A method for synthesizing N-alkylated indole derivatives with high stereoselectivity

Abstract

The invention belongs to the field of asymmetric catalytic synthesis, and specifically discloses a method for synthesizing N-alkylated indole derivatives with high stereoselectivity. The invention adopts a method for synthesizing N-alkylated indole derivatives with high enantioselectivity using a racemic rhodium salt catalyst combined with chiral phosphoric acid to synergistically catalyze 3-isopropyl indole derivatives and aryl or alkyl diazo esters, and obtains non-natural amino acid derivatives with high stereoselectivity. The method of the invention has the advantages of simple reaction operation, simple and easy-to-obtain raw materials, mild reaction conditions, wide substrate application range, high efficiency and good enantioselectivity.

Description

Technical Field

[0001] The invention belongs to the field of asymmetric catalytic organic synthesis, and specifically relates to an enantioselective synthesis of N-alkylated indole derivatives by an indole derivative and an aryl or alkyl diazo ester derivative. Background Art

[0002] Indole and its derivatives are present in many natural products, drugs and leading compounds with various biological activities. In particular, chiral N-alkylated indole derivatives containing a stereogenic carbon center attached to the indole nitrogen atom are hot structures in drug development research. The common methods for synthesizing such parent nuclei include direct stereoselective N-alkylation of simple indole derivatives or in situ construction of the indole ring from open-chain compounds. The Hartwig team, the You group and the Breit group reported methods for the enantioselective synthesis of N-allylic indole derivatives from electron-deficient 1H-indole and allyl carbonate catalyzed by iridium or rhodium (Hartwig, JF, Angew. Chem. Int. Ed. 2009, 48, 7841; You, S.-L, Angew. Chem. Int. Ed. 2012, 51, 5183-5187; Breit, B, Nat. Commun. 2015, 6, 7616). Van Vranken reported the asymmetric NH insertion reaction of palladium carbene to carbazole and indole, but only moderate enantioselectivity was obtained when indole derivatives were used, and it was limited to α-aryl diazoacetates (Arredondo, V, Hiew, SC, Van Vranken, DL, Angew. Chem. Int. Ed. 2017, 56, 4156). The reaction of metal carbene with indole has the problem of position selectivity of CH insertion and NH insertion.

[0003] A synergistic strategy of transition metal rhodium salts and organic small molecule chiral phosphoric acid catalysts was adopted to react α-aryl and α-alkyl diazoacetate derivatives with indole derivatives as carbene precursors to synthesize optically pure N-alkyl indole derivatives with high enantioselectivity. Summary of the invention

[0004] The invention discloses a method for synthesizing N-alkyl indole derivatives with high enantioselectivity by using rhodium and chiral phosphoric acid to synergistically catalyze the reaction of a diazo ester compound with an indole derivative.

[0005] The specific reaction formula of the present invention is as follows:

[0006]

[0007] in:

[0008] R 1for Me, Et, i-Pr, t-Bu, i-Bu, Ph, Br, One of the 2 is one of H, 4-Me, 4-Cl, 5-Me, 5-Cl, 6-Me, 6-Br, 7-Me, and 7-Br;

[0009] The diazo ester compound is an aryl diazo ester derivative or an alkyl diazo ester derivative, specifically:

[0010] R 3 is Et,n-Bu, n-hex, Bn, Ph, 2-MeC6H4, 2-FC6H4, 3-MeC6H4, 3-ClC6H4, 4-MeC6H4, 4-ClC6H4, 4-BrC6H4, 4-CF3C6H4, 4-BocNHC6H4, 2,4-diClC6H3, 3,4-diClC6H3, One of the 4 for Me, Et, i-Pr, t-Bu, Bn, One of them.

[0011] A method for synthesizing N-alkyl indole derivatives with high enantioselectivity by using rhodium salt and chiral phosphoric acid as synergistic catalysis and reacting diazo ester derivatives as carbene precursors with indole derivatives. The method comprises the following steps: adding racemic rhodium salt and chiral phosphoric acid to a clean and dry reaction tube, dissolving the indole derivative (1) in a redistilled solvent and adding the two together to the reaction tube, dissolving the diazo ester derivative (2) in a redistilled solvent after replacing argon and rapidly injecting the two into the reaction tube with a syringe, stirring the reaction at a certain temperature for a certain time, separating and purifying the two by using petroleum ether and ethyl acetate as an eluent system, and finally synthesizing N-alkyl indole derivatives with high enantioselectivity.

[0012] The chiral phosphoric acids used are as follows:

[0013]

[0014] Among them, the optimal chiral phosphoric acid when the indole derivative reacts with the aromatic diazo ester derivative is C1, and the optimal chiral phosphoric acid when the indole derivative reacts with the alkyl diazo ester derivative is C5 or C6.

[0015] The specific structural formula of indole derivatives is as follows:

[0016]

[0017] The diazo ester derivative is an aryl diazo ester derivative or an alkyl diazo ester derivative, and its specific structural formula is as follows:

[0018]

[0019] The solvent of the reaction is one of toluene, tetrahydrofuran, dichloromethane, dichloroethane, acetonitrile, cyclohexane, n-hexane and ether. The best solvent for the reaction of indole derivatives with aromatic diazo ester derivatives is dichloromethane, and the best solvent for the reaction of indole derivatives with alkyl diazo ester derivatives is toluene.

[0020] The rhodium catalyst used in the reaction can be: Rh2(Oct)4, Rh2(OAc)4, Rh2(OPiv)4, Rh2(PTTL)4, Rh2(esp)2, Rh2(TFA)4. Among them, the optimal rhodium catalyst when the indole derivative reacts with the aryl diazo ester derivative is Rh2(Oct)4, and the optimal rhodium catalyst when the indole derivative reacts with the alkyl diazo ester derivative is Rh2(OPiv)4.

[0021] In the reaction, the equivalent ratio of the rhodium catalyst, chiral phosphoric acid, indole derivative and diazo ester derivative is: 0.0001-0.0010:0.0025-0.0050:1:1-2.5, among which, when the indole derivative reacts with the aromatic diazo ester derivative, the optimal equivalent ratio is: 0.0001:0.0025:1:1.5, and when the indole derivative reacts with the alkyl diazo ester derivative, the optimal equivalent ratio is: 0.0001:0.0025:1:2.5.

[0022] When the indole derivative is 1 equivalent, the concentration of the reaction solution is: 0.05-0.20 mol / L, and the optimal concentration is 0.10 mol / L.

[0023] Reaction temperature: the reaction temperature is -20℃-40℃. The optimal temperature for the reaction of indole derivatives with aromatic diazo ester derivatives is 25℃, and the optimal temperature for the reaction of indole derivatives with alkyl diazo ester derivatives is -20℃.

[0024] Benefits and advantages

[0025] The present invention designs a method for synthesizing N-alkyl indole derivatives enantioselectively by using rhodium salt and chiral phosphoric acid to generate carbene in situ with a diazo compound, insert NH into indole derivatives chemoselectively and enantioselectively, and provide a simple way to synthesize optically pure N-alkyl indole derivatives and obtain non-natural amino acid derivatives containing indole.

[0026] The method of the invention has the following advantages: simple reaction operation, mild conditions, simple and readily available raw materials, wide applicable scope of substrates, high efficiency, and good diastereoselectivity and enantioselectivity. BRIEF DESCRIPTION OF THE DRAWINGS

[0027] Figure 1 The 3aa obtained in Example 1 1 H-NMR (nuclear magnetic resonance spectroscopy);

[0028] Figure 2 The 3aa obtained in Example 1 13 C-NMR (Nuclear Magnetic Carbon Spectroscopy);

[0029] Figure 3 HRMS (high resolution mass spectrometry) of 3aa obtained in Example 1;

[0030] Figure 4 This is the HPLC (high performance liquid chromatography) of 3aa obtained in Example 1. DETAILED DESCRIPTION

[0031] The present invention will be further described below by means of specific examples, but the present invention is not limited to the following examples.

[0032] Embodiment 1:

[0033]

[0034] Rh2(Oct)4 (0.08 mg, 0.0001 mmol, 0.001 equiv) and chiral phosphoric acid C1 (1.4 mg, 0.0025 mmol, 0.025 equiv) were added to a dry reaction tube, and then the indole derivative 1a (15.9 mg, 0.1 mmol, 1 equiv) was dissolved in 1 ml of redistilled dichloromethane. The reaction tube was evacuated and filled with argon (this operation was repeated three times). The diazo ester derivative 2a (26.4 mg, 0.15 mmol, 1.5 equiv) was dissolved in 1 ml of redistilled dichloromethane and injected into the reaction tube with a syringe, and stirred at 25°C for 15 min. The reaction solution was evaporated to dryness under reduced pressure, and the residue was purified by column chromatography (silica gel, eluent: EtOAc / PE=1:50-1:20) to give a white solid product (26.7 mg, 87%, 98% ee), melting point: 43-45°C; enantioselectivity: 98% ee; HPLC conditions: Daicel Chiralpak IA column, n-hexane / i-PrOH=99 / 1, flow rate=1.0 mL / min, I=215 nm, t R =5.62min(major)and 6.90min(minor).[α] D 20 :-114.1 (c 0.25, CH2Cl2; 98%ee). 1H NMR(400MHz, CDCl3)δ7.65(d,J=8.6Hz,1H),7.40-7.32(m,3H),7.35-7.25(m,3H),7.19(td,J=6.8,1.3Hz,1H),7 .11(td,J=8.0,1.1Hz,1H),6.89(s,1H),6.21(s,1H),3.77(s,3H),3.17(hept,1H),1.31(dd,J=8.2,6.9Hz,6H). 13 C NMR (100MHz, CDCl3) δ170.4,137.2,135.0,129.1,128.9,128.1,127.8,123.9,122 .0,121.9,119.9,119.4,109.2,61.9,52.8,25.7,23.4,23.3.HRMS(ESI)m / z:[M+H] + Calcd for C 20 H 22 NO2308.1645; Found 308.1644.

[0035] Embodiment 2:

[0036] Rh2(OAc)4 (0.05 mg, 0.0001 mmol, 0.001 equiv) and chiral phosphoric acid C1 (1.4 mg, 0.0025 mmol, 0.025 equiv) were added to a dry reaction tube, and then the indole derivative 1a (15.9 mg, 0.1 mmol, 1 equiv) was dissolved in 1 ml of redistilled dichloromethane. After the reaction tube was evacuated and filled with argon (this operation was repeated three times), the diazo ester derivative 2a (26.4 mg, 0.15 mmol, 1.5 equiv) was dissolved in 1 ml of redistilled dichloromethane and injected into the reaction tube by syringe, and stirred at 25°C for 15 min. The reaction solution was evaporated to dryness under reduced pressure, and the residue was purified by column chromatography (silica gel, eluent: EtOAc / PE = 1:50-1:20) to obtain a white solid product (20.9 mg, 68%, 98% ee).

[0037] Embodiment 3:

[0038] Rh2(Oct)4 (0.08 mg, 0.0001 mmol, 0.001 equiv) and chiral phosphoric acid C1 (2.8 mg, 0.005 mmol, 0.05 equiv) were added to a dry reaction tube, and then the indole derivative 1a (15.9 mg, 0.1 mmol, 1 equiv) was dissolved in 1 ml of redistilled dichloromethane. After the reaction tube was evacuated and filled with argon (this operation was repeated three times), the diazo ester derivative 2a (26.4 mg, 0.15 mmol, 1.5 equiv) was dissolved in 1 ml of redistilled dichloromethane and injected into the reaction tube by syringe, and stirred at 25°C for 15 min. The reaction solution was evaporated to dryness under reduced pressure, and the residue was purified by column chromatography (silica gel, eluent: EtOAc / PE=1:50-1:20) to obtain a white solid product (25.8 mg, 84%, 98% ee).

[0039] Embodiment 4:

[0040] Rh2(Oct)4 (1 mg, 0.001 mmol, 0.01 equiv) and chiral phosphoric acid C1 (2.8 mg, 0.005 mmol, 0.05 equiv) were added to a dry reaction tube, and then the indole derivative 1a (15.9 mg, 0.1 mmol, 1 equiv) was dissolved in 1 ml of redistilled dichloromethane. After the reaction tube was evacuated and filled with argon (this operation was repeated three times), the diazo ester derivative 2a (26.4 mg, 0.15 mmol, 1.5 equiv) was dissolved in 1 ml of redistilled dichloromethane and injected into the reaction tube by syringe, and stirred at 25°C for 15 min. The reaction solution was evaporated to dryness under reduced pressure, and the residue was purified by column chromatography (silica gel, eluent: EtOAc / PE=1:50-1:20) to obtain a white solid product (23.6 mg, 77%, 96% ee).

[0041] Embodiment 5:

[0042] Rh2(Oct)4 (0.08 mg, 0.0001 mmol, 0.001 equiv) and chiral phosphoric acid C2 (1.8 mg, 0.0025 mmol, 0.025 equiv) were added to a dry reaction tube, and then the indole derivative 1a (15.9 mg, 0.1 mmol, 1 equiv) was dissolved in 1 ml of redistilled dichloromethane. After the reaction tube was evacuated and filled with argon (this operation was repeated three times), the diazo ester derivative 2a (26.4 mg, 0.15 mmol, 1.5 equiv) was dissolved in 1 ml of redistilled dichloromethane and injected into the reaction tube by syringe, and stirred at 25°C for 15 min. The reaction solution was evaporated to dryness under reduced pressure, and the residue was purified by column chromatography (silica gel, eluent: EtOAc / PE = 1:50-1:20) to obtain a white solid product (13.8 mg, 45%, 7% ee).

[0043] Embodiment 6:

[0044] Rh2(Oct)4 (0.08 mg, 0.0001 mmol, 0.001 equiv) and chiral phosphoric acid C3 (1.5 mg, 0.0025 mmol, 0.025 equiv) were added to a dry reaction tube, and then the indole derivative 1a (15.9 mg, 0.1 mmol, 1 equiv) was dissolved in 1 ml of redistilled dichloromethane. After the reaction tube was evacuated and filled with argon (this operation was repeated three times), the diazo ester derivative 2a (26.4 mg, 0.15 mmol, 1.5 equiv) was dissolved in 1 ml of redistilled dichloromethane and injected into the reaction tube by syringe, and stirred at 25°C for 15 min. The reaction solution was evaporated to dryness under reduced pressure, and the residue was purified by column chromatography (silica gel, eluent: EtOAc / PE=1:50-1:20) to obtain a white solid product (25.2 mg, 82%, 93% ee).

[0045] Embodiment 7:

[0046] Rh2(Oct)4 (0.08 mg, 0.0001 mmol, 0.001 equiv) and chiral phosphoric acid C4 (1.8 mg, 0.0025 mmol, 0.025 equiv) were added to a dry reaction tube, and then the indole derivative 1a (15.9 mg, 0.1 mmol, 1 equiv) was dissolved in 1 ml of redistilled dichloromethane. After the reaction tube was evacuated and filled with argon (this operation was repeated three times), the diazoester derivative 2a (26.4 mg, 0.15 mmol, 1.5 equiv) was dissolved in 1 ml of redistilled dichloromethane and injected into the reaction tube by syringe, and stirred at 25°C for 15 min. The reaction solution was evaporated to dryness under reduced pressure, and the residue was purified by column chromatography (silica gel, eluent: EtOAc / PE=1:50-1:20) to obtain a white solid product (26.7 mg, 87%, 86% ee).

[0047] Embodiment 8:

[0048] Rh2(Oct)4 (0.08 mg, 0.0001 mmol, 0.001 equiv) and chiral phosphoric acid C5 (1.8 mg, 0.0025 mmol, 0.025 equiv) were added to a dry reaction tube, and then the indole derivative 1a (15.9 mg, 0.1 mmol, 1 equiv) was dissolved in 1 ml of redistilled dichloromethane. After the reaction tube was evacuated and filled with argon (this operation was repeated three times), the diazo ester derivative 2a (26.4 mg, 0.15 mmol, 1.5 equiv) was dissolved in 1 ml of redistilled dichloromethane and injected into the reaction tube by syringe, and stirred at 25°C for 15 min. The reaction solution was evaporated to dryness under reduced pressure, and the residue was purified by column chromatography (silica gel, eluent: EtOAc / PE = 1:50-1:20) to obtain a white solid product (17.2 mg, 56%, 90% ee).

[0049] Embodiment 9:

[0050] Rh2(Oct)4 (0.08 mg, 0.0001 mmol, 0.001 equiv) and chiral phosphoric acid C6 (1.8 mg, 0.0025 mmol, 0.025 equiv) were added to a dry reaction tube, and then the indole derivative 1a (15.9 mg, 0.1 mmol, 1 equiv) was dissolved in 1 ml of redistilled dichloromethane. After the reaction tube was evacuated and filled with argon (this operation was repeated three times), the diazo ester derivative 2a (26.4 mg, 0.15 mmol, 1.5 equiv) was dissolved in 1 ml of redistilled dichloromethane and injected into the reaction tube by syringe, and stirred at 25°C for 15 min. The reaction solution was evaporated to dryness under reduced pressure, and the residue was purified by column chromatography (silica gel, eluent: EtOAc / PE = 1:50-1:20) to obtain a white solid product (27.0 mg, 88%, 93% ee).

[0051] Embodiment 10:

[0052] Rh2(Oct)4 (0.08 mg, 0.0001 mmol, 0.001 equiv) and chiral phosphoric acid C1 (1.4 mg, 0.0025 mmol, 0.025 equiv) were added to a dry reaction tube, and then the indole derivative 1a (15.9 mg, 0.1 mmol, 1 equiv) was dissolved in 1 ml of redistilled tetrahydrofuran. After the reaction tube was evacuated and filled with argon (this operation was repeated three times), the diazo ester derivative 2a (26.4 mg, 0.15 mmol, 1.5 equiv) was dissolved in 1 ml of redistilled tetrahydrofuran and injected into the reaction tube by syringe, and stirred at 25°C for 15 min. The reaction solution was evaporated to dryness under reduced pressure, and the residue was purified by column chromatography (silica gel, eluent: EtOAc / PE=1:50-1:20) to obtain a white solid product (15.0 mg, 49%, 30% ee).

[0053] Embodiment 11:

[0054] Rh2(Oct)4 (0.08 mg, 0.0001 mmol, 0.001 equiv) and chiral phosphoric acid C1 (1.4 mg, 0.0025 mmol, 0.025 equiv) were added to a dry reaction tube, and then the indole derivative 1a (15.9 mg, 0.1 mmol, 1 equiv) was dissolved in 1 ml of redistilled acetonitrile. After the reaction tube was evacuated and filled with argon (this operation was repeated three times), the diazoester derivative 2a (26.4 mg, 0.15 mmol, 1.5 equiv) was dissolved in 1 ml of redistilled acetonitrile and injected into the reaction tube by syringe, and stirred at 25°C for 15 min. The reaction solution was evaporated to dryness under reduced pressure, and the residue was purified by column chromatography (silica gel, eluent: EtOAc / PE = 1:50-1:20) to obtain a white solid product (12.3 mg, 40%, <10% ee).

[0055] Embodiment 12:

[0056] Rh2(Oct)4 (0.08 mg, 0.0001 mmol, 0.001 equiv) and chiral phosphoric acid C1 (1.4 mg, 0.0025 mmol, 0.025 equiv) were added to a dry reaction tube, and then the indole derivative 1a (15.9 mg, 0.1 mmol, 1 equiv) was dissolved in 1 ml of redistilled dichloromethane. After the reaction tube was evacuated and filled with argon (this operation was repeated three times), the diazo ester derivative 2a (26.4 mg, 0.15 mmol, 1.5 equiv) was dissolved in 1 ml of redistilled dichloromethane and injected into the reaction tube by syringe, and stirred at -20°C for 40 min. The reaction solution was evaporated to dryness under reduced pressure, and the residue was purified by column chromatography (silica gel, eluent: EtOAc / PE = 1:50-1:20) to obtain a white solid product (12.9 mg, 42%, 92% ee).

[0057] Embodiment 13:

[0058] Rh2(Oct)4 (0.08 mg, 0.0001 mmol, 0.001 equiv) and chiral phosphoric acid C1 (1.4 mg, 0.0025 mmol, 0.025 equiv) were added to a dry reaction tube, and then the indole derivative 1a (15.9 mg, 0.1 mmol, 1 equiv) was dissolved in 1 ml of redistilled dichloromethane. After the reaction tube was evacuated and filled with argon (this operation was repeated three times), the diazo ester derivative 2a (26.4 mg, 0.15 mmol, 1.5 equiv) was dissolved in 1 ml of redistilled dichloromethane and injected into the reaction tube by syringe, and stirred at 0°C for 30 min. The reaction solution was evaporated to dryness under reduced pressure, and the residue was purified by column chromatography (silica gel, eluent: EtOAc / PE=1:50-1:20) to obtain a white solid product (16.6 mg, 54%, 97% ee).

[0059] Embodiment 14:

[0060] Rh2(Oct)4 (0.08 mg, 0.0001 mmol, 0.001 equiv) and chiral phosphoric acid C1 (1.4 mg, 0.0025 mmol, 0.025 equiv) were added to a dry reaction tube, and then the indole derivative 1a (15.9 mg, 0.1 mmol, 1 equiv) was dissolved in 1 ml of redistilled dichloromethane. After the reaction tube was evacuated and filled with argon (this operation was repeated three times), the diazo ester derivative 2a (26.4 mg, 0.15 mmol, 1.5 equiv) was dissolved in 1 ml of redistilled dichloromethane and injected into the reaction tube by syringe, and stirred at 15°C for 20 min. The reaction solution was evaporated to dryness under reduced pressure, and the residue was purified by column chromatography (silica gel, eluent: EtOAc / PE = 1:50-1:20) to obtain a white solid product (22.7 mg, 74%, 97% ee).

[0061] Embodiment 15:

[0062] Rh2(Oct)4 (0.08 mg, 0.0001 mmol, 0.001 equiv) and chiral phosphoric acid C1 (1.4 mg, 0.0025 mmol, 0.025 equiv) were added to a dry reaction tube, and then the indole derivative 1a (15.9 mg, 0.1 mmol, 1 equiv) was dissolved in 0.5 ml of redistilled dichloromethane. After the reaction tube was evacuated and filled with argon (this operation was repeated three times), the diazo ester derivative 2a (26.4 mg, 0.15 mmol, 1.5 equiv) was dissolved in 0.5 ml of redistilled dichloromethane and injected into the reaction tube by syringe, and stirred at 15°C for 20 min. The reaction solution was evaporated to dryness under reduced pressure, and the residue was purified by column chromatography (silica gel, eluent: EtOAc / PE=1:50-1:20) to obtain a white solid product (23.3 mg, 76%, 97% ee).

[0063] Embodiment 16:

[0064]

[0065] Rh2(Oct)4 (0.08 mg, 0.0001 mmol, 0.001 equiv) and chiral phosphoric acid C1 (1.4 mg, 0.0025 mmol, 0.025 equiv) were added to a dry reaction tube, and then the indole derivative 1a (15.9 mg, 0.1 mmol, 1 equiv) was dissolved in 1 ml of redistilled dichloromethane. The reaction tube was evacuated and filled with argon (this operation was repeated three times). The diazo ester derivative 2b (28.5 mg, 0.15 mmol, 1.5 equiv) was dissolved in 1 ml of redistilled dichloromethane and injected into the reaction tube with a syringe, and stirred at 25°C for 15 min. The reaction solution was evaporated to dryness under reduced pressure, and the residue was purified by column chromatography (silica gel, eluent: EtOAc / PE=1:50-1:20) to give a colorless oil (28.3 mg, 88%, 99% ee); enantioselectivity: 99% ee; HPLC conditions: DaicelChiralpak IA column, n-hexane / i-PrOH=90 / 10, flow rate=1.0 mL / min, I=215 nm, t R =4.73min(major)and5.44min(minor).[α] D 20 :-173.2 (c 0.25, CH2Cl2; 99%ee). 1 H NMR (400MHz, CDCl3) δ7.65(d,J=7.8Hz,1H),7.29(d,J=8.2Hz,1H),7.22-7.17(m,5H),7.13-7.09(m,1H ),6.86(s,1H),6.17(s,1H),3.77(s,3H),3.22-3.09(m,1H),2.35(s,3H),1.31(dd,J=8.7,6.9Hz,6H). 13 C NMR (100MHz, CDCl3) δ170.5,138.8,137.1,131.9,129.8,128.1,127.8,123.6,121.9, 121.8,119.8,119.3,109.1,61.7,52.8,25.6,23.4,23.3,21.3.HRMS(ESI)m / z:[M+H] + Calcd for C 21 H 24 NO2322.1802; Found 322.1799.

[0066] Embodiment 17:

[0067]

[0068] Rh2(Oct)4 (0.08 mg, 0.0001 mmol, 0.001 equiv) and chiral phosphoric acid C1 (1.4 mg, 0.0025 mmol, 0.025 equiv) were added to a dry reaction tube, and then the indole derivative 1a (15.9 mg, 0.1 mmol, 1 equiv) was dissolved in 1 ml of redistilled dichloromethane. After the reaction tube was evacuated and filled with argon (this operation was repeated three times), the diazo ester derivative 2c (30.9 mg, 0.15 mmol, 1.5 equiv) was dissolved in 1 ml of redistilled dichloromethane and injected into the reaction tube by syringe, and stirred at 25°C for 15 min. The reaction solution was evaporated to dryness under reduced pressure, and the residue was purified by column chromatography (silica gel, eluent: EtOAc / PE = 1:50-1:20) to obtain a yellow oil (31.7 mg, 94%, >99% ee). Enantioselectivity: >99% ee; HPLC conditions: DaicelChiralpak IA column, n-hexane / i-PrOH=90 / 10, flow rate=1.0 mL / min, I=215 nm, t R =6.04min(major)and6.58min(minor).[α] D 20 :-101.3 (c 0.40, CH2Cl2; >99%ee). 1 H NMR (400MHz, CDCl3) δ7.64(d,J=7.8Hz,1H),7.31-7.23(m,3H),7.23-7.17(m,1H),7.14-7.07(m,1H),6.90(d,J= 7.8Hz,2H),6.84(s,1H),6.14(s,1H),3.80(s,3H),3.77(s,3H),3.24-3.06(m,1H),1.31(dd,J=8.9,6.9Hz,6H). 13 C NMR (100MHz, CDCl3) δ170.6,159.9,137.1,129.5,127.8,126.7,123.6,121.8,119. 8,119.3,114.4,109.1,61.4,55.4,52.8,25.6,23.33,23.26.HRMS(ESI)m / z:[M+H] + Calcd for C 21 H 24 NO3338.1751; Found 338.1750.

[0069] Embodiment 18:

[0070]

[0071] Rh2(Oct)4 (0.08 mg, 0.0001 mmol, 0.001 equiv) and chiral phosphoric acid C1 (1.4 mg, 0.0025 mmol, 0.025 equiv) were added to a dry reaction tube, and then the indole derivative 1a (15.9 mg, 0.1 mmol, 1 equiv) was dissolved in 1 ml of redistilled dichloromethane. The reaction tube was evacuated and filled with argon (this operation was repeated three times). The diazo ester derivative 2d (43.7 mg, 0.15 mmol, 1.5 equiv) was dissolved in 1 ml of redistilled dichloromethane and injected into the reaction tube with a syringe, and stirred at 25 °C for 15 min. The reaction solution was evaporated to dryness under reduced pressure, and the residue was purified by column chromatography (silica gel, eluent: EtOAc / PE=1:50-1:20) to give a light yellow solid (25.8 mg, 61%, 88% ee), melting point: 106-108°C; enantioselectivity: 88% ee; HPLC conditions: Daicel Chiralpak IA column, n-hexane / i-PrOH=90 / 10, flow rate=1.0 mL / min, I=215 nm, t R =6.29min(major)and 7.52min(minor).[α] D 20 :-83.3 (c 0.25, CH2Cl2; 88%ee). 1 H NMR (400MHz, CDCl3) δ7.64(d,J=7.8Hz,1H),7.36(d,J=8.7Hz,2H),7.29-7.23(m,3H),7.21-7.17(m,1H),7.13-7.09(m ,1H),6.83(s,1H),6.61(s,1H),6.14(s,1H),3.77(s,3H),3.23-3.08(m,1H),1.51(s,9H),1.30(dd,J=9.0,6.9Hz,6H). 13 C NMR (100MHz, CDCl3) δ170.5,152.7,139.0,137.1,129.01,128.96,127.8,123.7,121.8,1 19.8,119.3,118.7,109.1,80.9,61.4,52.8,28.4,25.6,23.3,23.2.HRMS(ESI)m / z:[M+H] + Calcd for C 25 H 31N2O4423.2278;Found423.2279.

[0072] Embodiment 19:

[0073]

[0074] Rh2(Oct)4 (0.08 mg, 0.0001 mmol, 0.001 equiv) and chiral phosphoric acid C1 (1.4 mg, 0.0025 mmol, 0.025 equiv) were added to a dry reaction tube, and then the indole derivative 1a (15.9 mg, 0.1 mmol, 1 equiv) was dissolved in 1 ml of redistilled dichloromethane. The reaction tube was evacuated and filled with argon (this operation was repeated three times). The diazo ester derivative 2e (31.6 mg, 0.15 mmol, 1.5 equiv) was dissolved in 1 ml of redistilled dichloromethane and injected into the reaction tube with a syringe, and stirred at 25 °C for 15 min. The reaction solution was evaporated to dryness under reduced pressure, and the residue was purified by column chromatography (silica gel, eluent: EtOAc / PE=1:50-1:20) to give a yellow oil (29.7 mg, 87%, 92% ee), enantioselectivity: 92% ee; HPLC conditions: DaicelChiralpak IA column, n-hexane / i-PrOH=90 / 10, flow rate=1.0 mL / min, I=215 nm, t R =6.66min(major)and7.33min(minor).[α] D 20 :-90.5 (c 0.35, CH2Cl2; 92%ee). 1 H NMR (400MHz, CDCl3) δ7.58(d,J=7.8Hz,1H),7.26(d,J=8.5Hz,2H),7.19-7.16(m,2H),7.16-7.08(m,2H ),7.07-7.01(m,1H),6.81(s,1H),6.09(s,1H),3.72(s,3H),3.19-3.00(m,1H),1.24(t,J=6.6Hz,6H). 13 C NMR (100MHz, CDCl3) δ169.9,137.0,134.9,133.6,129.3,129.2,127.8,124.2,122. 0,121.7,119.9,119.5,109.1,61.2,52.9,25.6,23.29,23.26.HRMS(ESI)m / z:[M+H] + Calcd for C 20 H21 ClNO2342.1255; Found 342.1255.

[0075] Embodiment 20:

[0076]

[0077] Rh2(Oct)4 (0.08 mg, 0.0001 mmol, 0.001 equiv) and chiral phosphoric acid C1 (1.4 mg, 0.0025 mmol, 0.025 equiv) were added to a dry reaction tube, and then the indole derivative 1a (15.9 mg, 0.1 mmol, 1 equiv) was dissolved in 1 ml of redistilled dichloromethane. The reaction tube was evacuated and filled with argon (this operation was repeated three times). The diazo ester derivative 2f (38.3 mg, 0.15 mmol, 1.5 equiv) was dissolved in 1 ml of redistilled dichloromethane and injected into the reaction tube with a syringe, and stirred at 25 °C for 15 min. The reaction solution was evaporated to dryness under reduced pressure, and the residue was purified by column chromatography (silica gel, eluent: EtOAc / PE=1:50-1:20) to give a colorless oil (33.1 mg, 86%, 94% ee), enantioselectivity: 94% ee; HPLC conditions: DaicelChiralpak IA column, n-hexane / i-PrOH=90 / 10, flow rate=0.8 mL / min, I=215 nm, t R =6.66min(major)and7.33min(minor).[α] D 20 :-90.5 (c 0.35, CH2Cl2; 92%ee). 1 H NMR (400MHz, CDCl3) δ7.65 (d, J = 7.8Hz, 1H), 7.51-7.48 (m, 2H), 7.26-7.22 (m, 1H), 7.19-7.10 ( m,4H),6.88(s,1H),6.15(s,1H),3.79(s,3H),3.25-3.10(m,1H),1.32(dd,J=6.7,6.2Hz,6H). 13 C NMR (100MHz, CDCl3) δ169.9,137.1,134.2,132.3,129.6,127.8,124.3,123.1,122 .1,121.7,120.0,119.6,109.2,61.4,53.0,25.7,23.4,23.3.HRMS(ESI)m / z:[M+H] + Calcd for C 20 H21 BrNO2386.0750; Found 386.0752.

[0078] Embodiment 21:

[0079]

[0080] Rh2(Oct)4 (0.08 mg, 0.0001 mmol, 0.001 equiv) and chiral phosphoric acid C1 (1.4 mg, 0.0025 mmol, 0.025 equiv) were added to a dry reaction tube, and then the indole derivative 1a (15.9 mg, 0.1 mmol, 1 equiv) was dissolved in 1 ml of redistilled dichloromethane. The reaction tube was evacuated and filled with argon (this operation was repeated three times). 2 g of the diazo ester derivative (28.5 mg, 0.15 mmol, 1.5 equiv) was dissolved in 1 ml of redistilled dichloromethane and injected into the reaction tube with a syringe, and stirred at 25 °C for 15 min. The reaction solution was evaporated to dryness under reduced pressure, and the residue was purified by column chromatography (silica gel, eluent: EtOAc / PE=1:50-1:20) to give a colorless oil (27.3 mg, 85%, 88% ee), enantioselectivity: 88% ee; HPLC conditions: DaicelChiralpak IA column, n-hexane / i-PrOH=90 / 10, flow rate=1 mL / min, I=215 nm, t R =5.14min(major)and5.90min(minor).[α] D 20 :-4.5 (c 0.25, CH2Cl2; 88%ee). 1 H NMR (400MHz, CDCl3) δ7.65(d,J=7.8Hz,1H),7.32-7.26(m,4H),7.22(t,J=8.8Hz,2H),7.13(t,J=7.4Hz,1 H),6.59(s,1H),6.31(s,1H),3.78(s,3H),3.24-3.05(m,1H),2.15(s,3H),1.27(dd,J=12.9,6.9Hz,6H). 13 C NMR (100MHz, CDCl3) δ171.0,137.9,137.2,133.0,131.3,129.2,127.9,127.7,126.6,123.7, 121.9,121.6,120.0,119.4,108.8,59.4,52.8,25.7,23.4,23.3,19.3.HRMS(ESI)m / z:[M+H]+ Calcd for C 21 H 24 NO2322.1802; Found 322.1800.

[0081] Embodiment 22:

[0082]

[0083] Rh2(Oct)4 (0.08 mg, 0.0001 mmol, 0.001 equiv) and chiral phosphoric acid C1 (1.4 mg, 0.0025 mmol, 0.025 equiv) were added to a dry reaction tube, and then the indole derivative 1a (15.9 mg, 0.1 mmol, 1 equiv) was dissolved in 1 ml of redistilled dichloromethane. The reaction tube was evacuated and filled with argon (this operation was repeated three times). The diazo ester derivative 2h (29.1 mg, 0.15 mmol, 1.5 equiv) was dissolved in 1 ml of redistilled dichloromethane and injected into the reaction tube with a syringe, and stirred at 25 °C for 15 min. The reaction solution was evaporated to dryness under reduced pressure, and the residue was purified by column chromatography (silica gel, eluent: EtOAc / PE=1:50-1:20) to give a yellow oil (29.9 mg, 92%, 98% ee), enantioselectivity: 98% ee; HPLC conditions: DaicelChiralpak IA column, n-hexane / i-PrOH=90 / 10, flow rate=2 mL / min, I=215 nm, t R =4.82min(major)and6.35min(minor).[α] D 20 :-23.7 (c 0.25, CH2Cl2; 98%ee). 1 H NMR (400MHz, CDCl3) δ7.65 (d, J = 7.9Hz, 1H), 7.37-7.32 (m, 2H), 7.24-7.16 (m, 2H), 7.15-7. 07(m,3H),6.95(s,1H),6.45(s,1H),3.80(s,3H),3.25-3.10(m,1H),1.33(t,J=6.9Hz,6H). 13C NMR (100MHz, CDCl3) δ169.6, 160.5 (d, J = 248.3Hz), 137.0, 130.7 (d, J = 8.4Hz), 129.1 (d, J = 3.0Hz), 127.7, 124.6 (d, J = 3.6Hz), 1 24.3, 123.2 (d, J = 14.3Hz), 122.0, 121.5, 119.8, 119.4, 115.9 (d, J = 21.5Hz), 109.1, 55.8 (d, J = 3.7Hz), 53.0, 25.6, 23.3, 23.2. 19 FNMR(376MHz,CDCl3)δ-116.3.HRMS(ESI)m / z:[M+H] + Calcd for C 20 H 21 FNO2326.1551;Found326.1548.

[0084] Embodiment 23:

[0085]

[0086] Rh2(Oct)4 (0.08 mg, 0.0001 mmol, 0.001 equiv) and chiral phosphoric acid C1 (1.4 mg, 0.0025 mmol, 0.025 equiv) were added to a dry reaction tube, and then the indole derivative 1a (15.9 mg, 0.1 mmol, 1 equiv) was dissolved in 1 ml of redistilled dichloromethane. The reaction tube was evacuated and filled with argon (this operation was repeated three times). The diazo ester derivative 2i (36.9 mg, 0.15 mmol, 1.5 equiv) was dissolved in 1 ml of redistilled dichloromethane and injected into the reaction tube with a syringe, and stirred at 25 °C for 15 min. The reaction solution was evaporated to dryness under reduced pressure, and the residue was purified by column chromatography (silica gel, eluent: EtOAc / PE=1:50-1:20) to give a colorless oil (34.1 mg, 91%, 98% ee), enantioselectivity: 98% ee; HPLC conditions: DaicelChiralpak IA column, n-hexane / i-PrOH=99 / 1, flow rate=1 mL / min, I=215 nm, t R =4.73min(major)and 5.29min(minor).[α] D 20 :-50.4 (c 0.45, CH2Cl2; 98%ee). 1H NMR (400MHz, CDCl3) δ7.66(d,J=7.8Hz,1H),7.46(d,J=2.0Hz,1H),7.25(d,J=4.4Hz,1H),7.23-7.17(m,2H),7.16-7.1 0(m,1H),7.00(d,J=8.4Hz,1H),6.86(s,1H),6.49(s,1H),3.81(s,3H),3.26-3.12(m,1H),1.34(dd,J=6.9,1.7Hz,6H). 13 C NMR (100MHz, CDCl3) δ169.2,136.9,135.4,134.6,132.3,129.9,129.5,127.8,127.7,124. 7,122.3,121.2,119.9,119.7,109.2,59.1,53.2,25.6,23.29,23.26.HRMS(ESI)m / z:[M+H] + Calcd for C 20 H 20 Cl2NO2376.0866; Found 376.0866.

[0087] Embodiment 24:

[0088]

[0089] Rh2(Oct)4 (0.08 mg, 0.0001 mmol, 0.001 equiv) and chiral phosphoric acid C1 (1.4 mg, 0.0025 mmol, 0.025 equiv) were added to a dry reaction tube, and then the indole derivative 1a (15.9 mg, 0.1 mmol, 1 equiv) was dissolved in 1 ml of redistilled dichloromethane. The reaction tube was evacuated and filled with argon (this operation was repeated three times). The diazo ester derivative 2j (28.5 mg, 0.15 mmol, 1.5 equiv) was dissolved in 1 ml of redistilled dichloromethane and injected into the reaction tube with a syringe, and stirred at 25°C for 15 min. The reaction solution was evaporated to dryness under reduced pressure, and the residue was purified by column chromatography (silica gel, eluent: EtOAc / PE=1:50-1:20) to give a colorless oil (27.3 mg, 85%, 98% ee), enantioselectivity: 98% ee; HPLC conditions: DaicelChiralpak IA column, n-hexane / i-PrOH=90 / 10, flow rate=1 mL / min, I=215 nm, t R =4.28min(major)and4.70min(minor).[α] D20 :-37.9 (c 0.25, CH2Cl2; 98%ee). 1 H NMR (400MHz, CDCl3) δ7.65 (d, J = 7.8Hz, 1H), 7.30-7.24 (m, 2H), 7.23-7.16 (m, 2H), 7.13-7.10 (m ,3H),6.88(s,1H),6.17(s,1H),3.78(s,3H),3.25-3.08(m,1H),2.33(s,3H),1.35-1.26(m,6H). 13 C NMR (100MHz, CDCl3) δ170.5,138.9,137.2,134.8,129.7,128.9,128.8,127.8,125.1,123.7, 121.9,121.8,119.8,119.4,109.1,61.9,52.8,25.7,23.4,23.3,21.6.HRMS(ESI)m / z:[M+H] + Calcd for C 21 H 24 NO2322.1802; Found 322.1800.

[0090] Embodiment 25:

[0091]

[0092] Rh2(Oct)4 (0.08 mg, 0.0001 mmol, 0.001 equiv) and chiral phosphoric acid C1 (1.4 mg, 0.0025 mmol, 0.025 equiv) were added to a dry reaction tube, and then the indole derivative 1a (15.9 mg, 0.1 mmol, 1 equiv) was dissolved in 1 ml of redistilled dichloromethane. The reaction tube was evacuated and filled with argon (this operation was repeated three times). The diazo ester derivative 2k (33.9 mg, 0.15 mmol, 1.5 equiv) was dissolved in 1 ml of redistilled dichloromethane and injected into the reaction tube with a syringe, and stirred at 25 °C for 15 min. The reaction solution was evaporated to dryness under reduced pressure, and the residue was purified by column chromatography (silica gel, eluent: EtOAc / PE=1:50-1:20) to give a yellow oil (33.9 mg, 95%, 97% ee), enantioselectivity: 97% ee; HPLC conditions: DaicelChiralpak IA column, n-hexane / i-PrOH=90 / 10, flow rate=1 mL / min, I=215 nm, t R =6.79min(major)and7.77min(minor).[α]D 20 :-26.3 (c 0.25, CH2Cl2; 97% ee). 1 1H NMR (400 MHz, CDCl3) δ 7.86 - 7.80 (m, 4H), 7.67 (d, J = 7.8 Hz, 1H), 7.53 - 7.49 (m, 2H), 7.41 - 7.34 (m, 2H), 7.23 - 7.19 (m, 1H), 7.15 - 7.11 (m, 1H), 6.90 (s, 1H), 6.38 (s, 1H), 3.83 (s, 3H), 3.20 - 3.13 (m, 1H), 1.30 (dd, J = 11.0, 6.9 Hz, 6H). 13 13C NMR (100 MHz, CDCl3) δ 170.4, 137.2, 133.3, 133.2, 132.3, 129.0, 128.3, 127.82, 127.78, 127.3, 126.9, 126.7, 125.6, 123.9, 122.0, 121.9, 119.9, 119.4, 109.1, 62.0, 52.9, 25.6, 23.33, 23.26. HRMS (ESI) m / z: [M + H] + Calcd for C 24 H 24 NO2 358.1802; Found 358.1799.

[0093] Example 26:

[0094]

[0095] Rh2(Oct)4 (0.08 mg, 0.0001 mmol, 0.001 equiv) and chiral phosphoric acid C1 (1.4 mg, 0.0025 mmol, 0.025 equiv) were added to a dry reaction tube, and then the indole derivative 1a (15.9 mg, 0.1 mmol, 1 equiv) was dissolved in 1 ml of redistilled dichloromethane. The reaction tube was evacuated and filled with argon (this operation was repeated three times). The diazo ester derivative 2l (28.2 mg, 0.15 mmol, 1.5 equiv) was dissolved in 1 ml of redistilled dichloromethane and injected into the reaction tube with a syringe, and stirred at 25°C for 15 min. The reaction solution was evaporated to dryness under reduced pressure, and the residue was purified by column chromatography (silica gel, eluent: EtOAc / PE=1:20-1:10) to give a brown oil (29.1 mg, 93%, 98% ee), enantioselectivity: 98% ee; HPLC conditions: DaicelChiralpak IA column, n-hexane / i-PrOH=90 / 10, flow rate=1 mL / min, I=215 nm, t R =4.93min(major)and5.51min(minor).[α] D 20 :-106.6 (c 0.35, CH2Cl2; 98%ee). 1 H NMR (400MHz, CDCl3) δ7.58 (d, J = 7.8Hz, 1H), 7.28-7.26 (m, 1H), 7.23-7.20 (m, 2H), 7.15-7.10 (m, 1H), 7.07-7. 03(m,1H),6.96-6.95(m,1H),6.80(s,1H),6.17(s,1H),3.71(s,3H),3.18-3.00(m,1H),1.25(t,J=6.8Hz,6H). 13 C NMR (100MHz, CDCl3) δ170.1,136.9,135.2,127.8,127.3,126.8,124.5,123.9,121. 9,121.8,119.8,119.4,109.1,57.8,52.8,25.6,23.32,23.25.HRMS(ESI)m / z:[M+H] + Calcd for C 18 H 20 NO2S 314.1209; Found 314.1207.

[0096] Embodiment 27:

[0097]

[0098] Rh2(Oct)4 (0.08 mg, 0.0001 mmol, 0.001 equiv) and chiral phosphoric acid C1 (1.4 mg, 0.0025 mmol, 0.025 equiv) were added to a dry reaction tube, and then the indole derivative 1a (15.9 mg, 0.1 mmol, 1 equiv) was dissolved in 1 ml of redistilled dichloromethane. The reaction tube was evacuated and filled with argon (this operation was repeated three times). The diazo ester derivative 2m (55.4 mg, 0.15 mmol, 1.5 equiv) was dissolved in 1 ml of redistilled dichloromethane and injected into the reaction tube with a syringe, and stirred at 25°C for 15 min. The reaction solution was evaporated to dryness under reduced pressure, and the residue was purified by column chromatography (silica gel, eluent: EtOAc / PE=1:20-1:10) to give a light yellow solid (25.0 mg, 50%, 97% ee), melting point: 133-135°C, enantioselectivity: 98% ee; HPLC conditions: Daicel Chiralpak IA column, n-hexane / i-PrOH=90 / 10, flow rate=1 mL / min, I=215 nm, t R =6.60min(major)and 8.42min(minor).[α] D 20 :-18.3 (c 0.4, CH2Cl2; 97%ee). 1 HNMR (400MHz, CDCl3) δ7.99(d,J=8.4Hz,1H),7.81-7.72(m,3H),7.64(d,J=7.8Hz,1H),7.39(d,J=8.2Hz,1H),7.33-7.28(m,1H),7.25-7.18(m ,3H),7.16-7.08(m,3H),6.69(s,1H),6.34(s,1H),3.81(s,3H),3.18- 3.00(m,1H),2.36(s,3H),1.25(d,J=6.9Hz,3H),1.19(d,J=6.9Hz,3H). 13 C NMR (100MHz, CDCl3) δ169.5,145.3,136.8,135.2,135.0,130.0,129.1,128.0,126.9,125.9,125.4,124.1,123.8, 122.0,121.5,119.9,119.6,119.4,116.5,113.8,109.0,54.5,53.0,25.5,23.2,23.1,21.6.HRMS(ESI)m / z:[M+H]+ Calcd for C 29 H 29 N2O4S 501.1843; Found 501.1844.

[0099] Embodiment 28:

[0100]

[0101] Rh2(Oct)4 (0.08 mg, 0.0001 mmol, 0.001 equiv) and chiral phosphoric acid C1 (1.4 mg, 0.0025 mmol, 0.025 equiv) were added to a dry reaction tube, and then the indole derivative 1a (15.9 mg, 0.1 mmol, 1 equiv) was dissolved in 1 ml of redistilled dichloromethane. The reaction tube was evacuated and filled with argon (this operation was repeated three times). The diazo ester derivative 2n (28.5 mg, 0.15 mmol, 1.5 equiv) was dissolved in 1 ml of redistilled dichloromethane and injected into the reaction tube with a syringe, and stirred at 25°C for 15 min. The reaction solution was evaporated to dryness under reduced pressure, and the residue was purified by column chromatography (silica gel, eluent: EtOAc / PE=1:20-1:10) to give a yellow oil (24.4 mg, 76%, 97% ee), enantioselectivity: 97% ee; HPLC conditions: DaicelChiralpak IA column, n-hexane / i-PrOH=99 / 1, flow rate=1 mL / min, I=215 nm, t R =5.29min(major)and 6.59min(minor).[α] D 20 :-118.3 (c 0.2, CH2Cl2; 97%ee). 1 H NMR (400MHz, CDCl3) δ7.65(d,J=7.8Hz,1H),7.5.43-5.35(m,3H),7.34-7.28(m,3H),7.20(t,J=7.4Hz,1H),7.12(t,J=7 .4Hz,1H),6.90(s,1H),6.20(s,1H),4.34-4.18(m,2H),3.24-3.10(m,1H),1.31(t,J=7.3Hz,6H),1.27(t,J=7.3Hz,3H). 13C NMR (100MHz, CDCl3) δ169.8,137.2,135.1,129.0,128.8,128.0,127.7,123.7,122.0,12 1.7,119.8,119.3,109.1,61.93,61.91,25.6,23.31,23.28,14.2.HRMS(ESI)m / z:[M+H] + Calcd for C 21 H 24 NO2322.1802; Found 322.1801.

[0102] Embodiment 29:

[0103]

[0104] Rh2(Oct)4 (0.08 mg, 0.0001 mmol, 0.001 equiv) and chiral phosphoric acid C1 (1.4 mg, 0.0025 mmol, 0.025 equiv) were added to a dry reaction tube, and then the indole derivative 1a (15.9 mg, 0.1 mmol, 1 equiv) was dissolved in 1 ml of redistilled dichloromethane. The reaction tube was evacuated and filled with argon (this operation was repeated three times). The diazo ester derivative 2o (37.8 mg, 0.15 mmol, 1.5 equiv) was dissolved in 1 ml of redistilled dichloromethane and injected into the reaction tube with a syringe, and stirred at 25°C for 15 min. The reaction solution was evaporated to dryness under reduced pressure, and the residue was purified by column chromatography (silica gel, eluent: EtOAc / PE=1:20-1:10) to give a light yellow solid (27.6 mg, 72%, 96% ee), melting point: 276-278°C, enantioselectivity: 96% ee; HPLC conditions: Daicel Chiralpak IC column, n-hexane / i-PrOH=99.5 / 0.5, flow rate=1 mL / min, I=215 nm, t R =6.19min(major)and 7.09min(minor).[α] D 20 :-62.7 (c 0.2, CH2Cl2; 96%ee). 1H NMR (400MHz, CDCl3) δ7.65(d,J=7.6Hz,1H),7.38-7.33(m,3H),7.33-7.29(m,3H),7.29-7.21(m,5H),7.17(t,J=7.4H z,1H),7.12(t,J=7.4Hz,1H),6.87(s,1H),6.25(s,1H),5.29-5.16(m,2H),3.23-3.08(m,1H),1.30(t,J=7.2Hz,6H). 13 C NMR (100MHz, CDCl3) δ169.7,137.2,135.1,134.9,129.0,128.8,128.6,128.5,128.4,128.0,1 27.8,123.8,121.9,121.8,119.8,119.4,109.2,67.5,62.0,25.6,23.3.HRMS(ESI)m / z:[M+H] + Calcdfor C 26 H 26 NO2384.1958;Found 384.1961.

[0105] Embodiment 30:

[0106]

[0107] Rh2(Oct)4 (0.08 mg, 0.0001 mmol, 0.001 equiv) and chiral phosphoric acid C1 (1.4 mg, 0.0025 mmol, 0.025 equiv) were added to a dry reaction tube, and then the indole derivative 1a (15.9 mg, 0.1 mmol, 1 equiv) was dissolved in 1 ml of redistilled dichloromethane. The reaction tube was evacuated and filled with argon (this operation was repeated three times). The diazo ester derivative 2p (30.6 mg, 0.15 mmol, 1.5 equiv) was dissolved in 1 ml of redistilled dichloromethane and injected into the reaction tube with a syringe, and stirred at 25°C for 15 min. The reaction solution was evaporated to dryness under reduced pressure, and the residue was purified by column chromatography (silica gel, eluent: EtOAc / PE=1:20-1:10) to give a light yellow oil (28.1 mg, 84%, 57% ee), enantioselectivity: 57% ee; HPLC conditions: DaicelChiralpak IA column, n-hexane / i-PrOH=99 / 1, flow rate=1 mL / min, I=215 nm, t R =4.85min(major)and 5.40min(minor).[α] D20 :-39.2 (c 0.15, CH2Cl2; 57% ee). 1 1H NMR (400 MHz, CDCl3) δ 7.65 (d, J = 7.8 Hz, 1H), 7.41 - 7.34 (m, 3H), 7.31 (dd, J = 8.0, 3.2 Hz, 3H), 7.19 (t, J = 7.5 Hz, 1H), 7.12 (t, J = 7.4 Hz, 1H), 6.91 (s, 1H), 6.16 (s, 1H), 5.12 (hept, J = 6.3 Hz, 1H), 3.16 (h, J = 6.9 Hz, 1H), 1.31 (t, J = 7.0 Hz, 6H), 1.27 (d, J = 6.3 Hz, 3H), 1.21 (d, J = 6.2 Hz, 3H). 13 13C NMR (100 MHz, CDCl3) δ 169.3, 137.2, 135.3, 129.0, 128.7, 127.9, 127.7, 123.6, 122.0, 121.7, 119.8, 119.3, 109.2, 69.8, 62.0, 25.6, 23.33, 23.31, 21.8, 21.6. HRMS (ESI) m / z: [M+H] + Calcd for C 22 H 26 NO2 336.1958; Found 336.1957. HRMS (ESI) m / z: [M+H] + Calcd for C 22 H 26 NO2 336.1958; Found 336.1957.

[0108] Example 31:

[0109]

[0110] Rh2(Oct)4 (0.08 mg, 0.0001 mmol, 0.001 equiv) and chiral phosphoric acid C1 (1.4 mg, 0.0025 mmol, 0.025 equiv) were added to a dry reaction tube, and then the indole derivative 1b (13.1 mg, 0.1 mmol, 1 equiv) was dissolved in 1 ml of redistilled dichloromethane. The reaction tube was evacuated and filled with argon (this operation was repeated three times). The diazo ester derivative 2a (26.4 mg, 0.15 mmol, 1.5 equiv) was dissolved in 1 ml of redistilled dichloromethane and injected into the reaction tube with a syringe, and stirred at 25°C for 15 min. The reaction solution was evaporated to dryness under reduced pressure, and the residue was purified by column chromatography (silica gel, eluent: EtOAc / PE=1:20-1:10) to give a colorless oil (14.5 mg, 52%, 98% ee), enantioselectivity: 98% ee; HPLC conditions: DaicelChiralpak IA column, n-hexane / i-PrOH=90 / 10, flow rate=1 mL / min, I=215 nm, t R =5.36min(major)and5.91min(minor).[α] D 20 :-147.8 (c 0.25, CH2Cl2; 98%ee). 1 H NMR (400MHz, CDCl3) δ7.57 (d, J = 9.4Hz, 1H), 7.42-7.35 (m, 3H), 7.34-7.29 (m, 3H), 7.24- 7.18(m,1H),7.14(t,J=7.4Hz,1H),6.87(s,1H),6.22(s,1H),3.79(s,3H),2.28(s,3H). 13 C NMR (100MHz, CDCl3) δ170.4,136.8,134.9,129.2,129.1,128.9,128.1,124. 1,121.9,119.5,119.3,111.7,108.8,61.8,52.8,9.8.HRMS(ESI)m / z:[M+H] + Calcd for C 18 H 18 NO2280.1332; Found 280.1331.

[0111] Embodiment 32:

[0112]

[0113] Rh2(Oct)4 (0.08 mg, 0.0001 mmol, 0.001 equiv) and chiral phosphoric acid C1 (1.4 mg, 0.0025 mmol, 0.025 equiv) were added to a dry reaction tube, and then the indole derivative 1c (14.5 mg, 0.1 mmol, 1 equiv) was dissolved in 1 ml of redistilled dichloromethane. The reaction tube was evacuated and filled with argon (this operation was repeated three times). The diazo ester derivative 2a (26.4 mg, 0.15 mmol, 1.5 equiv) was dissolved in 1 ml of redistilled dichloromethane and injected into the reaction tube with a syringe, and stirred at 25 °C for 15 min. The reaction solution was evaporated to dryness under reduced pressure, and the residue was purified by column chromatography (silica gel, eluent: EtOAc / PE=1:20-1:10) to give a colorless oil (14.1 mg, 48%, 99% ee), enantioselectivity: 99% ee; HPLC conditions: DaicelChiralpak IA column, n-hexane / i-PrOH=90 / 10, flow rate=1 mL / min, I=215 nm, t R =5.25min(major)and6.05min(minor).[α] D 20 :-115.0 (c 0.25, CH2Cl2; 99%ee). 1 H NMR (400MHz, CDCl3) δ7.61 (d, J = 7.8Hz, 1H), 7.39-7.37 (m, 3H), 7.33-7.29 (m, 3H), 7.24-7.21 (m, 1H), 7. 13(t,J=7.4Hz,1H),6.89(s,1H),6.22(s,1H),3.80(s,3H),2.74(q,J=7.6Hz,2H),1.27(t,J=7.6Hz,3H). 13 C NMR (100MHz, CDCl3) δ170.4,137.0,134.9,129.1,128.9,128.4,128.1,123.0,1 21.9,119.5,119.4,118.7,109.0,61.8,52.8,18.5,14.4.HRMS(ESI)m / z:[M+H] + Calcd for C 19 H 20 NO2294.1489; Found 294.1487.

[0114] Embodiment 33:

[0115]

[0116] Rh2(Oct)4 (0.08 mg, 0.0001 mmol, 0.001 equiv) and chiral phosphoric acid C1 (1.4 mg, 0.0025 mmol, 0.025 equiv) were added to a dry reaction tube, and then the indole derivative 1d (17.3 mg, 0.1 mmol, 1 equiv) was dissolved in 1 ml of redistilled dichloromethane. The reaction tube was evacuated and filled with argon (this operation was repeated three times). The diazo ester derivative 2a (26.4 mg, 0.15 mmol, 1.5 equiv) was dissolved in 1 ml of redistilled dichloromethane and injected into the reaction tube with a syringe, and stirred at 25 °C for 15 min. The reaction solution was evaporated to dryness under reduced pressure, and the residue was purified by column chromatography (silica gel, eluent: EtOAc / PE=1:20-1:10) to give a colorless oil (22.5 mg, 70%, 96% ee), enantioselectivity: 96% ee; HPLC conditions: DaicelChiralpak IA column, n-hexane / i-PrOH=90 / 10, flow rate=2 mL / min, I=215 nm, t R =4.95min(major)and5.92min(minor).[α] D 20 :-71.0 (c 0.10, CH2Cl2; 96%ee). 1 H NMR (400MHz, CDCl3) δ7.59 (d, J = 7.8Hz, 1H), 7.41-7.35 (m, 3H), 7.34-7.28 (m, 3H), 7.24-7.18 (m, 1H), 7.14-7.10 (m ,1H),6.90(s,1H),6.23(s,1H),3.79(s,3H),2.56(d,J=7.1Hz,2H),2.00-1.88(m,1H),0.91(dd,J=6.5,4.9Hz,6H). 13 C NMR (100MHz, CDCl3) δ170.4,137.0,135.1,129.1,129.0,128.9,128.0,124.7,121 .8,119.7,119.5,115.9,109.0,61.9,52.9,34.7,29.2,22.8.HRMS(ESI)m / z:[M+H] + Calcd for C 21 H 24 NO2322.1802; Found 322.1799.

[0117] Embodiment 34:

[0118]

[0119] Rh2(Oct)4 (0.08 mg, 0.0001 mmol, 0.001 equiv) and chiral phosphoric acid C1 (1.4 mg, 0.0025 mmol, 0.025 equiv) were added to a dry reaction tube, and then the indole derivative 1e (17.3 mg, 0.1 mmol, 1 equiv) was dissolved in 1 ml of redistilled dichloromethane. The reaction tube was evacuated and filled with argon (this operation was repeated three times). The diazo ester derivative 2a (26.4 mg, 0.15 mmol, 1.5 equiv) was dissolved in 1 ml of redistilled dichloromethane and injected into the reaction tube with a syringe, and stirred at 25 °C for 15 min. The reaction solution was evaporated to dryness under reduced pressure, and the residue was purified by column chromatography (silica gel, eluent: EtOAc / PE=1:20-1:10) to give a colorless oil (27.9 mg, 87%, 97% ee), enantioselectivity: 97% ee; HPLC conditions: DaicelChiralpak IB column, n-hexane / i-PrOH=99 / 1, flow rate=1 mL / min, I=215 nm, t R =5.45min(major)and 5.85min(minor).[α] D 20 :-94.9 (c 0.38, CH2Cl2; 97%ee). 1 H NMR (400MHz, CDCl3) δ7.81 (d, J = 7.7Hz, 1H), 7.40-7.33 (m, 3H), 7.33-7.27 (m, 3H), 7.2 0-7.15(m,1H),7.13-7.07(m,1H),6.87(s,1H),6.20(s,1H),3.77(s,3H),1.40(s,9H). 13 C NMR (100MHz, CDCl3) δ170.4,137.8,135.0,129.1,128.9,128.1,127.0,126.5,1 22.0,121.7,121.5,119.2,109.3,61.9,52.8,31.8,30.8.HRMS(ESI)m / z:[M+H] + Calcd for C 21 H 24 NO2322.1802; Found 322.1803.

[0120] Embodiment 35:

[0121]

[0122] Rh2(Oct)4 (0.08 mg, 0.0001 mmol, 0.001 equiv) and chiral phosphoric acid C1 (1.4 mg, 0.0025 mmol, 0.025 equiv) were added to a dry reaction tube, and then the indole derivative 1f (18.5 mg, 0.1 mmol, 1 equiv) was dissolved in 1 ml of redistilled dichloromethane. The reaction tube was evacuated and filled with argon (this operation was repeated three times). The diazo ester derivative 2a (26.4 mg, 0.15 mmol, 1.5 equiv) was dissolved in 1 ml of redistilled dichloromethane and injected into the reaction tube with a syringe, and stirred at 25°C for 15 min. The reaction solution was evaporated to dryness under reduced pressure, and the residue was purified by column chromatography (silica gel, eluent: EtOAc / PE=1:20-1:10) to give a yellow oil (31.0 mg, 93%, 92% ee), enantioselectivity: 92% ee; HPLC conditions: DaicelChiralpak IA column, n-hexane / i-PrOH=99.7 / 0.3, flow rate=1 mL / min, I=215 nm, t R =6.83min(major)and7.35min(minor).[α] D 20 :-37.8 (c 0.40, CH2Cl2; 92%ee). 1 H NMR (400MHz, CDCl3) δ7.72(d,J=8.3Hz,1H),7.40-7.34(m,3H),7.33-7.25(m,3H),7.21-7.14(m,1H),7.10-7.02(m,1H),6.93(s,1 H), 6.21 (s, 1H), 6.09 (dd, J = 17.4, 10.5Hz, 1H), 5.06 (d, J = 17.4Hz, 1H), 4.99 (d, J = 10.5Hz, 1H), 3.78 (s, 3H), 1.46 (d, J = 5.2Hz, 6H). 13 C NMR (100MHz, CDCl3) δ170.3,147.7,137.7,134.9,129.1,128.9,128.0,127.1,123.7,1 22.8,121.8,121.6,119.2,110.7,109.2,61.9,52.8,37.6,28.1.HRMS(ESI)m / z:[M+H] + Calcdfor C 22 H 24 NO2334.1802; Found 334.1800.

[0123] Embodiment 36:

[0124]

[0125] Rh2(Oct)4 (0.08 mg, 0.0001 mmol, 0.001 equiv) and chiral phosphoric acid C1 (1.4 mg, 0.0025 mmol, 0.025 equiv) were added to a dry reaction tube, and then the indole derivative 1i (24.1 mg, 0.1 mmol, 1 equiv) was dissolved in 1 ml of redistilled dichloromethane. The reaction tube was evacuated and filled with argon (this operation was repeated three times). The diazo ester derivative 2a (26.4 mg, 0.15 mmol, 1.5 equiv) was dissolved in 1 ml of redistilled dichloromethane and injected into the reaction tube with a syringe, and stirred at 25 °C for 15 min. The reaction solution was evaporated to dryness under reduced pressure, and the residue was purified by column chromatography (silica gel, eluent: EtOAc / PE=1:20-1:10) to give a yellow oil (26.5 mg, 68%, >99% ee), enantioselectivity: >99% ee; HPLC conditions: DaicelChiralpak IB column, n-hexane / i-PrOH=90 / 10, flow rate=1 mL / min, I=215 nm, t R =9.14min(major)and9.73min(minor).[α] D 20 :-93.3 (c 0.25, CH2Cl2; >99%ee). 1 H NMR (400MHz, CDCl3) δ7.43-7.36(m,4H),7.35-7.28(m,3H),7.24-7.12(m,5H ),7.08(t,J=7.0Hz,1H),6.94(s,1H),6.23(s,1H),4.03(s,2H),3.81(s,3H). 13 C NMR (100MHz, CDCl3) δ170.2,139.6,137.1,134.7,131.5,129.9,129.1,129.0,128.4,128. 2,128.0,125.1,122.2,119.9,119.6,114.7,109.2,61.9,52.9,31.0.HRMS(ESI)m / z:[M+H] + Calcd for C 24 H 21 ClNO2390.1255; Found 390.1252.

[0126] Embodiment 37:

[0127]

[0128] Rh2(Oct)4 (0.08 mg, 0.0001 mmol, 0.001 equiv) and chiral phosphoric acid C1 (1.4 mg, 0.0025 mmol, 0.025 equiv) were added to a dry reaction tube, and then the indole derivative 1j (19.3 mg, 0.1 mmol, 1 equiv) was dissolved in 1 ml of redistilled dichloromethane. The reaction tube was evacuated and filled with argon (this operation was repeated three times). The diazo ester derivative 2a (26.4 mg, 0.15 mmol, 1.5 equiv) was dissolved in 1 ml of redistilled dichloromethane and injected into the reaction tube with a syringe, and stirred at 25 °C for 15 min. The reaction solution was evaporated to dryness under reduced pressure, and the residue was purified by column chromatography (silica gel, eluent: EtOAc / PE=1:20-1:10) to give a light yellow oil (26.9 mg, 79%, 96% ee), enantioselectivity: 96% ee; HPLC conditions: DaicelChiralpak IB column, n-hexane / i-PrOH=98 / 2, flow rate=0.8 mL / min, I=215 nm, t R =15.30min(major)and16.30min(minor).[α] D 20 :-0.8 (c 0.20, CH2Cl2; 96%ee). 1 H NMR (400MHz, CDCl3) δ7.95 (d, J = 7.5Hz, 1H), 7.65-7.58 (m, 2H), 7.44-7.34 (m, 8H), 7.32-7.18 (m, 4H), 6.29 (s, 1H), 3.82 (s, 3H). 13 C NMR (100MHz, CDCl3) δ170.0,137.3,135.3,134.4,129.21,129.16,128.7,128.2,127.6,1 26.7,126.0,124.4,122.4,120.7,120.3,118.1,109.3,62.0,52.6.HRMS(ESI)m / z:[M+H] + Calcd for C 23 H 20 NO2342.1489; Found 342.1484.

[0129] Embodiment 38:

[0130]

[0131] Rh2(Oct)4 (0.08 mg, 0.0001 mmol, 0.001 equiv) and chiral phosphoric acid C1 (1.4 mg, 0.0025 mmol, 0.025 equiv) were added to a dry reaction tube, and then the indole derivative 1k (17.3 mg, 0.1 mmol, 1 equiv) was dissolved in 1 ml of redistilled dichloromethane. The reaction tube was evacuated and filled with argon (this operation was repeated three times). The diazo ester derivative 2a (26.4 mg, 0.15 mmol, 1.5 equiv) was dissolved in 1 ml of redistilled dichloromethane and injected into the reaction tube with a syringe, and stirred at 25 °C for 15 min. The reaction solution was evaporated to dryness under reduced pressure, and the residue was purified by column chromatography (silica gel, eluent: EtOAc / PE=1:20-1:10) to give a colorless oil (23.1 mg, 72%, 90% ee), enantioselectivity: 90% ee; HPLC conditions: DaicelChiralpak IA column, n-hexane / i-PrOH=90 / 10, flow rate=1 mL / min, I=215 nm, t R =4.36min(major)and4.76min(minor).[α] D 20 :-38.8 (c 0.25, CH2Cl2; 90%ee). 1 H NMR (400MHz, CDCl3) δ7.42-7.32(m,3H),7.35-7.26(m,2H),7.14(d,J=8.2Hz,1H),7.07(t,J=7.2Hz,1H),6.91(s,1H),6.86(d ,J=7.0Hz,1H),6.21(s,1H),3.79(s,3H),3.46(hept,J=6.8Hz,1H),2.72(s,3H),1.29(d,J=6.8Hz,3H),1.25(d,J=6.8Hz,3H). 13 C NMR (100MHz, CDCl3) δ170.3,137.2,134.9,131.2,129.0,128.8,128.0,126.3,125 .3,121.8,121.7,106.9,61.9,52.8,26.0,25.0,24.9,20.4.HRMS(ESI)m / z:[M+H] + Calcd for C 21 H 24 NO2322.1802; Found 322.1802.

[0132] Embodiment 39:

[0133]

[0134] Rh2(Oct)4 (0.08 mg, 0.0001 mmol, 0.001 equiv) and chiral phosphoric acid C1 (1.4 mg, 0.0025 mmol, 0.025 equiv) were added to a dry reaction tube, and then the indole derivative 1m (17.3 mg, 0.1 mmol, 1 equiv) was dissolved in 1 ml of redistilled dichloromethane. The reaction tube was evacuated and filled with argon (this operation was repeated three times). The diazo ester derivative 2a (26.4 mg, 0.15 mmol, 1.5 equiv) was dissolved in 1 ml of redistilled dichloromethane and injected into the reaction tube with a syringe, and stirred at 25°C for 15 min. The reaction solution was evaporated to dryness under reduced pressure, and the residue was purified by column chromatography (silica gel, eluent: EtOAc / PE=1:20-1:10) to give a colorless oil (24.1 mg, 75%, 97% ee), enantioselectivity: 97% ee; HPLC conditions: DaicelChiralpak IA column, n-hexane / i-PrOH=95 / 5, flow rate=1 mL / min, I=215 nm, t R =5.28min(major)and 5.80min(minor).[α] D 20 :-101.7 (c 0.15, CH2Cl2; 97%ee). 1 H NMR (400MHz, CDCl3) δ7.43 (s, 1H), 7.41-7.33 (m, 3H), 7.33-7.25 (m, 2H), 7.17 (d, J = 8.4Hz, 1H), 7.06-6.98 ( m,1H),6.85(s,1H),6.18(s,1H),3.79(s,3H),3.14(hept,J=6.9Hz,1H),2.45(s,3H),1.30(t,J=7.2Hz,6H). 13 CNMR (100MHz, CDCl3) δ170.4,135.5,135.1,129.0,128.8,128.6,127.9,123.33,123 .30,122.1,119.5,108.9,62.0,52.7,25.6,23.29,23.27,21.5.HRMS(ESI)m / z:[M+H] + Calcd for C 21 H 24NO2322.1802; Found 322.1802.

[0135] Embodiment 40:

[0136]

[0137] Rh2(Oct)4 (0.08 mg, 0.0001 mmol, 0.001 equiv) and chiral phosphoric acid C1 (1.4 mg, 0.0025 mmol, 0.025 equiv) were added to a dry reaction tube, and then the indole derivative 1n (17.3 mg, 0.1 mmol, 1 equiv) was dissolved in 1 ml of redistilled dichloromethane. The reaction tube was evacuated and filled with argon (this operation was repeated three times). The diazo ester derivative 2a (26.4 mg, 0.15 mmol, 1.5 equiv) was dissolved in 1 ml of redistilled dichloromethane and injected into the reaction tube with a syringe, and stirred at 25 °C for 15 min. The reaction solution was evaporated to dryness under reduced pressure, and the residue was purified by column chromatography (silica gel, eluent: EtOAc / PE=1:20-1:10) to give a colorless oil (27.6 mg, 81%, 93% ee), enantioselectivity: 93% ee; HPLC conditions: DaicelChiralpak IA column, n-hexane / i-PrOH=90 / 10, flow rate=1 mL / min, I=215 nm, t R =5.13min(major)and5.56min(minor).[α] D 20 :-95.5 (c 0.30, CH2Cl2; 93%ee). 1 H NMR(400MHz, CDCl3)δ7.60(s,1H),7.42-7.34(m,3H),7.32-7.26(m,2H),7.20-7.10(m ,2H),6.90(s,1H),6.15(s,1H),3.79(s,3H),3.18-3.03(m,1H),1.29(t,J=7.8Hz,6H). 13 C NMR (100MHz, CDCl3) δ170.1,135.5,134.5,129.2,129.1,128.9,128.0,125.1,123. 5,123.4,122.1,119.3,110.3,62.1,52.9,25.5,23.23,23.20.HRMS(ESI)m / z:[M+H] + Calcd for C 20 H 21ClNO2342.1255; Found 342.1253.

[0138] Embodiment 41:

[0139]

[0140] Rh2(Oct)4 (0.08 mg, 0.0001 mmol, 0.001 equiv) and chiral phosphoric acid C1 (1.4 mg, 0.0025 mmol, 0.025 equiv) were added to a dry reaction tube, and then the indole derivative 1o (17.3 mg, 0.1 mmol, 1 equiv) was dissolved in 1 ml of redistilled dichloromethane. The reaction tube was evacuated and filled with argon (this operation was repeated three times). The diazo ester derivative 2a (26.4 mg, 0.15 mmol, 1.5 equiv) was dissolved in 1 ml of redistilled dichloromethane and injected into the reaction tube with a syringe, and stirred at 25 °C for 15 min. The reaction solution was evaporated to dryness under reduced pressure, and the residue was purified by column chromatography (silica gel, eluent: EtOAc / PE=1:20-1:10) to give a colorless oil (22.5 mg, 70%, 93% ee), enantioselectivity: 93% ee; HPLC conditions: DaicelChiralpak IA column, n-hexane / i-PrOH=90 / 10, flow rate=1 mL / min, I=215 nm, t R =5.13min(major)and5.56min(minor).[α] D 20 :-100.2 (c 0.25, CH2Cl2; 93%ee). 1 H NMR (400MHz, CDCl3) δ7.53 (d, J = 8.0 Hz, 1H), 7.41-7.34 (m, 3H), 7.34-7.25 (m, 2H), 7.09 (s, 1H), 6.95 (d, J = 9. 4Hz,1H),6.80(s,1H),6.19(s,1H),3.79(s,3H),3.19-3.06(m,1H),2.46(s,3H),1.29(dd,J=7.8,6.9Hz,6H). 13 CNMR (100MHz, CDCl3) δ170.4,137.6,135.1,131.7,129.0,128.8,128.0,125.6,123.7, 121.2,121.1,119.5,109.1,61.7,52.8,25.7,23.30,23.25,22.0.HRMS(ESI)m / z:[M+H] +Calcd for C 21 H 24 NO2322.1802; Found 322.1799.

[0141] Embodiment 42:

[0142]

[0143] Rh2(Oct)4 (0.08 mg, 0.0001 mmol, 0.001 equiv) and chiral phosphoric acid C1 (1.4 mg, 0.0025 mmol, 0.025 equiv) were added to a dry reaction tube, and then the indole derivative 1p (23.7 mg, 0.1 mmol, 1 equiv) was dissolved in 1 ml of redistilled dichloromethane. The reaction tube was evacuated and filled with argon (this operation was repeated three times). The diazo ester derivative 2a (26.4 mg, 0.15 mmol, 1.5 equiv) was dissolved in 1 ml of redistilled dichloromethane and injected into the reaction tube with a syringe, and stirred at 25°C for 15 min. The reaction solution was evaporated to dryness under reduced pressure, and the residue was purified by column chromatography (silica gel, eluent: EtOAc / PE=1:20-1:10) to give a colorless oil (36.6 mg, 95%, 96% ee), enantioselectivity: 96% ee; HPLC conditions: DaicelChiralpak IA column, n-hexane / i-PrOH=90 / 10, flow rate=1 mL / min, I=215 nm, t R =4.64min(major)and5.59min(minor).[α] D 20 :-132.3 (c 0.35, CH2Cl2; 96%ee). 1 H NMR (400MHz, CDCl3) δ7.49 (d, J = 8.4Hz, 1H), 7.45 (s, 1H), 7.40-7.38 (m, 3H), 7.31-7.29 (m, 2H), 7.23 -7.20(m,1H),6.86(s,1H),6.13(s,1H),3.81(s,3H),3.19-3.03(m,1H),1.28(dd,J=9.5,6.9Hz,6H). 13 C NMR (100MHz, CDCl3) δ170.1,137.9,134.5,129.2,129.1,128.0,126.6,124.0,122. 6,122.5,121.1,115.6,112.2,61.8,53.0,25.5,23.24,23.20.HRMS(ESI)m / z:[M+H]+ Calcd for C 20 H 21 NO2386.0750;Found386.0749.

[0144] Embodiment 43:

[0145]

[0146] Rh2(OPiv)4 (0.06 mg, 0.0001 mmol, 0.001 equiv) and chiral phosphoric acid C5 (1.75 mg, 0.0025 mmol, 0.025 equiv) were added to a dry reaction tube, and then the indole derivative 1a (15.9 mg, 0.1 mmol, 1 equiv) was dissolved in 1 ml of redistilled toluene. The reaction tube was evacuated and filled with argon (this operation was repeated three times). The diazo ester derivative 2q (58.0 mg, 0.25 mmol, 2.5 equiv) was dissolved in 1 ml of redistilled toluene and injected into the reaction tube with a syringe, and stirred at -20°C for 15 min. The reaction solution was evaporated to dryness under reduced pressure, and the residue was purified by column chromatography (silica gel, eluent: EtOAc / PE=1:100-1:30) to give a white solid, melting point: 57-59°C (30.2 mg, 83%, 97% ee), enantioselectivity: 97% ee; HPLC conditions: Daicel Chiralpak OD-H column, n-hexane / i-PrOH=99 / 1, flow rate=0.8 mL / min, I=215 nm, t R =9.07min(major)and9.83min(minor).[α] D 20 :+24.8 (c 0.25, CH2Cl2; 97%ee). 1 HNMR(400MHz, CDCl3)δ7.62(d,J=7.8Hz,1H),7.26(d,J=8.2Hz,1H),7.18- 7.05(m,3H),7.02(s,1H),7.00(s,2H),5.21(d,J=12.0Hz,1H),5.17(d,J=1 2.0Hz, 1H), 4.85 (dd, J=8.9, 6.6Hz, 1H), 3.18 (hept, J=6.8Hz, 1H), 2.32-2. 18(m,7H),2.18-2.07(m,1H),1.33(d,J=6.8Hz,6H),0.88(t,J=7.4Hz,3H). 13C NMR (100MHz, CDCl3) δ171.3,138.5,137.3,131.5,129.0,128.4,127.5,124.0,121.7,120.6,1 19.7,119.1,109.2,62.2,59.8,25.63,25.55,23.44,23.42,19.6,10.9.HRMS(ESI)m / z:[M+H] + Calcd for C 24 H 30 NO2364.2271; Found364.2271.

[0147] Embodiment 44:

[0148]

[0149] Rh2(OPiv)4 (0.06 mg, 0.0001 mmol, 0.001 equiv) and chiral phosphoric acid C5 (1.75 mg, 0.0025 mmol, 0.025 equiv) were added to a dry reaction tube, and then the indole derivative 1a (15.9 mg, 0.1 mmol, 1 equiv) was dissolved in 1 ml of redistilled toluene. The reaction tube was evacuated and filled with argon (this operation was repeated three times). The diazo ester derivative 2r (68.3 mg, 0.25 mmol, 2.5 equiv) was dissolved in 1 ml of redistilled toluene and injected into the reaction tube with a syringe, and stirred at -20°C for 15 min. The reaction solution was evaporated to dryness under reduced pressure, and the residue was purified by column chromatography (silica gel, eluent: EtOAc / PE=1:100-1:30) to give a white solid, melting point: 75-77°C (34.7 mg, 86%, 98% ee), enantioselectivity: 98% ee; HPLC conditions: Daicel Chiralpak IB column, n-hexane / i-PrOH=99 / 1, flow rate=0.8 mL / min, I=215 nm, t R =7.00min(major)and7.44min(minor).[α] D 20 :+29.2(c 0.20,CH2Cl2; 98%ee).[α] D 25 :+29.2(c 0.20,CH2Cl2). 1H NMR (400MHz, CDCl3) δ7.62 (d, J = 7.8Hz, 1H), 7.34-7.25 (m, 3H), 7.24-7.12 (m ,2H),7.11-7.05(m,1H),7.04(s,1H),5.42(d,J=11.8Hz,1H),5.37(d,J=11. 8Hz,1H),4.89(dd,J=9.0,6.4Hz,1H),3.19(hept,J=6.8Hz,1H),2.34-2.21( m,1H),2.21-2.06(m,1H),1.34(dd,J=6.8,2.9Hz,6H),0.89(t,J=7.4Hz,3H). 13 C NMR (100MHz, CDCl3) δ170.7,137.3,137.1,131.0,130.8,128.6,127.5,124.0,121.7,12 0.7,119.7,119.1,109.3,62.2,59.5,25.8,25.6,23.5,23.4,10.9.HRMS(ESI)m / z:[M+H] + Calcdfor C 22 H 24 Cl2NO2404.1179; Found 404.1181.

[0150] Embodiment 45:

[0151]

[0152] Rh2(OPiv)4 (0.06 mg, 0.0001 mmol, 0.001 equiv) and chiral phosphoric acid C5 (1.75 mg, 0.0025 mmol, 0.025 equiv) were added to a dry reaction tube, and then the indole derivative 1a (15.9 mg, 0.1 mmol, 1 equiv) was dissolved in 1 ml of redistilled toluene. The reaction tube was evacuated and filled with argon (this operation was repeated three times). The diazo ester derivative 2s (75.3 mg, 0.25 mmol, 2.5 equiv) was dissolved in 1 ml of redistilled toluene and injected into the reaction tube with a syringe, and stirred at -20°C for 15 min. The reaction solution was evaporated to dryness under reduced pressure, and the residue was purified by column chromatography (silica gel, eluent: EtOAc / PE=1:100-1:30) to give a colorless viscous oil (25.9 mg, 60%, 96% ee), enantioselectivity: 96% ee; HPLC conditions: DaicelChiralpak ID column, n-hexane / i-PrOH=99 / 1, flow rate=0.8 mL / min, I=215 nm, tR = 5.99分钟(次要)和6.45分钟(主要)。[α] D 20 :+10.5(c 0.15,二氯甲烷;96%ee)。 1 1H NMR(400MHz,CDCl3)δ7.62(d,J = 7.8Hz,1H),7.36 - 7.26(m,3H),7.26 - 7.20(m,1H),7.16(t,J = 7.4Hz,1H),7.08(t,J = 7.4Hz,1H),7.04(s,1H),5.42(d,J = 11.8Hz,1H),5.37(d,J = 11.8Hz,1H),4.97(dd,J = 8.8,6.7Hz,1H),3.19(七重峰,J = 6.8Hz,1H),2.32 - 2.18(m,1H),2.18 - 2.04(m,1H),1.41 - 1.16(m,10H),0.84(t,J = 7.1Hz,3H)。 13 13C NMR(100MHz,CDCl3)δ171.0,137.3,137.1,131.0,130.8,128.6,127.5,123.9,121.7 120.7,119.6,119.1,109.3,62.2,58.0,32.0,28.2,25.6,23.5,22.3,13.9。高分辨质谱(ESI)m / z:[M + H] + 计算值为C 24 H 28 Cl2NO2 432.1492;实测值432.1494。

[0153] Example 46:

[0154]

[0155] Rh2(OPiv)4 (0.06 mg, 0.0001 mmol, 0.001 equiv) and chiral phosphoric acid C5 (1.75 mg, 0.0025 mmol, 0.025 equiv) were added to a dry reaction tube, and then the indole derivative 1a (15.9 mg, 0.1 mmol, 1 equiv) was dissolved in 1 ml of redistilled toluene. The reaction tube was evacuated and filled with argon (this operation was repeated three times). The diazo ester derivative 2t (78.8 mg, 0.25 mmol, 2.5 equiv) was dissolved in 1 ml of redistilled toluene and injected into the reaction tube with a syringe, and stirred at -20°C for 15 min. The reaction solution was evaporated to dryness under reduced pressure, and the residue was purified by column chromatography (silica gel, eluent: EtOAc / PE=1:100-1:30) to give a colorless viscous oil (24.6 mg, 55%, 97% ee), enantioselectivity: 97% ee; HPLC conditions: DaicelChiralpak ID column, n-hexane / i-PrOH=99 / 1, flow rate=0.8 mL / min, I=215 nm, t R =5.63min(minor)and 6.00min(major).[α] D 20 :+16.9 (c 0.30, CH2Cl2; 97%ee). 1 H NMR (400MHz, CDCl3) δ7.62 (d, J = 7.8Hz, 1H), 7.35-7.27 (m, 3H), 7.25-7.20 (m, 1H), 7.19-7.13 (m, 1H ),7.11-7.06(m,1H),7.05(s,1H),5.42(d,J=11.8Hz,1H),5.37(d,J=11.8Hz,1H),4.93(dd,J=8.6, 6.8Hz,1H),3.19(hept,J=6.8Hz,1H),2.32-2.18(m,1H),2.16-2.04(m,1H),1.55(hept,J=6.6Hz,1 H),1.34(dd,J=6.8,3.2Hz,6H),1.24-1.17(m,1H),1.15-1.06(m,1H),0.84(dd,J=6.6,1.5Hz,6H). 13C NMR (100MHz, CDCl3) δ171.0,137.3,137.1,131.0,130.8,128.6,127.5,124.0,121.7,120.6,1 19.6,119.1,109.3,62.1,58.3,35.1,30.3,27.8,25.6,23.5,22.6,22.4.HRMS(ESI)m / z:[M+H] + Calcd for C 25 H 30 Cl2NO2446.1648; Found446.1649.

[0156] Embodiment 47:

[0157]

[0158] Rh2(OPiv)4 (0.06 mg, 0.0001 mmol, 0.001 equiv) and chiral phosphoric acid C5 (1.75 mg, 0.0025 mmol, 0.025 equiv) were added to a dry reaction tube, and then the indole derivative 1a (15.9 mg, 0.1 mmol, 1 equiv) was dissolved in 1 ml of redistilled toluene. The reaction tube was evacuated and filled with argon (this operation was repeated three times). The diazo ester derivative 2u (164.5 mg, 0.25 mmol, 2.5 equiv) was dissolved in 1 ml of redistilled toluene and injected into the reaction tube with a syringe, and stirred at -20°C for 15 min. The reaction solution was evaporated to dryness under reduced pressure, and the residue was purified by column chromatography (silica gel, eluent: EtOAc / PE=1:100-1:30) to give a colorless viscous oil (33.1 mg, 72%, 97% ee), enantioselectivity: 97% ee; HPLC conditions: DaicelChiralpak OD-H column, n-hexane / i-PrOH=99 / 1, flow rate=1 mL / min, I=215 nm, t R =5.77min(minor)and 6.20min(major).[α] D 20 :+11.2 (c 0.10, CH2Cl2; 97%ee). 11H NMR (400 MHz, CDCl3) δ 7.66 - 7.60 (m, 1H), 7.37 - 7.28 (m, 3H), 7.27 - 7.21 (m, 1H), 7.20 - 7.14 (m, 1H), 7.12 - 7.07 (m, 1H), 7.05 (s, 1H), 5.43 (d, J = 11.8 Hz, 1H), 5.38 (d, J = 11.8 Hz, 1H), 4.98 (dd, J = 8.8, 6.6 Hz, 1H), 3.26 - 3.13 (m, 1H), 2.29 - 2.18 (m, 1H), 2.18 - 2.06 (m, 1H), 1.35 (dd, J = 6.9, 3.2 Hz, 6H), 1.32 - 1.17 (m, 8H), 0.84 (t, J = 6.9 Hz, 3H). 13 13C NMR (100 MHz, CDCl3) δ 171.0, 137.3, 137.1, 131.0, 130.8, 128.6, 127.5, 124.0, 121.7, 120.7, 119.6, 119.1, 109.3, 62.1, 58.1, 32.3, 31.6, 28.9, 26.1, 25.7, 23.5, 22.6, 14.1. HRMS (ESI) m / z: [M + H] + Calcd for C 26 H 32 Cl2NO2 460.1805; Found 460.1810.

[0159] Example 48:

[0160]

[0161] Rh2(OPiv)4 (0.06 mg, 0.0001 mmol, 0.001 equiv) and chiral phosphoric acid C5 (1.75 mg, 0.0025 mmol, 0.025 equiv) were added to a dry reaction tube, and then the indole derivative 1a (15.9 mg, 0.1 mmol, 1 equiv) was dissolved in 1 ml of redistilled toluene. The reaction tube was evacuated and filled with argon (this operation was repeated three times). The diazo ester derivative 2v (79.3 mg, 0.25 mmol, 2.5 equiv) was dissolved in 1 ml of redistilled toluene and injected into the reaction tube with a syringe, and stirred at -20°C for 15 min. The reaction solution was evaporated to dryness under reduced pressure, and the residue was purified by column chromatography (silica gel, eluent: EtOAc / PE=1:80-1:10) to give a white solid, melting point: 73-74°C (22.4 mg, 50%, 96% ee), enantioselectivity: 96% ee; HPLC conditions: Daicel Chiralpak ID column, n-hexane / i-PrOH=99 / 1, flow rate=1 mL / min, I=215 nm, t R =9.34min(minor)and10.26min(major).[α] D 20 :+10.2(c 0.10, CH2Cl2; 96%ee). 1 H NMR (400MHz, CDCl3) δ7.54 (d, J = 7.8Hz, 1H), 7.27-7.19 (m, 3H), 7.19-7.13 (m, 1H), 7.12-7 .05(m,1H),7.00(t,J=7.4Hz,1H),6.96(s,1H),5.34(d,J=11.8Hz,1H),5.30(d,J=11.8Hz ,1H),4.94(dd,J=9.3,6.3Hz,1H),3.30-3.21(m,2H),3.19(s,3H),3.11(hept,J=6.9Hz,1 H),2.32-2.20(m,1H),2.19-2.08(m,1H),1.50-1.36(m,2H),1.26(dd,J=6.9,3.1Hz,6H). 13 C NMR (100MHz, CDCl3) δ170.7,137.2,137.1,130.9,130.8,128.5,127.6,124.1,121.7,120.7,1 19.7,119.1,109.3,71.8,62.2,58.7,57.9,29.1,26.2,25.6,23.5,23.4.HRMS(ESI)m / z:[M+H]+ Calcd for C 24 H 28 Cl2NO3448.1441; Found448.1443.

[0162] Embodiment 49:

[0163]

[0164] Rh2(OPiv)4 (0.06 mg, 0.0001 mmol, 0.001 equiv) and chiral phosphoric acid C5 (1.75 mg, 0.0025 mmol, 0.025 equiv) were added to a dry reaction tube, and then the indole derivative 1a (15.9 mg, 0.1 mmol, 1 equiv) was dissolved in 1 ml of redistilled toluene. The reaction tube was evacuated and filled with argon (this operation was repeated three times). The diazo ester derivative 2w (104.2 mg, 0.25 mmol, 2.5 equiv) was dissolved in 1 ml of redistilled toluene and injected into the reaction tube with a syringe, and stirred at -20°C for 15 min. The reaction solution was evaporated to dryness under reduced pressure, and the residue was purified by column chromatography (silica gel, eluent: EtOAc / PE=1:80-1:10) to give a colorless viscous oil (37.2 mg, 68%, 96% ee), enantioselectivity: 96% ee; HPLC conditions: DaicelChiralpak ID column, n-hexane / i-PrOH=99 / 1, flow rate=0.8 mL / min, I=215 nm, t R =5.55min(minor)and 5.83min(major).[α] D 20 :+4.5 (c 0.10, CH2Cl2; 96%ee). 1 H NMR(400MHz, CDCl3) δ7.63(d,J=7.8Hz,1H),7.39-7.20(m,4H),7.17(t,J=7.4Hz,1H),7.09 (t,J=7.4Hz,1H),7.06(s,1H),5.44(d,J=11.8Hz,1H),5.38(d,J=11.8Hz,1H),5.05(dd,J=9 .7,5.8Hz,1H),3.58(t,J=6.0Hz,2H),3.20(hept,J=6.8Hz,1H),2.42-2.29(m,1H),2.29-2. 16(m,1H),1.54-1.41(m,2H),1.35(d,J=6.8Hz,6H),0.86(s,9H),0.01(s,3H),0.00(s,3H).13 C NMR (100MHz, CDCl3) δ170.9,137.3,137.1,131.0,130.8,128.5,127.6,124.1,121.7,120.7,119.7,1 19.1,109.3,62.23,62.15,57.8,29.1,28.9,26.0,25.7,23.5,23.4,18.4,-5.3.HRMS(ESI)m / z:[M+H] + Calcd for C 29 H 40 Cl2NO3Si 548.2149; Found548.2151.

[0165] Embodiment 50:

[0166]

[0167] Rh2(OPiv)4 (0.06 mg, 0.0001 mmol, 0.001 equiv) and chiral phosphoric acid C5 (1.75 mg, 0.0025 mmol, 0.025 equiv) were added to a dry reaction tube, and then the indole derivative 1a (15.9 mg, 0.1 mmol, 1 equiv) was dissolved in 1 ml of redistilled toluene. The reaction tube was evacuated and filled with argon (this operation was repeated three times). The diazo ester derivative 2x (83.8 mg, 0.25 mmol, 2.5 equiv) was dissolved in 1 ml of redistilled toluene and injected into the reaction tube with a syringe, and stirred at -20°C for 15 min. The reaction solution was evaporated to dryness under reduced pressure, and the residue was purified by column chromatography (silica gel, eluent: EtOAc / PE=1:80-1:10) to give a colorless viscous oil (29.8 mg, 64%, 96% ee), enantioselectivity: 96% ee; HPLC conditions: DaicelChiralpak ID column, n-hexane / i-PrOH=99 / 1, flow rate=0.8 mL / min, I=215 nm, t R =5.68min(major)and 6.17min(minor).[α] D 20 :+24.6 (c 0.20, CH2Cl2; 96%ee). 1H NMR (400MHz, CDCl3) δ7.59 (d, J=7.7Hz, 1H), 7.34-7.22 (m, 3H), 7.22-7.11 (m, 5H), 7.11-7.00 (m, 4H), 5.36 (s, 2H), 5.19 (t, J= 7.6Hz, 1H), 3.54 (dd, J=13.7, 7.6Hz, 1H), 3.33 (dd, J=13.7, 7.6Hz, 1H), 3.17 (hept, J=6.8Hz, 1H), 1.32 (dd, J=6.8, 5.2Hz, 6H). 13 C NMR (100MHz, CDCl3) δ170.0,137.1,136.9,136.3,130.80,130.75,129.1,128.6,128.5,127.6,127.1 ,124.0,121.7,121.1,119.6,119.1,109.4,62.2,59.9,38.5,25.6,23.5,23.4.HRMS(ESI)m / z:[M+H] + Calcd for C 27 H 26 Cl2NO2466.1335; Found 466.1335.

[0168] Embodiment 51:

[0169]

[0170] Rh2(OPiv)4 (0.06 mg, 0.0001 mmol, 0.001 equiv) and chiral phosphoric acid C5 (1.75 mg, 0.0025 mmol, 0.025 equiv) were added to a dry reaction tube, and then the indole derivative 1a (15.9 mg, 0.1 mmol, 1 equiv) was dissolved in 1 ml of redistilled toluene. The reaction tube was evacuated and filled with argon (this operation was repeated three times). The diazo ester derivative 2y (74.7 mg, 0.25 mmol, 2.5 equiv) was dissolved in 1 ml of redistilled toluene and injected into the reaction tube with a syringe, and stirred at -20°C for 15 min. The reaction solution was evaporated to dryness under reduced pressure, and the residue was purified by column chromatography (silica gel, eluent: EtOAc / PE=1:80-1:10) to give a colorless viscous oil (27.2 mg, 63%, 98% ee), enantioselectivity: 98% ee; HPLC conditions: DaicelChiralpak IE column, n-hexane / i-PrOH=99 / 1, flow rate=0.8 mL / min, I=215 nm, t R= 6.74 分钟(主峰)和 7.43 分钟(次峰)。[α] D 20 :+1.2(c 0.30,二氯甲烷;98%ee)。 1 1H NMR(400MHz,CDCl3)δ7.62(d,J = 7.8Hz,1H),7.37 - 7.30(m,2H),7.29 - 7.20(m,2H),7.19 - 7.12(m,1H),7.11 - 7.05(m,1H),7.02(s,1H),5.80 - 5.67(m,1H),5.43(d,J = 11.8Hz,1H),5.37(d,J = 11.8Hz,1H),5.08 - 4.90(m,3H),3.19(七重峰,J = 6.9Hz,1H),2.40 - 2.17(m,2H),2.07 - 1.89(m,2H),1.34(dd,J = 6.9,3.6Hz,6H)。 13 13C NMR(100MHz,CDCl3)δ170.8,137.2,137.1,136.6,130.93,130.85,128.6,127.6,124.1,121.7,120.7,119.7,119.1,116.5,109.4,62.2,57.2,31.4,30.0,25.6,23.4。高分辨质谱(电喷雾电离)m / z:[M + H] + 计算值为 C 24 H 26 Cl2NO2 430.1335;实测值 430.1334。

[0171] Example 52:

[0172]

[0173] Rh2(OPiv)4 (0.06 mg, 0.0001 mmol, 0.001 equiv) and chiral phosphoric acid C5 (1.75 mg, 0.0025 mmol, 0.025 equiv) were added to a dry reaction tube, and then the indole derivative 1a (15.9 mg, 0.1 mmol, 1 equiv) was dissolved in 1 ml of redistilled toluene. The reaction tube was evacuated and filled with argon (this operation was repeated three times). The diazo ester derivative 2z (77.7 mg, 0.25 mmol, 2.5 equiv) was dissolved in 1 ml of redistilled toluene and injected into the reaction tube with a syringe, and stirred at -20°C for 15 min. The reaction solution was evaporated to dryness under reduced pressure, and the residue was purified by column chromatography (silica gel, eluent: EtOAc / PE=1:80-1:10) to give a colorless viscous oil (26.5 mg, 60%, 97% ee), enantioselectivity: 97% ee; HPLC conditions: DaicelChiralpak ID column, n-hexane / i-PrOH=99 / 1, flow rate=1 mL / min, I=215 nm, t R =5.18min(major)and 5.48min(minor).[α] D 20 :+55.2 (c 0.40, CH2Cl2; 97%ee). 1 H NMR (400MHz, CDCl3) δ7.61 (d, J = 7.8Hz, 1H), 7.34-7.27 (m, 3H), 7.26-7.19 (m, 1 H),7.19-7.13(m,1H),7.12-7.04(m,1H),6.97(s,1H),5.46-5.36(m,2H),5.22 (dd,J=9.7,5.6Hz,1H),3.17(hept,J=6.9Hz,1H),2.45-2.23(m,2H),2.20-2.0 8(m,1H),2.01-1.89(m,1H),1.77(t,J=2.5Hz,3H),1.33(dd,J=6.9,3.7Hz,6H). 13 CNMR (100MHz, CDCl3) δ170.6,137.3,137.1,130.9,130.8,128.5,127.6,124.3,121.7,120.8,1 19.6,119.1,109.6,77.1,62.3,56.9,31.4,25.6,23.42,23.41,15.7,3.7.HRMS(ESI)m / z:[M+H] + Calcd for C 25 H 26Cl2NO2442.1335; Found 442.1336.

[0174] Embodiment 53:

[0175]

[0176] Rh2(OPiv)4 (0.06 mg, 0.0001 mmol, 0.001 equiv) and chiral phosphoric acid C5 (1.75 mg, 0.0025 mmol, 0.025 equiv) were added to a dry reaction tube, and then the indole derivative 1b (13.1 mg, 0.1 mmol, 1 equiv) was dissolved in 1 ml of redistilled toluene. The reaction tube was evacuated and filled with argon (this operation was repeated three times). The diazo ester derivative 2r (68.2 mg, 0.25 mmol, 2.5 equiv) was dissolved in 1 ml of redistilled toluene and injected into the reaction tube with a syringe, and stirred at -20°C for 15 min. The reaction solution was evaporated to dryness under reduced pressure, and the residue was purified by column chromatography (silica gel, eluent: EtOAc / PE=1:80-1:25) to give a colorless viscous oil (19.9 mg, 53%, 98% ee), enantioselectivity: 98% ee; HPLC conditions: DaicelChiralpak IB column, n-hexane / i-PrOH=99 / 1, flow rate=0.9 mL / min, I=215 nm, t R =10.56min(major)and 11.68min(minor).[α] D 20 :+12.8 (c 0.10, CH2Cl2; 98%ee). 1 H NMR (400MHz, CDCl3) δ7.55(d,J=7.8Hz,1H),7.35-7.20(m,4H),7.19-7.14(m,1H),7.13-7.06(m,2H),5.44(d,J=11.8Hz ,1H),5.36(d,J=11.8Hz,1H),4.89(dd,J=9.3,6.2Hz,1H),2.36-2.21(m,4H),2.21-2.07(m,1H),0.89(t,J=7.4Hz,3H). 13 C NMR (100MHz, CDCl3) δ170.9,137.1,137.0,131.0,130.8,129.0,128.6,123.0,121 .7,119.2,119.1,111.8,109.1,62.2,59.4,25.8,10.9,9.9.HRMS(ESI)m / z:[M+H]+ Calcd for C 20 H 20 Cl2NO2376.0866; Found 376.0869.

[0177] Embodiment 54:

[0178]

[0179] Rh2(OPiv)4 (0.06 mg, 0.0001 mmol, 0.001 equiv) and chiral phosphoric acid C5 (1.75 mg, 0.0025 mmol, 0.025 equiv) were added to a dry reaction tube, and then the indole derivative 1c (14.5 mg, 0.1 mmol, 1 equiv) was dissolved in 1 ml of redistilled toluene. The reaction tube was evacuated and filled with argon (this operation was repeated three times). The diazo ester derivative 2r (68.2 mg, 0.25 mmol, 2.5 equiv) was dissolved in 1 ml of redistilled toluene and injected into the reaction tube with a syringe, and stirred at -20°C for 15 min. The reaction solution was evaporated to dryness under reduced pressure, and the residue was purified by column chromatography (silica gel, eluent: EtOAc / PE=1:80-1:10) to give a colorless viscous oil (23.8 mg, 61%, 98% ee), enantioselectivity: 98% ee; HPLC conditions: DaicelChiralpak IB column, n-hexane / i-PrOH=99 / 1, flow rate=0.9 mL / min, I=215 nm, t R =8.56min(major)and 9.44min(minor).[α] D 20 :+8.3 (c 0.15, CH2Cl2; 98%ee). 1 H NMR (400MHz, CDCl3) δ7.57(d,J=7.8Hz,1H),7.35-7.26(m,3H),7.25-7.13(m,2H),7.12-7.04(m,2H),5.43(d,J=11.8Hz,1H),5.37(d,J=11.8H z,1H),4.90(dd,J=9.2,6.3Hz,1H),2.77(q,J=7.5Hz,2H),2.35-2.22(m,1H),2.22-2.07(m,1H),1.31(t,J=7.5Hz,3H),0.89(t,J=7.4Hz,3H). 13C NMR (100MHz, CDCl3) δ170.9,137.2,137.1,131.0,130.8,128.5,128.1,121.9,121.7,1 19.22,119.15,118.8,109.2,62.2,59.5,25.8,18.5,14.5,10.9.HRMS(ESI)m / z:[M+H] + Calcd for C 21 H 22 Cl2NO2390.1022; Found390.1024.

[0180] Embodiment 55:

[0181]

[0182] Rh2(OPiv)4 (0.06 mg, 0.0001 mmol, 0.001 equiv) and chiral phosphoric acid C5 (1.75 mg, 0.0025 mmol, 0.025 equiv) were added to a dry reaction tube, and then the indole derivative 1d (17.3 mg, 0.1 mmol, 1 equiv) was dissolved in 1 ml of redistilled toluene. The reaction tube was evacuated and filled with argon (this operation was repeated three times). The diazo ester derivative 2r (68.2 mg, 0.25 mmol, 2.5 equiv) was dissolved in 1 ml of redistilled toluene and injected into the reaction tube with a syringe, and stirred at -20°C for 15 min. The reaction solution was evaporated to dryness under reduced pressure, and the residue was purified by column chromatography (silica gel, eluent: EtOAc / PE=1:80-1:10) to give a colorless viscous oil (25.9 mg, 62%, 99% ee), enantioselectivity: 99% ee; HPLC conditions: DaicelChiralpak IB column, n-hexane / i-PrOH=99 / 1, flow rate=0.9 mL / min, I=215 nm, t R =6.77min(major)and 7.18min(minor).[α] D 20 :+6.6 (c 0.25, CH2Cl2; 99%ee). 1H NMR (400MHz, CDCl3) δ7.49(d,J=7.6Hz,1H),7.28-7.13(m,4H),7.11-7.05(m,1H),7.04-6.99(m,1H),6.98(s,1H),5.35(d,J=11.8Hz,1H),5.30( d,J=11.8Hz,1H),4.84(dd,J=9.4,6.1Hz,1H),2.52(d,J=7.0Hz,2H),2.2 8-2.15(m,1H),2.14-2.02(m,1H),1.95-1.83(m,1H),0.90-0.77(m,9H). 13 C NMR (100MHz, CDCl3) δ170.9,137.1,131.0,130.8,128.7,128.6,123.4,121.6,119.5,119 .1,115.9,109.1,62.2,59.5,34.7,29.2,25.8,22.83,22.82,10.8.HRMS(ESI)m / z:[M+H] + Calcd for C 23 H 26 Cl2NO2418.1335; Found418.1335.

[0183] Embodiment 56:

[0184]

[0185] Rh2(OPiv)4 (0.06 mg, 0.0001 mmol, 0.001 equiv) and chiral phosphoric acid C5 (1.75 mg, 0.0025 mmol, 0.025 equiv) were added to a dry reaction tube, and then the indole derivative 1e (17.3 mg, 0.1 mmol, 1 equiv) was dissolved in 1 ml of redistilled toluene. The reaction tube was evacuated and filled with argon (this operation was repeated three times). The diazo ester derivative 2r (68.2 mg, 0.25 mmol, 2.5 equiv) was dissolved in 1 ml of redistilled toluene and injected into the reaction tube with a syringe, and stirred at -20°C for 15 min. The reaction solution was evaporated to dryness under reduced pressure, and the residue was purified by column chromatography (silica gel, eluent: EtOAc / PE=1:80-1:10) to give a colorless viscous oil (29.3 mg, 70%, 96% ee), enantioselectivity: 96% ee; HPLC conditions: DaicelChiralpak OD-H column, n-hexane / i-PrOH=99 / 1, flow rate=0.8 mL / min, I=215 nm, t R= 7.26 min (major) and 8.18 min (minor). [α] D 20 : +12.2 (c 0.10, CH2Cl2; 96% ee). 1 1H NMR (400 MHz, CDCl3) δ 7.79 (d, J = 7.8 Hz, 1H), 7.35 - 7.27 (m, 3H), 7.25 - 7.19 (m, 1H), 7.18 - 7.12 (m, 1H), 7.11 - 7.04 (m, 1H), 7.01 (s, 1H), 5.42 (d, J = 11.8 Hz, 1H), 5.38 (d, J = 11.8 Hz, 1H), 4.90 (dd, J = 8.9, 6.5 Hz, 1H), 2.35 - 2.22 (m, 1H), 2.21 - 2.07 (m, 1H), 1.43 (s, 9H), 0.90 (t, J = 7.4 Hz, 3H). 13 13C NMR (100 MHz, CDCl3) δ 170.8, 137.9, 137.1, 131.0, 130.8, 128.5, 126.7, 126.6, 121.5, 121.3, 120.7, 118.8, 109.4, 62.1, 59.5, 31.8, 30.9, 25.7, 10.9. HRMS (ESI) m / z: [M+H] + Calcd for C 23 H 26 Cl2NO2 418.1335; Found 418.1338.

[0186] Example 57:

[0187]

[0188] Rh2(OPiv)4 (0.06 mg, 0.0001 mmol, 0.001 equiv) and chiral phosphoric acid C5 (1.75 mg, 0.0025 mmol, 0.025 equiv) were added to a dry reaction tube, and then the indole derivative 1f (18.5 mg, 0.1 mmol, 1 equiv) was dissolved in 1 ml of redistilled toluene. The reaction tube was evacuated and filled with argon (this operation was repeated three times). The diazo ester derivative 2r (68.2 mg, 0.25 mmol, 2.5 equiv) was dissolved in 1 ml of redistilled toluene and injected into the reaction tube with a syringe, and stirred at -20°C for 15 min. The reaction solution was evaporated to dryness under reduced pressure, and the residue was purified by column chromatography (silica gel, eluent: EtOAc / PE=1:80-1:10) to give a colorless viscous oil (25.8 mg, 60%, 98% ee), enantioselectivity: 98% ee; HPLC conditions: DaicelChiralpak OD-H column, n-hexane / i-PrOH=99 / 1, flow rate=0.9 mL / min, I=215 nm, t R =6.64min(major)and 7.36min(minor).[α] D 20 :+13.1 (c 0.20, CH2Cl2; 98%ee). 1 H NMR (400MHz, CDCl3) δ7.61 (d, J = 7.9Hz, 1H), 7.28-7.19 (m, 3H), 7.18-7.11 (m, 1H), 7.10-7 .03(m,1H),7.01-6.93(m,2H),6.02(dd,J=17.4,10.5Hz,1H),5.35(d,J=11.8Hz,1H),5.30 (d,J=11.8Hz,1H),4.97(dd,J=17.4,1.4Hz,1H),4.92(dd,J=10.5,1.4Hz,1H),4.83(dd,J= 9.0,6.5Hz,1H),2.27-2.16(m,1H),2.13-2.01(m,1H),1.41(s,6H),0.82(t,J=7.4Hz,3H). 13 C NMR (100MHz, CDCl3) δ170.8,147.9,137.8,137.1,130.93,130.85,128.5,126.7,123.8,121.7,12 1.6,121.5,118.9,110.7,109.3,62.2,59.5,37.7,28.23,28.16,25.8,10.9.HRMS(ESI)m / z:[M+H]+ Calcd for C 24 H 26 Cl2NO2430.1335; Found430.1338.

[0189] Embodiment 58:

[0190]

[0191] Rh2(OPiv)4 (0.06 mg, 0.0001 mmol, 0.001 equiv) and chiral phosphoric acid C5 (1.75 mg, 0.0025 mmol, 0.025 equiv) were added to a dry reaction tube, and then 1 g of the indole derivative (20.3 mg, 0.1 mmol, 1 equiv) was dissolved in 1 ml of redistilled toluene. The reaction tube was evacuated and filled with argon (this operation was repeated three times). The diazo ester derivative 2r (68.2 mg, 0.25 mmol, 2.5 equiv) was dissolved in 1 ml of redistilled toluene and injected into the reaction tube with a syringe, and stirred at -20°C for 15 min. The reaction solution was evaporated to dryness under reduced pressure, and the residue was purified by column chromatography (silica gel, eluent: EtOAc / PE=1:80-1:10) to give a white solid, melting point: 79-81°C (26.0 mg, 58%, 97% ee), enantioselectivity: 97% ee; HPLC conditions: Daicel Chiralpak ID column, n-hexane / i-PrOH=80 / 20, flow rate=1.5 mL / min, I=215 nm, t R =6.62min(major)and8.06min(minor).[α] D 20 :+6.2(c 0.10, CH2Cl2; 97%ee). 1 HNMR (400MHz, CDCl3) δ7.62 (d, J = 7.7Hz, 1H), 7.37-7.23 (m, 5H), 7.19 (t, J = 7. 4Hz,1H),7.13(t,J=7.4Hz,1H),5.45(d,J=11.8Hz,1H),5.38(d,J=11.8Hz,1H) ,4.92(dd,J=8.9,6.5Hz,1H),4.15(q,J=7.1Hz,2H),3.84-3.68(m,2H),2.36-2 .24(m,1H),2.2.24-2.10(m,1H),1.25(t,J=7.1Hz,3H),0.91(t,J=7.3Hz,3H). 13C NMR (100MHz, CDCl3) δ172.0,170.7,137.1,136.9,130.92,130.87,128.6,128.0,124.5,122. 1,119.8,119.4,109.4,108.7,62.3,60.8,59.7,31.7,25.7,14.4,10.9.HRMS(ESI)m / z:[M+H] + Calcd for C 23 H 24 Cl2NO4448.1077; Found 448.1081.

[0192] Embodiment 59:

[0193]

[0194] Rh2(OPiv)4 (0.31 mg, 0.0005 mmol, 0.005 equiv) and chiral phosphoric acid C6 (1.77 mg, 0.0025 mmol, 0.025 equiv) were added to a dry reaction tube, and then the indole derivative 1h (26.0 mg, 0.1 mmol, 1 equiv) was dissolved in 1 ml of redistilled toluene. The reaction tube was evacuated and filled with argon (this operation was repeated three times). The diazo ester derivative 2r (68.2 mg, 0.25 mmol, 2.5 equiv) was dissolved in 1 ml of redistilled toluene and injected into the reaction tube with a syringe, and stirred at -20°C for 15 min. The reaction solution was evaporated to dryness under reduced pressure, and the residue was purified by column chromatography (silica gel, eluent: EtOAc / PE=1:80-1:10) to give a colorless viscous oil (34.9 mg, 69%, 87% ee), enantioselectivity: 87% ee; HPLC conditions: DaicelChiralpak OD-H column, n-hexane / i-PrOH=90 / 10, flow rate=1.5 mL / min, I=215 nm, t R =13.30min(major)and 15.50min(minor).[α] D 20 :+5.2(c 0.30, CH2Cl2; 87%ee). 11H NMR (400 MHz, CDCl3) δ 7.58 (d, J = 7.8 Hz, 1H), 7.35 - 7.27 (m, 3H), 7.26 - 7.16 (m, 2H), 7.14 (s, 1H), 7.10 (t, J = 7.4 Hz, 1H), 5.43 (d, J = 11.8 Hz, 1H), 5.37 (d, J = 11.8 Hz, 1H), 4.90 (dd, J = 9.2, 6.2 Hz, 1H), 4.62 (s, 1H), 3.59 - 3.25 (m, 2H), 2.94 (t, J = 6.8 Hz, 2H), 2.37 - 2.23 (m, 1H), 2.22 - 2.08 (m, 1H), 1.44 (s, 9H), 0.90 (t, J = 7.4 Hz, 3H). 13 13C NMR (100 MHz, CDCl3) δ 170.7, 156.1, 137.2, 137.1, 130.9, 128.6, 128.1, 123.5, 122.0, 119.6, 119.2, 113.3, 109.4, 79.1, 62.2, 59.6, 41.0, 28.6, 25.9, 25.7, 10.8. HRMS (ESI) m / z: [M + Na] + Calcd for C 26 H 30 Cl2N2NaO4 527.1475; Found 527.1479.

[0195] Example 60:

[0196]

[0197] Rh2(OPiv)4 (0.06 mg, 0.0001 mmol, 0.001 equiv) and chiral phosphoric acid C5 (1.75 mg, 0.0025 mmol, 0.025 equiv) were added to a dry reaction tube, and then the indole derivative 1i (24.2 mg, 0.1 mmol, 1 equiv) was dissolved in 1 ml of redistilled toluene. The reaction tube was evacuated and filled with argon (this operation was repeated three times). The diazo ester derivative 2r (68.2 mg, 0.25 mmol, 2.5 equiv) was dissolved in 1 ml of redistilled toluene and injected into the reaction tube with a syringe, and stirred at -20°C for 15 min. The reaction solution was evaporated to dryness under reduced pressure, and the residue was purified by column chromatography (silica gel, eluent: EtOAc / PE=1:80-1:25) to give a colorless viscous oil (34.1 mg, 70%, 98% ee), enantioselectivity: 98% ee; HPLC conditions: DaicelChiralpak IB column, n-hexane / i-PrOH=99 / 1, flow rate=1.2 mL / min, I=215 nm, t R =6.87min(major)and 7.52min(minor).[α] D 20 :+9.9 (c 0.35, CH2Cl2; 98%ee). 1 H NMR (400MHz, CDCl3) δ7.41(d,J=7.8Hz,1H),7.36-7.27(m,3H),7.26-7.13(m,6H),7.09-7.00(m,2H),5.42(d,J=11.8Hz,1H), 5.37(d,J=11.8Hz,1H),4.91(dd,J=9.1,6.3Hz,1H),4.06(s,2H),2.36-2.21(m,1H),2.20-2.04(m,1H),0.89(t,J=7.3Hz,3H). 13 C NMR (100MHz, CDCl3) δ170.7,139.7,137.3,137.1,131.6,130.9,130.8,130.1,128.6,128.5,127 .9,123.9,122.1,119.6,119.4,115.0,109.3,62.3,59.6,31.1,25.7,10.9.HRMS(ESI)m / z:[M+H] + Calcd for C 26 H 23 Cl3NO2486.0789; Found 486.0789.

[0198] Embodiment 61:

[0199]

[0200] Rh2(OPiv)4 (0.06 mg, 0.0001 mmol, 0.001 equiv) and chiral phosphoric acid C5 (1.75 mg, 0.0025 mmol, 0.025 equiv) were added to a dry reaction tube, and then the indole derivative 1j (19.3 mg, 0.1 mmol, 1 equiv) was dissolved in 1 ml of redistilled toluene. The reaction tube was evacuated and filled with argon (this operation was repeated three times). The diazo ester derivative 2r (68.2 mg, 0.25 mmol, 2.5 equiv) was dissolved in 1 ml of redistilled toluene and injected into the reaction tube with a syringe, and stirred at -20°C for 15 min. The reaction solution was evaporated to dryness under reduced pressure, and the residue was purified by column chromatography (silica gel, eluent: EtOAc / PE=1:80-1:25) to give a colorless viscous oil (22.8 mg, 52%, 96% ee), enantioselectivity: 96% ee; HPLC conditions: DaicelChiralpak IA column, n-hexane / i-PrOH=99 / 1, flow rate=1 mL / min, I=215 nm, t R =8.55min(minor)and 10.27min(major).[α] D 20 :-13.5 (c 0.25, CH2Cl2; 96%ee). 1 H NMR(400MHz, CDCl3)δ7.93(d,J=7.6Hz,1H),7.70-7.60(m,2H),7.48(s,1H),7.43(t,J=7.7Hz,2H),7.39-7.30(m,3H),7.30-7.15(m,4H), 5.47(d,J=11.8Hz,1H),5.41(d,J=11.8Hz,1H),4.99(dd,J=9.1,6.3Hz,1H),2.42-2.29(m,1H),2.28-2.14(m,1H),0.94(t,J=7.4Hz,3H). 13 C NMR (100MHz, CDCl3) δ170.5,137.5,137.1,135.6,130.9,130.8,128.8,128.6,127.6,126.5,1 26.0,123.4,122.3,120.5,120.1,118.3,109.6,62.4,59.7,25.8,10.8.HRMS(ESI)m / z:[M+H]+ Calcd for C 25 H 22 Cl2NO2438.1022; Found438.1020.

[0201] Embodiment 62:

[0202]

[0203] Rh2(OPiv)4 (0.06 mg, 0.0001 mmol, 0.001 equiv) and chiral phosphoric acid C5 (1.75 mg, 0.0025 mmol, 0.025 equiv) were added to a dry reaction tube, and then the indole derivative 1k (17.3 mg, 0.1 mmol, 1 equiv) was dissolved in 1 ml of redistilled toluene. The reaction tube was evacuated and filled with argon (this operation was repeated three times). The diazo ester derivative 2r (68.2 mg, 0.25 mmol, 2.5 equiv) was dissolved in 1 ml of redistilled toluene and injected into the reaction tube with a syringe, and stirred at -20°C for 15 min. The reaction solution was evaporated to dryness under reduced pressure, and the residue was purified by column chromatography (silica gel, eluent: EtOAc / PE=1:100-1:20) to give a white solid, melting point: 103-105°C (28.8 mg, 69%, 98% ee), enantioselectivity: 98% ee; HPLC conditions: Daicel Chiralpak OD-H column, n-hexane / i-PrOH=99 / 1, flow rate=0.8 mL / min, I=215 nm, t R =8.19min(major)and 10.01min(minor).[α] D 20 :+8.4(c 0.20, CH2Cl2; 98%ee). 1 H NMR (400MHz, CDCl3) δ7.38-7.29(m,2H),7.27-7.21(m,1H),7.13(d,J=8.3Hz,1H),7. 08(s,1H),7.04(t,J=7.7Hz,1H),6.82(d,J=7.1Hz,1H),5.43(d,J=11.8Hz,1H),5.38 (d,J=11.8Hz,1H),4.90(dd,J=8.9,6.5Hz,1H),3.62-3.38(m,1H),2.71(s,3H),2.34 -2.21(m,1H),2.21-2.06(m,1H),1.31(dd,J=6.6,5.7Hz,6H),0.89(t,J=7.4Hz,3H). 13C NMR (100MHz, CDCl3) δ170.8,137.4,137.1,131.03,130.97,130.8,128.5,126.0,125.5,1 21.6,121.4,120.6,107.0,62.1,59.4,26.1,25.7,25.1,20.5,10.9.HRMS(ESI)m / z:[M+H] + Calcdfor C 23 H 26 Cl2NO2418.1335; Found 418.1332.

[0204] Embodiment 63:

[0205]

[0206] Rh2(OPiv)4 (0.06 mg, 0.0001 mmol, 0.001 equiv) and chiral phosphoric acid C5 (1.75 mg, 0.0025 mmol, 0.025 equiv) were added to a dry reaction tube, and then the indole derivative 1l (19.3 mg, 0.1 mmol, 1 equiv) was dissolved in 1 ml of redistilled toluene. The reaction tube was evacuated and filled with argon (this operation was repeated three times). The diazo ester derivative 2r (68.2 mg, 0.25 mmol, 2.5 equiv) was dissolved in 1 ml of redistilled toluene and injected into the reaction tube with a syringe, and stirred at -20°C for 15 min. The reaction solution was evaporated to dryness under reduced pressure, and the residue was purified by column chromatography (silica gel, eluent: EtOAc / PE=1:100-1:20) to give a colorless viscous oil (22.8 mg, 52%, 96% ee), enantioselectivity: 98% ee; HPLC conditions: DaicelChiralpak OD-H column, n-hexane / i-PrOH=99 / 1, flow rate=0.8 mL / min, I=215 nm, t R =8.19min(major)and 10.01min(minor).[α] D 20 :+3.7(c 0.20, CH2Cl2; 96%ee). 1H NMR (400MHz, CDCl3) δ7.32 (d, J = 8.1Hz, 2H), 7.28-7.21 (m, 1H), 7.20-7.14 (m, 1H), 7.10 (s, 1H), 7.06-7.00 (m, 2H), 5.45-5.36 (m, 2H) ,4.87(dd,J=9.1,6.3Hz,1H),3.80-3.66(m,1H),2.36-2.23(m,1H),2.21-2.08(m,1H),1.31(t,J=6.7Hz,6H),0.89(t,J=7.4Hz,3H). 13 CNMR (100MHz, CDCl3) δ170.5,138.7,137.1,130.9,130.8,128.6,126.6,124.9,124.3 ,122.1,121.9,120.7,107.9,62.3,59.8,25.6,25.4,24.6,10.8.HRMS(ESI)m / z:[M+H] + Calcd for C 22 H 23 Cl3NO2438.0789; Found 438.0787.

[0207] Embodiment 64:

[0208]

[0209] Rh2(OPiv)4 (0.06 mg, 0.0001 mmol, 0.001 equiv) and chiral phosphoric acid C5 (1.75 mg, 0.0025 mmol, 0.025 equiv) were added to a dry reaction tube, and then the indole derivative 1m (17.3 mg, 0.1 mmol, 1 equiv) was dissolved in 1 ml of redistilled toluene. The reaction tube was evacuated and filled with argon (this operation was repeated three times). The diazo ester derivative 2r (68.2 mg, 0.25 mmol, 2.5 equiv) was dissolved in 1 ml of redistilled toluene and injected into the reaction tube with a syringe, and stirred at -20°C for 15 min. The reaction solution was evaporated to dryness under reduced pressure, and the residue was purified by column chromatography (silica gel, eluent: EtOAc / PE=1:100-1:20) to give a colorless viscous oil (30.0 mg, 72%, 98% ee), enantioselectivity: 98% ee; HPLC conditions: DaicelChiralpak ID column, n-hexane / i-PrOH=99 / 1, flow rate=0.8 mL / min, I=215 nm, t R= 6.29 min (minor) and 7.01 min (major). [α] D 20 : +18.2 (c 0.30, CH2Cl2; 98% ee). 1 1H NMR (400 MHz, CDCl3) δ 7.32 (s, 1H), 7.22 (d, J = 7.9 Hz, 2H), 7.13 (d, J = 8.2 Hz, 1H), 7.10 (d, J = 7.8 Hz, 1H), 6.90 (d, J = 10.1 Hz, 2H), 5.34 (d, J = 11.8 Hz, 1H), 5.29 (d, J = 11.8 Hz, 1H), 4.77 (t, J = 7.6 Hz, 1H), 3.07 (hept, J = 6.8 Hz, 1H), 2.36 (s, 3H), 2.25 - 2.11 (m, 1H), 2.11 - 2.00 (m, 1H), 1.25 (d, J = 6.8 Hz, 6H), 0.80 (t, J = 7.3 Hz, 3H). 13 13C NMR (100 MHz, CDCl3) δ 170.9, 137.1, 135.7, 131.0, 130.8, 128.5, 128.2, 127.7, 123.5, 123.2, 120.9, 119.4, 109.0, 62.1, 59.7, 25.8, 25.6, 23.47, 23.45, 21.6, 10.8. HRMS (ESI) m / z: [M + H] + Calcd for C 23 H 26 Cl2NO2 418.1335; Found 418.1334.

[0210] Example 65:

[0211]

[0212] Rh2(OPiv)4 (0.06 mg, 0.0001 mmol, 0.001 equiv) and chiral phosphoric acid C5 (1.75 mg, 0.0025 mmol, 0.025 equiv) were added to a dry reaction tube, and then the indole derivative 1n (19.3 mg, 0.1 mmol, 1 equiv) was dissolved in 1 ml of redistilled toluene. The reaction tube was evacuated and filled with argon (this operation was repeated three times). The diazo ester derivative 2r (68.2 mg, 0.25 mmol, 2.5 equiv) was dissolved in 1 ml of redistilled toluene and injected into the reaction tube with a syringe, and stirred at -20°C for 15 min. The reaction solution was evaporated to dryness under reduced pressure, and the residue was purified by column chromatography (silica gel, eluent: EtOAc / PE=1:100-1:25) to give a white solid (22.8 mg, 52%, 95% ee), enantioselectivity: 95% ee; HPLC conditions: Daicel Chiralpak ID column, n-hexane / i-PrOH=99 / 1, flow rate=0.8 mL / min, I=215 nm, t R =6.77min(minor)and 7.36min(major).[α] D 20 :+16.4 (c 0.20, CH2Cl2; 95%ee). 1 H NMR (400MHz, CDCl3) δ7.56 (d, J = 1.9Hz, 1H), 7.36-7.28 (m, 2H), 7.27-7.22 (m, 1H), 7. 19(d,J=8.7Hz,1H),7.09(dd,J=8.7,1.9Hz,1H),7.05(s,1H),5.42(d,J=11.8Hz,1H) ,5.38(d,J=11.8Hz,1H),4.83(dd,J=9.1,6.4Hz,1H),3.12(hept,J=6.9Hz,1H),2.37 -2.22(m,1H),2.20-2.06(m,1H),1.31(dd,J=6.9,3.0Hz,6H),0.89(t,J=7.4Hz,3H). 13 C NMR (100MHz, CDCl3) δ170.5,137.0,135.7,130.9,130.8,128.6,124.8,123.7,122.2 ,121.9,119.1,110.3,62.2,59.9,25.6,25.5,23.4,23.3,10.8.HRMS(ESI)m / z:[M+H] + Calcd for C 22 H 23Cl3NO2438.0789; Found 438.0793.

[0213] Embodiment 66:

[0214]

[0215] Rh2(OPiv)4 (0.06 mg, 0.0001 mmol, 0.001 equiv) and chiral phosphoric acid C5 (1.75 mg, 0.0025 mmol, 0.025 equiv) were added to a dry reaction tube, and then the indole derivative 1o (17.3 mg, 0.1 mmol, 1 equiv) was dissolved in 1 ml of redistilled toluene. The reaction tube was evacuated and filled with argon (this operation was repeated three times). The diazo ester derivative 2r (68.2 mg, 0.25 mmol, 2.5 equiv) was dissolved in 1 ml of redistilled toluene and injected into the reaction tube with a syringe, and stirred at -20°C for 15 min. The reaction solution was evaporated to dryness under reduced pressure, and the residue was purified by column chromatography (silica gel, eluent: EtOAc / PE=1:100-1:30) to give a white solid, melting point: 78-80°C (28.0 mg, 67%, 98% ee), enantioselectivity: 98% ee; HPLC conditions: Daicel Chiralpak OD-H column, n-hexane / i-PrOH=99 / 1, flow rate=0.9 mL / min, I=215 nm, t R =6.56min(minor)and7.23min(major).[α] D 20 :+23.1 (c 0.15, CH2Cl2; 98%ee). 1 HNMR (400MHz, CDCl3) δ7.49 (d, J = 8.0Hz, 1H), 7.36-7.28 (m, 2H), 7.25-7.20 (m, 1H), 7. 08(s,1H),6.96(s,1H),6.91(dd,J=8.0,0.8Hz,1H),5.42(d,J=11.8Hz,1H),5.38(d,J =11.8Hz,1H),4.86(dd,J=8.9,6.5Hz,1H),3.15(hept,J=6.9Hz,1H),2.44(s,3H),2.3 2-2.21(m,1H),2.19-2.07(m,1H),1.32(dd,J=6.9,2.4Hz,6H),0.91(t,J=7.4Hz,3H). 13CNMR (100MHz, CDCl3) δ170.9,137.8,137.1,131.4,131.1,130.8,128.5,125.4,123.8,120.8 ,120.1,119.3,109.4,62.1,59.6,25.72,25.67,23.5,23.4,22.0,10.9.HRMS(ESI)m / z:[M+H] + Calcd for C 23 H 26 Cl2NO2418.1335; Found 418.1337.

[0216] Embodiment 67:

[0217]

[0218] Rh2(OPiv)4 (0.06 mg, 0.0001 mmol, 0.001 equiv) and chiral phosphoric acid C5 (1.75 mg, 0.0025 mmol, 0.025 equiv) were added to a dry reaction tube, and then the indole derivative 1p (23.8 mg, 0.1 mmol, 1 equiv) was dissolved in 1 ml of redistilled toluene. The reaction tube was evacuated and filled with argon (this operation was repeated three times). The diazo ester derivative 2r (68.2 mg, 0.25 mmol, 2.5 equiv) was dissolved in 1 ml of redistilled toluene and injected into the reaction tube with a syringe, and stirred at -20°C for 15 min. The reaction solution was evaporated to dryness under reduced pressure, and the residue was purified by column chromatography (silica gel, eluent: EtOAc / PE=1:80-1:25) to give a white solid, melting point: 81-83°C (27.5 mg, 57%, 98% ee), enantioselectivity: 98% ee; HPLC conditions: Daicel Chiralpak OD-H column, n-hexane / i-PrOH=99 / 1, flow rate=0.8 mL / min, I=215 nm, t R =7.12min(minor)and7.82min(major).[α] D 20 :+23.6 (c 0.25, CH2Cl2; 98%ee). 11H NMR (400 MHz, CDCl3) δ 7.38 (d, J = 8.4, 1H), 7.36 (d, J = 1.7 Hz, 1H), 7.28 - 7.21 (m, 2H), 7.19 - 7.13 (m, 1H), 7.09 (dd, J = 8.4, 1.7 Hz, 1H), 6.92 (d, J = 0.7 Hz, 1H), 5.36 (d, J = 11.8 Hz, 1H), 5.32 (d, J = 11.8 Hz, 1H), 4.72 (dd, J = 9.1, 6.4 Hz, 1H), 3.14 - 2.99 (m, 1H), 2.27 - 2.14 (m, 1H), 2.13 - 1.98 (m, 1H), 1.24 (dd, J = 6.9, 2.9 Hz, 6H), 0.82 (t, J = 7.4 Hz, 3H). 13 13C NMR (100 MHz, CDCl3) δ 170.5, 138.1, 137.1, 130.9, 130.8, 128.6, 126.4, 124.2, 122.4, 121.4, 120.8, 115.5, 112.4, 62.3, 59.8, 25.6, 25.5, 23.37, 23.35, 10.8. HRMS (ESI) m / z: [M + H] + Calcd for C 22 H 23 BrCl2NO2 482.0284; Found 482.0286.

[0219] Example 68:

[0220]

[0221] Rh2(OPiv)4 (0.06 mg, 0.0001 mmol, 0.001 equiv) and chiral phosphoric acid C5 (1.75 mg, 0.0025 mmol, 0.025 equiv) were added to a dry reaction tube, and then the indole derivative 1r (19.6 mg, 0.1 mmol, 1 equiv) was dissolved in 1 ml of redistilled toluene. The reaction tube was evacuated and filled with argon (this operation was repeated three times). The diazo ester derivative 2r (68.2 mg, 0.25 mmol, 2.5 equiv) was dissolved in 1 ml of redistilled toluene and injected into the reaction tube with a syringe, and stirred at -20°C for 15 min. The reaction solution was evaporated to dryness under reduced pressure, and the residue was purified by column chromatography (silica gel, eluent: EtOAc / PE=1:80-1:25) to give a white solid, melting point: 86-88°C (31.8 mg, 72%, 95% ee), enantioselectivity: 95% ee; HPLC conditions: Daicel Chiralpak ID column, n-hexane / i-PrOH=99 / 1, flow rate=1.3 mL / min, I=215 nm, t R =5.16min(minor)and5.81min(major).[α] D 20 :-2.2 (c 0.30, CH2Cl2; 95%ee). 1 HNMR(400MHz, CDCl3) δ7.55(d,J=8.0Hz,1H),7.39-7.27(m,4H),7.27-7.15(m,3H),5.45(d,J=11.8Hz,1H),5. 39(d,J=11.8Hz,1H),4.92(dd,J=9.3,6.1Hz,1H),2.38-2.21(m,1H),2.21-2.06(m,1H),0.90(t,J=7.4Hz,3H). 13 C NMR (100MHz, CDCl3) δ170.2,137.1,136.2,131.0,130.7,128.6,127.5,124.8, 123.0,120.8,119.6,109.5,91.7,62.4,59.9,25.8,10.8.HRMS(ESI)m / z:[M+H] + Calcd for C 19 H 17 BrCl2NO2439.9814. Found 439.9817.

[0222] Embodiment 69:

[0223]

[0224] Rh2(OPiv)4 (0.06 mg, 0.0001 mmol, 0.001 equiv) and chiral phosphoric acid C5 (1.75 mg, 0.0025 mmol, 0.025 equiv) were added to a dry reaction tube, and then the indole derivative 1s (17.3 mg, 0.1 mmol, 1 equiv) was dissolved in 1 ml of redistilled toluene. After the reaction tube was evacuated and filled with argon (this operation was repeated three times), the diazo ester derivative 2r (68.2 mg, 0.25 mmol, 2.5 equiv) was dissolved in 1 ml of redistilled toluene and injected into the reaction tube with a syringe, and stirred at -20°C for 15 min. The reaction activity was poor, and the starting material was almost not consumed (<5%, <10% ee).

[0225] Embodiment 70:

[0226]

[0227] Rh2(OPiv)4 (0.06 mg, 0.0001 mmol, 0.001 equiv) and chiral phosphoric acid C5 (1.75 mg, 0.0025 mmol, 0.025 equiv) were added to a dry reaction tube, and then indole 1q (23.8 mg, 0.1 mmol, 1 equiv) was dissolved in 1 ml of redistilled toluene. After the reaction tube was evacuated and filled with argon (this operation was repeated three times), the diazo ester derivative 2r (68.2 mg, 0.25 mmol, 2.5 equiv) was dissolved in 1 ml of redistilled toluene and injected into the reaction tube with a syringe, and stirred at -20°C for 15 min. The reaction activity was poor, and the raw material was almost not consumed (<5%, <10% ee).

[0228] Embodiment 71:

[0229]

[0230] Rh2(Oct)4 (0.08 mg, 0.0001 mmol, 0.001 equiv) and chiral phosphoric acid C1 (1.4 mg, 0.0025 mmol, 0.025 equiv) were added to a dry reaction tube, and then the indole derivative 1s (17.3 mg, 0.1 mmol, 1 equiv) was dissolved in 1 ml of redistilled dichloromethane. After the reaction tube was evacuated and filled with argon (this operation was repeated three times), the diazo ester derivative 2a (26.4 mg, 0.15 mmol, 1.5 equiv) was dissolved in 1 ml of redistilled dichloromethane and injected into the reaction tube with a syringe, and stirred at 25°C for 15 min. The reaction activity was poor, and the starting material was almost not consumed (<5%, <10% ee).

[0231] Embodiment 72:

[0232]

[0233] Rh2(Oct)4 (0.08 mg, 0.0001 mmol, 0.001 equiv) and chiral phosphoric acid C1 (1.4 mg, 0.0025 mmol, 0.025 equiv) were added to a dry reaction tube, and then the indole derivative 1q (23.7 mg, 0.1 mmol, 1 equiv) was dissolved in 1 ml of redistilled dichloromethane. The reaction tube was evacuated and filled with argon (this operation was repeated three times), and then the diazo ester derivative 2a (26.4 mg, 0.15 mmol, 1.5 equiv) was dissolved in 1 ml of redistilled dichloromethane and injected into the reaction tube with a syringe, and stirred at 25 °C for 15 min. The reaction solution was evaporated to dryness under reduced pressure, and the residue was purified by column chromatography (silica gel, eluent: EtOAc / PE=1:20-1:10) to give an orange solid, melting point: 58-60°C (19.3 mg, 50%, 30% ee), enantioselectivity: 30% ee; HPLC conditions: Daicel Chiralpak OD-H column, n-hexane / i-PrOH=90 / 10, flow rate=1 mL / min, I=215 nm, t R =4.17min(major)and 6.63min(minor).[α] D 20 :+3.1(c 0.35, CH2Cl2; 30%ee). 1 HNMR (400MHz, CDCl3) δ9.08 (s, 1H), 7.65 (d, J = 8.0Hz, 1H), 7.34-7.23 (m, 6H), 6.95 (t, J = 7.8Hz, 1H),5.37(s,1H),3.81(s,3H),3.18-3.06(m,1H),1.41(d,J=7.1Hz,3H),1.24(d,J=7.1Hz,3H). 13 C NMR (100MHz, CDCl3) δ172.7,137.5,134.6,129.01,128.97,127.7,127.6,124.0 ,121.0,120.1,119.5,105.0,52.9,47.9,26.2,23.0,22.8.HRMS(ESI)m / z:[M+H] + Calcd for C 20 H 21 BrNO2386.0750; Found 386.0750.

Claims

1. A method for synthesizing N-alkylated indole derivatives with high stereoselectivity, characterized in that: Add a rhodium catalyst and chiral phosphoric acid to a reaction container, dissolve an indole derivative in a solvent and add the two together to the reaction container, dissolve a diazo ester derivative in a solvent after replacing argon and inject the diazo ester derivative into the reaction container through a syringe, stir and react at a certain temperature for a certain time, and after the reaction is complete, separate and purify by column chromatography to obtain an N-alkylated indole derivative; R 1 for Me, Et, i-Pr, t-Bu, i-Bu, Ph, Br, One of the 2 is one of H, 4-Me, 4-Cl, 5-Me, 5-Cl, 6-Me, and 6-Br; R 3 is Et,n-Bu, n-hex, Bn, Ph, 2-MeC6H4, 2-FC6H4, 3-MeC6H4, 3-ClC6H4, 4-MeC6H4, 4-ClC6H4, 4-BrC6H4, 4-CF3C6H4, 4-BocNHC6H4, 2,4-diClC6H3, 3,4-diClC6H3, One of the 4 for Me, Et, i-Pr, t-Bu, Bn, One of; The chiral phosphoric acid is as follows: The rhodium catalyst is one of Rh2(Oct)4, Rh2(OAc)4 and Rh2(OPiv)4; the solvent is one of toluene and dichloromethane.

2. The method for synthesizing N-alkylated indole derivatives with high stereoselectivity according to claim 1, characterized in that: The specific structural formula of the indole derivative is as follows:

3. The method for synthesizing N-alkylated indole derivatives with high stereoselectivity according to claim 1, characterized in that: The specific structural formula of the diazo ester derivative is as follows:

4. The method for synthesizing N-alkylated indole derivatives with high stereoselectivity according to claim 1, characterized in that: The equivalent ratio of the rhodium catalyst, chiral phosphoric acid, indole derivative and diazo ester derivative is: 0.0001-0.0010: 0.0025-0.0050: 1: 1-2.

5.

5. The method for synthesizing N-alkylated indole derivatives with high stereoselectivity according to claim 1, characterized in that: The reaction temperature is -20 to 40°C, and the reaction time is 15 to 40 minutes.

Images