppm.

[0081] 8ve(white solid, 40% yield,, 1H NMR (600MHz, MeOD) δ = 6.75 (s, 1H), 4.32 (s, 9H), 2.29-1.90 (m, 8H), 1.74-1.23 (m, 9H), 1.05-0.83 (m, 4H) ppm. 13 C NMR (151MHz, MeOD) δ = 176.37, 176.35, 171.8, 140.0, 127.3, 69.2, 61.8, 49.8, 47.9, 45.2, 41.8, 39.4, 39.3, 36.4, 32.7, 32.0, 31.8, 22.5, 14.2ppm.

[0082] 8wd(white solid, 61% yield, 1 H NMR (600MHz, CDCl3) δ = 7.66 (t, J = 6Hz, 1H), 7.52-7.42 (m, 5H), 4.73 (s, 1H), 3.66 (d, 2.4Hz, 2H), 1.17 (s, 9H) ppm. 13 C NMR (151MHz, CDCl3) δ = 173.8, 172.5, 170.7, 135.4, 133.9, 130.3, 130.2, 129.1, 122.6, 60.5, 35.7, 33.9, 28.0ppm.

[0083] 8xd (white solid, 42% yield, 1 H NMR (600MHz, CDCl3) δ = 4.62 (s, 1H), 3.28 (s, 2H), 2.34 (s, 3H), 1.90 (s, 3H), 1.12 (s, 9H) ppm. 13 C NMR (151MHz, CDCl3) δ = 173.7, 172.8, 169.2, 151.0, 59.9, 35.5, 33.9, 28.0, 24.2, 20.9ppm.

[0084] Example 2: Preparation of a compound of formula (5) from a compound of formula (8)

[0085]

[0086] Example 2-1: Preparation of Compound 5aa from Compound 8aa

[0087] Compound 8aa (385.0 mg, 1.2 mmol) and rhodium acetate dimer (100.0 mg, 0.23 mmol) were added to a 100 mL dry two-necked round-bottom flask equipped with a Soxhlet extractor (containing a 1:1 mixture of quartz sand and anhydrous sodium carbonate) in sequence, replaced with an argon atmosphere, and dry chlorobenzene (50 mL) was added with a syringe, stirred evenly, and heated to reflux. After reacting for 24 hours, the heating was stopped, and the product 5aa was obtained by column chromatography after decompression and desolventizing.

[0088] Example 2-2: Preparation of compounds 5ab-5ae, 5bd-5xd, 5oe and 5ve from compounds 8ab-8ae, 8bd-8xd, 8oe and 8ve

[0089] The preparation process is similar to that of Example 2-1, except that the raw material 8aa is replaced by compounds 8ab-8ae, 8bd-8xd, 8oe and 8ve.

[0090] The yields and related analytical data of compounds 5aa-5ae, 5bd-5xd, 5oe and 5ve obtained in the above stages are shown below:

[0091] 5aa(green solid, 83% yield, 1 H NMR (400MHz, CDCl3) δ = 7.48-7.25 (m, 10H), 5.00-4.85 (m, 1H), 1.59-1.51 (m, 1H), 1.41-1.33 (m, 1H), 1.18 (dd, J = 12.0, 8.0Hz, 1H) ppm. 13 C NMR(151MHz, CDCl3)δ=189.0,169.3,136.0,130.0,129.91,129.89,129.86,129.7 ,129.64,129.59,128.6,128.49,128.47,128.44,49.1,17.6,16.0,15.7,15.3ppm.

[0092] 5ab (green solid, 77% yield, 1 H NMR (400MHz, CDCl3) δ=7.50-7.25(m,10H),4.63-4.49(m,1H),2.67-2.34(m,1H),1.53-0.50(m,6H)ppm. 13C NMR (101MHz, CDCl3) δ=188.0,169.8,135.8,135.7,130.1,130.0,129.6,128.6,128.5,128.4,128.4,59.0,29.0,28.7,20.9,20.8,19.2ppm.

[0093] 5ac (green solid, 82% yield, 1 H NMR (600MHz, CDCl3) δ=7.51-6.93(m,15H),5.28-5.13(m,1H),3.63-3.18(m,2H)ppm. 13 C NMR (151MHz, CDCl3) δ = 188.5, 169.4, 169.4, 137.3, 135.9, 129.9, 129.8, 129.8, 129.5, 129.2, 128.6, 128.39, 128.37, 54.6, 35.0ppm.

[0094] 5ad (green solid, 90% yield, 1 H NMR (600MHz, CDCl3) δ = 7.49-7.26 (m, 10H), 4.73 (s, 1H), 1.12 (s, 9H) ppm. 13 C NMR (151MHz, CDCl3) δ = 186.9, 169.9, 135.8, 130.1, 129.5, 128.7, 128.5, 61.3, 35.8, 27.8ppm.

[0095] 5ae (green solid, 40% yield, 1 H NMR (600MHz, CDCl3) δ = 7.76-6.73 (m, 10H), 4.56 (s, 1H), 3.06-0.51 (m, 14H) ppm. 13 C NMR(151MHz, CDCl3)δ=186.1,170.3,169.9,136.2,135.4,130.1,129.6,12 8.6,128.4,69.2,61.0,60.5,46.0,44.4,41.0,38.6,37.4,35.3,30.5ppm.

[0096] 5bd (green solid, 59% yield, 1H NMR (600MHz, CDCl3) δ = 7.87-6.77 (m, 14H), 4.62 (s, 1H), 1.05 (s, 9H) ppm. 13 C NMR (151MHz, CDCl3) δ = 187.7, 169.6, 133.3, 129.9, 128.1, 125.8, 125.2, 62.0, 34.6, 27.9ppm.

[0097] 5cd (green solid, 75% yield, 1 H NMR (600MHz, CDCl3) δ = 7.56-7.13 (m, 6H), 4.71 (s, 1H), 1.11 (s, 18H), 1.01 (s, 9H) ppm. 13 C NMR (151MHz, CDCl3) δ = 187.1, 167.0, 150.5, 136.3, 128.6, 127.6, 126.8, 126.4, 61.2, 35.9, 34.4, 31.0, 27.9ppm.

[0098] 5dd (green solid, 75% yield, 1 H NMR (600MHz, CDCl3) δ = 7.44-6.83 (m, 18H), 4.82 (s, 4H), 4.60 (s, 1H), 1.07 (s, 9H) ppm. 13 C NMR(151MHz, CDCl3)δ=187.2,169.6,158.5,136.8,136.9,136.6,135.7,129.8 ,129.8,128.5,127.9,127.4,123.2,116.9,115.7,70.0,61.4,35.7,27.8ppm.

[0099] 5ed (green solid, 54% yield, 1 H NMR (600MHz, CDCl3) δ = 7.76-7.21 (m, 18H), 4.83 (s, 1H), 1.16 (s, 9H) ppm. 13 C NMR (151MHz, CDCl3) δ = 186.2, 168.8, 141.1, 139.3, 129.6, 127.7, 126.6, 126.1, 60.4, 34.8, 26.9ppm.

[0100] 5fd (green solid, 60% yield, 1 H NMR (600MHz, CDCl3) δ=7.59-7.21(m,8H),4.75(s,1H),1.30(s,18H),1.13-1.01(m,9H)ppm. 13 C NMR (151MHz, CDCl3) δ = 186.1, 170.0, 152.3, 129.8, 125.4, 61.1, 35.9, 34.7, 31.2, 27.9, 27.8ppm.

[0101] 5gd(green solid, 89% yield, 1 H NMR (600MHz, CDCl3) δ = 7.16-6.83 (m, 4H), 4.15 (s, 1H), 1.03 (s, 9H) ppm. 13 C NMR(151MHz, CDCl3)δ=186.9,168.7,168.2,152.6,152.2,151.0,150.5,14 2.6,142.0,140.9,140.3,134.2,123.2,122.8,114.3,62.0,35.3,27.4ppm.

[0102] 5hd (green solid, 82% yield, 1 H NMR (600MHz, CDCl3) δ = 7.46 (s, 2H), 7.33 (s, 2H), 3.96 (s, 1H), 1.02 (s, 9H) ppm. 13 C NMR (151MHz, CDCl3) δ = 186.9, 168.2, 168.1, 135.2, 135.0, 134.7, 134.1, 133.0, 129.4, 129.2, 127.3, 126.8, 61.7, 35.3, 27.5ppm.

[0103] 5id(green solid, 59% yield, 1 H NMR (600MHz, CDCl3) δ = 7.33 (s, 2H), 7.18 (s, 4H), 4.56 (s, 1H), 1.18 (s, 36H), 1.00 (s, 9H) ppm. 13 C NMR (151MHz, CDCl3) δ = 188.3, ​​170.1, 150.5, 137.5, 128.5, 124.2, 123.2, 62.8, 35.4, 34.7, 31.3, 28.5ppm.

[0104] 5jd (yellow-green solid, 62% yield, 1 H NMR (600MHz, CDCl3) δ = 7.78 (s, 2H), 7.69-7.44 (m, 2H), 7.21-7.04 (m, 2H), 4.84 (s, 1H), 1.11 (s, 9H) ppm. 13 C NMR (151MHz, CDCl3) δ = 186.9, 171.6, 131.5, 127.4, 61.8, 36.0, 27.8ppm.

[0105] 5kd (green solid, 48% yield, 1 H NMR (600MHz, CDCl3) δ = 7.63-7.23 (m, 5H), 4.56 (s, 1H), 2.10 (s, 1H), 1.00 (s, 9H) ppm. 13 C NMR (151MHz, CDCl3) δ = 187.3, 170.3, 136.7, 129.6, 129.4, 129.2, 128.5, 61.4, 35.4, 27.7, 10.0ppm.

[0106] 5ld (green solid, 63% yield, 1 H NMR (400MHz, CDCl3) δ = 4.47 (s, 1H), 1.89 (s, 6H), 1.00 (s, 9H) ppm. 13 C NMR (101MHz, CDCl3) δ = 187.3, 171.6, 137.0, 61.2, 35.0, 27.6, 8.7ppm.

[0107] 5md (green solid, 29% yield, 1 H NMR (600MHz, CDCl3) δ = 7.93 (d, J = 6.0Hz, 2H), 7.53-7.37 (m, 3H), 6.78 (s, 1H), 4.63 (s, 1H), 1.17 (s, 9H) ppm. 13 C NMR (151MHz, CDCl3) δ = 187.0, 173.6, 173.4, 170.1, 170.0, 143.6, 131.3, 128.9, 128.7, 128.5, 123.9, 59.9, 35.5, 27.9ppm.

[0108] 5nd (green solid, 51% yield, 1H NMR (600MHz, CDCl3) δ = 6.22 (s, 1H), 4.49 (s, 1H), 1.99 (s, 3H), 0.98 (s, 9H) ppm. 13 C NMR (151MHz, CDCl3) δ = 187.0, 171.2, 170.8, 145.2, 127.3, 61.1, 35.2, 27.7, 11.0ppm.

[0109] 5od(green solid, 73% yield, 1 HNMR (600MHz, CDCl3) δ = 4.47 (s, 1H), 2.28 (s, 4H), 1.73 (s, 4H), 1.01 (s, 9H) ppm. 13 C NMR (151MHz, CDCl3) δ = 187.7, 170.6, 141.3, 61.0, 35.1, 27.7, 21.4, 19.9ppm.

[0110] 5oe(green solid, 50% yield, 1 HNMR(600MHz, (CD3)2SO)δ=4.29(s,1H),4.14(s,1H),2.19(brs,4H),2.04-1.96(m,2H),1.79-1.58(m,4H),1.50-1.38(m,9H),1.32-1.20(m,3H)ppm. 13 C NMR (151MHz, (CD3)2SO) δ = 170.0, 140.9, 79.2, 66.7, 61.0, 47.2, 44.5, 40.1, 38.2, 36.7, 35.0, 30.0, 29.8, 20.8, 19.5ppm.

[0111] 5pd (green solid, 61% yield, 1 HNMR (600MHz, CDCl3) δ = 4.47 (s, 1H), 2.53-2.41 (m, 4H), 1.81-1.71 (m, 2H), 1.69-1.56 (m, 4H), 1.01 (s, 9H) ppm. 13 C NMR (151MHz, CDCl3) δ = 187.3, 171.4, 142.2, 61.6, 35.0, 30.2, 27.7, 26.7, 24.6ppm.

[0112] 5qd(green solid, 56% yield, 1HNMR (600MHz, CDCl3) δ = 4.52 (s, 1H), 2.51 (s, 4H), 1.69 (s, 4H), 1.49 (s, 4H), 1.02 (s, 9H) ppm. 13 C NMR (151MHz, CDCl3) δ = 187.6, 171.6, 141.0, 61.6, 34.9, 27.6, 26.9, 25.7, 22.0ppm.

[0113] 5rd (green solid, 38% yield, 1 HNMR (600MHz, CDCl3) δ=9.40-8.98(m,2H),8.62(s,2H),8.27-7.57(m,4H),5.11(s,1H),1.32(s,9H)ppm. 13 C NMR (151MHz, CDCl3) δ = 187.4, 133.2, 129.2, 125.5, 122.8, 61.1, 36.2, 28.1ppm.

[0114] 5sd (green solid, 79% yield, 1 HNMR (600MHz, CDCl3) δ = 6.85 (s, 1H), 4.62 (s, 1H), 3.47-3.11 (m, 1H), 2.82-2.19 (m, 3H), 1.87-1.17 (m, 7H), 1.00 (s, 9H) ppm. 13 C NMR (151MHz, CDCl3) δ = 186.6, 177.8, 176.5, 176.0, 173.0, 169.9, 168.4, 137.9, 137.0, 131.1, 129.7 ,61.9,61.0,43.4,42.7,42.1,35.5,35.1,33.6,31.6,27.8,27.7,27.4,27.1,25.9,25.3,23.9ppm.

[0115] 5td(green solid, 44% yield, 1 HNMR (600MHz, CDCl3) δ=4.76-4,32(m,2H),3.22-3.01(m,2H),2.52(s,1H),1.38(s,9H),1.03(s,9H)ppm. 13C NMR(151MHz, CDCl3)δ=186.8,177.5,173.9,168.3,130.4,130.2,107.9,61.2, 43.5,39.9,39.0,38.5,35.5,35.3,28.39,28.37,27.91,27.88,27.7,21.7ppm.

[0116] 5ud(green solid, 80%yield, 1 HNMR (600MHz, CDCl3) δ = 6.81 (s, 1H), 4.67 (s, 1H), 3.14 (s, 2H), 1.81 (d, J = 6.0Hz, 3H), 1.00 (s, 9H) ppm. 13 C NMR (151MHz, CDCl3) δ = 186.5, 174.6, 173.0, 172.5, 169.4, 168.5, 133.5, 125.9, 125.5, 61.5, 35.5, 27.9, 15.3ppm.

[0117] 5vd (green solid, 69% yield, 1 HNMR (600MHz, CDCl3) δ = 6.77 (s, 1H), 4.69 (s, 1H), 3.14 (s, 2H), 2.13 (q, J = 12.0Hz, 2H), 1.58-1.47 (m, 2H), 1.03 (s, 9H), 0.93 (t, J = 12.0Hz, 3H) ppm. 13 C NMR (151MHz, CDCl3) δ = 186.6, 173.8, 169.1, 138.1, 125.9, 61.5, 35.5, 31.8, 27.9, 27.8, 21.4, 13.9ppm.

[0118] 5ve(green solid, 28% yield, 1 H NMR (600MHz, CDCl3) δ = 6.75 (s, 1H), 4.56 (s, 1H), 3.11 (s, 2H), 2.60-0.47 (m, 21H) ppm. 13 C NMR (151MHz, CDCl3) δ = 185.5, 174.0, 169.6, 138.7, 125.9, 69.1, 61.2, 44.1, 35.7, 31.9, 30.4, 29.6, 21.5, 14.1, 13.9ppm.

[0119] 5wd(green solid, 73% yield, 1 H NMR (600MHz, CDCl3) δ = 7.75–7.30 (m, 6H), 4.86 (s, 1H), 3.76–3.33 (m, 2H), 1.11 (s, 9H) ppm. 13 C NMR (151MHz, CDCl3) δ = 186.5, 174.0, 172.3, 171.0, 169.8, 134.5, 134.1, 130.3, 129.7, 128.9, 124.2, 123.0, 61.79, 35.7, 34.1, 27.9ppm.

[0120] 5xd (green solid, 50% yield, 1 H NMR (600MHz, CDCl3) δ=4.68–4.37(m,1H),3.30–2.94(m,2H),2.40–2.27(m,3H),1.82(s,3H),1.01(s,9H)ppm. 13 C NMR (151MHz, CDCl3) δ = 186.6, 186.4, 173.8, 172.0, 169.6, 168.1, 149.1, 148.2, 119.7, 118.3, 60.7, 35.6, 34.1, 33.6, 29.7, 27.9, 20.9ppm.

[0121] Example 3: Asymmetric (2+3) Cyclization of Enamides and Enol Diazoacetates Catalyzed by Chiral Imidocarboxylic Acid Dirhodium

[0122]

[0123] Example 3-1: Asymmetric (2+3) cyclization reaction of 9a and 10 catalyzed by 5aa to prepare compound 11a

[0124] Under argon atmosphere, enamide 9a (48.6 mg, 0.2 mmol) and rhodium catalyst 5aa (5.9 mg, 0.004 mmol) were placed in a 10 mL Schneider reaction tube with a magnet, 2 mL of acetone was added, and 10a (512.8 mg, 1 mmol) was added dropwise at a rate of 1 mL / h using a feed pump at room temperature. After the addition was completed and the raw material disappeared completely by TLC monitoring, 10 mL of petroleum ether was added to the above reaction solution, and a white solid precipitated in the reaction system. Filter by suction, wash the filter cake with 10 mL of petroleum ether, and obtain a white solid 11a.

[0125] Example 3-2: Preparation of compound 11a by asymmetric (2+3) cyclization reaction of 9a and 10 catalyzed by 5ab-5ae, 5bd-5xd, 5oe or 5ve

[0126] The preparation process is similar to that of Example 3-1, except that the catalyst used is replaced by 5ab-5ae, 5bd-5xd, 5oe or 5ve instead of 5aa.

[0127] The yield and optical purity (ee value) of compound 11a obtained in the above stages are shown in Table 1 below:

[0128] Table 1. Asymmetric (2+3) cyclization of enamides and enol diazoacetates catalyzed by chiral imide carboxylic acid bis-rhodium 5

[0129]

Claims

1. A chiral imide carboxylic acid double rhodium complex or its enantiomer, racemate, characterized in that: The chiral imide carboxylic acid double rhodium complex has a structure shown in formula (5): Wherein, n and m represent the number of atoms participating in the ring formation, n=5-10, m=5-8; the ring is a saturated or unsaturated ring; X and Y are independently selected from hydrogen, alkyl, chloroalkyl, phenyl, substituted phenyl, naphthyl, furyl, thienyl, benzyl or R'CH=; the substituent on the phenyl is hydroxyl, cyano, nitro, halogen, trifluoromethyl, benzyloxy, benzylsulfonyl, p-toluenesulfonyl, mesyl, aryl or heteroaryl, C3-C9 cycloalkyl, C1-C4 alkyloxy C1-C4 alkyl, unsubstituted, singly substituted or polysubstituted straight or branched C1-C 18 Alkyl, unsubstituted, singly substituted or polysubstituted, straight or branched chain C1-C 18 Alkoxy, unsubstituted, singly or polysubstituted, straight-chain or branched C1-C 18 Alkyl-substituted amino, the number of substituents is 1 to 5; R' is selected from C1-C6 straight chain or branched alkyl or phenyl; X and Y can be the same or different; or X and Y form a saturated or unsaturated five- to ten-membered carbon ring or heterocycle through a chemical bond or a saturated or unsaturated five- to ten-membered carbon ring or heterocycle substituted with a substituent; Wherein, R is a C1-C6 alkyl group, 1-adamantyl group, 3-hydroxy-1-adamantyl group, benzyl group or phenyl group; in, It means that X and Y may or may not be connected by a chemical bond.

2. The chiral imide carboxylic acid double rhodium complex or its enantiomer or racemate according to claim 1, characterized in that: The chiral imide carboxylic acid double rhodium complex has a structure shown in formula (5'): Wherein, X and Y are independently selected from hydrogen, methyl, phenyl or substituted phenyl, 2-thienyl, CH3CH=, CH3(CH2)2CH=, PhCH=, (CH3)2C=; the substituent on the phenyl is tert-butyl, phenyl, benzyl, fluorine or chlorine, and the number of substituents is 1 to 3; or X and Y form a saturated or unsaturated five- to ten-membered carbon ring or heterocycle or a saturated or unsaturated five- to ten-membered carbon ring or heterocycle substituted by a substituent through a chemical bond; the saturated or unsaturated five- to ten-membered carbon ring or heterocycle or a saturated or unsaturated five- to ten-membered carbon ring or heterocycle substituted by a substituent includes a nitrogen-containing six-membered unsaturated heterocycle substituted with cyclohexane, cycloheptane, cyclooctane, dibenzocyclohexane, cyclooctene or pivaloyl; and R is tert-butyl, 1-adamantyl, 3-hydroxy-1-adamantyl, benzyl or phenyl.

3. The chiral imide carboxylic acid double rhodium complex or its enantiomer or racemate according to claim 1 or 2, characterized in that: The chiral imide carboxylic acid di-rhodium complex is selected from the following compounds:

4. A method for preparing a chiral imide carboxylic acid di-rhodium complex or its enantiomer or racemate according to any one of claims 1 to 3, characterized in that: In the presence of an organic solvent and a base, a compound having a structure represented by formula (6) and a compound having a structure represented by formula (7) are reacted in a reactor for 2 to 12 hours to prepare a compound having a structure represented by formula (8); the compound having a structure represented by formula (8) is reacted with dimerized rhodium acetate to exchange and replace acetate to obtain a compound represented by formula (5): Among them, n, m, X, Y, R and The meaning represented is as described in any one of claims 1 to 3.

5. The preparation method according to claim 4, characterized in that: The base is triethylamine, diisopropylethylamine, 1,8-diazacyclo[5.4.0]undecene-7 or triethylenediamine; the organic solvent is one of toluene, xylene, mesitylene, 1,4-dioxane, tetrahydrofuran, methyl tert-butyl ether, N,N-dimethylformamide and chlorobenzene or a mixed solvent of several of them.

6. Use of the chiral imidocarboxylic acid bis-rhodium complex or its enantiomer or racemate according to any one of claims 1 to 3 in the preparation of a catalyst for catalyzing the asymmetric (2+3) annulation reaction of enamide and enol diazoacetate.

7. The use according to claim 6, characterized in that: In an organic solvent, the chiral imide carboxylic acid bis-rhodium complex or its enantiomer described in any one of claims 1 to 3 is used as a chiral catalyst to catalyze the asymmetric (2+3) cyclization reaction of enamide and enol diazoacetate to obtain a nitrogen-containing quaternary carbon chiral center functionalized five-membered ring.

8. The use according to claim 7, characterized in that: In an acetone solvent, the chiral imide carboxylic acid bis-rhodium complex or its enantiomer as described in claim 1 or 2 is a chiral catalyst, the enamide shown in formula (9) is a substrate, and the diazo compound shown in formula (10) is added dropwise to the reaction system to obtain a highly enantioselective compound shown in formula (11). The reaction formula for the asymmetric catalytic (2+3) cyclization reaction of the enamide and the enol diazoacetate is: Among them, R 1 ,R 2 ,R 3 and R 4 are the same or different and are each independently selected from: hydrogen, hydroxy, cyano, nitro, halogen, trifluoromethyl, benzyl, alkyl, alkoxy, aryl or heteroaryl; or R 1 ,R 2 ,R 3 and R 4 Adjacent groups form a full carbon ring or a heterocyclic ring, wherein the full carbon ring or the heterocyclic ring is selected from the following structures:

9. The use according to claim 8, characterized in that: The concentration of the enamide substrate is 0.1 M; the molar ratio of the enamide substrate to the catalyst is 1000:1 to 50:1; and the reaction temperature is 25°C.

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