Chiral sulfimine lipid compound, preparation method and application thereof

Abstract

The application discloses a chiral thioimine lipid compound and a preparation method and application thereof, and the preparation method comprises the following steps: stirring sulfenamide, isobutyl alcohol, MS, a metal center chiral cobalt (III) complex anion and super-dry tetrahydrofuran at-40 DEG C for 30 minutes, then adding N-iodosuccinimide, and reacting at the same temperature for 36 hours; after the reaction is completed, the reaction is quenched by using an aqueous Na2S2O3 solution, and the chiral thioimine lipid compound is obtained through separation and purification; the chiral thioimine lipid compound prepared by the application provides a robust and practical method for solving the challenging asymmetric problem in sulfur stereochemistry, and opens up a road for a new type of chiral sulfur-containing compound which has a wide application in the fields of medicine and pesticides.

Description

Technical Field

[0001] This invention relates to chiral thioimine ester compounds, specifically, to a chiral thioimine ester compound, its preparation method, and its applications. Background Technology

[0002] Sulfur-chiral compounds are of great significance in asymmetric synthesis and drug development. In recent years, extensive research has been conducted on the catalytic control of S-chiral compound synthesis. Currently, research on the catalytic synthesis of chiral thioimine esters mainly focuses on constructing sulfur-chiral compounds, particularly utilizing transition metal catalysis or organocatalysis strategies to achieve highly enantioselective synthesis of thioimine esters with different aryl or alkyl substitutions. These breakthroughs have not only solved key challenges in the synthesis of thioimine ester compounds but also provided important tools for drug development and organic synthesis.

[0003] Among numerous chiral sulfur compounds, chiral thioimine esters, as aza-analogs of sulfinic acid esters, are common precursors for various azathiosteromeric centers. Their azathiosteromeric centers can provide additional modification sites due to their N-substitution, forming more hydrogen bonds and enhancing structural diversity, thereby greatly improving the pharmacological parameters and physicochemical properties of some candidate drugs.

[0004] However, the asymmetric catalytic synthesis of chiral thioimine esters has always been a research challenge in the field of asymmetric catalysis, lacking effective asymmetric catalytic synthesis strategies. In 2023, Japanese chemists achieved the stereospecific synthesis of chiral thioimine esters through the asymmetric O-isopropylation of chiral sulfinamides (Angew. Chem. Int. Ed. 2023, 62, e202300637). Recently, Professor Wu Xingxing's research group at Guizhou University achieved the asymmetric catalytic synthesis of chiral thioimine esters through the dynamic kinetic resolution of racemic sulfinamides (Angew. Chem. Int. Ed. 2025, e202500170). In recent years, the sulfur functionalization reaction of sulfenamides has gradually attracted the interest of chemists both domestically and internationally, providing novel ideas for the asymmetric catalytic synthesis of chiral thioimine esters (J. Am. Chem. Soc. 2023, 145, 6310; Org. Lett. 2023, 25, 2830; J. Org. Chem. 2023, 88, 16116.). Therefore, developing new catalytic strategies is essential for the synthesis of chiral thioimine esters, and it is expected to advance the creation of chiral thioimine ester pesticides and drugs. Summary of the Invention

[0005] The purpose of this invention is to provide a chiral thioimine ester compound, its preparation method, and its application, so as to fill the gap in the prior art and meet the needs of related fields.

[0006] To achieve the above objectives, the present invention provides a chiral thioimine ester compound, wherein the general structural formula of the chiral thioimine ester compound is:

[0007]

[0008] Among them, R 1 C 1-8 Straight-chain or branched alkyl / cycloalkyl / alkynyl groups, C3 halogenated straight-chain alkyl groups, C 6-9 One of the aryl or substituted aryl or naphthyl groups;

[0009] The substituted aryl group is C. 1-3 One of the following: alkyl-substituted aryl, C2-oxoalkyl-substituted aryl, nitro-substituted phenethyl, trifluoromethyl-substituted benzyl, or halobenzyl;

[0010] R 2 It is n-butyl or cyclohexyl, C 6-9 One of aryl, benzyl or substituted aryl, substituted benzyl or thiophene;

[0011] The substituted aryl group is one of methyl or isopropyl substituted aryl, cyano substituted aryl, methyl formate substituted aryl, nitro substituted aryl, methoxy substituted aryl, trifluoromethyl substituted aryl, or haloaryl; the substituted benzyl group is methyl substituted benzyl.

[0012] R 3 C 3 / 4 / 6 Straight-chain or branched alkyl / cycloalkyl, C 6-8 One of the substituted aryl, naphthyl, thiophene, or 4-methylaniline groups;

[0013] The substituted aryl group is one of cyano-substituted aryl, trifluoromethyl-substituted aryl, nitro-substituted aryl, methyl formate-substituted aryl, benzoyl-substituted aryl, methyl-substituted aryl, methoxy-substituted aryl, or haloaryl.

[0014] In a preferred embodiment of the present invention, the alkyl group is one of methyl, ethyl, n-propyl, isopropyl, isobutyl, tert-butyl, 3-pentyl, n-hexyl, n-octyl or β-cholestyl;

[0015] In a preferred embodiment of the present invention, the cycloalkyl group is one of cyclopropyl, cyclopropylmethyl, cyclobutyl, cyclohexyl, cyclopentylethyl or cyclohexylethyl.

[0016] In a preferred embodiment of the present invention, the halogen is one of fluorine, chlorine or bromine.

[0017] This invention also provides a method for preparing chiral thioimine ester compounds, the method comprising:

[0018] 1) Combine sulfenamide (Formula 2), alcohol (Formula 3), Chiral cobalt(III) with a metal center and an anion, ultra-dry tetrahydrofuran were mixed and reacted at -45°C to -35°C for 25-35 min.

[0019] 2) Then N-iodosuccinimide was added, and the whole system was reacted at -45℃ to -35℃ for 35-37h. Na2S2O3 aqueous solution was added to separate the organic layer from the aqueous phase to quench the reaction. The chiral thioimide ester compound (Formula 4) was obtained by separation and purification.

[0020]

[0021] The above-mentioned method for preparing chiral thioimine esters involves the asymmetric oxidative esterification reaction of sulfenamides catalyzed by a chiral cobalt(III) anion sodium salt. This method is applicable to a series of reactions of sulfenamides and alcohols and can produce chiral thioimine esters with extremely high enantioselectivity, regioselectivity and chemoselectivity.

[0022] In a preferred embodiment of the present invention, the amount of isobutanol used is 0.20 mmol relative to 0.10 mmol of sulfenamide, the amount of the chiral cobalt(III) anion with a metal center is 0.01 mmol, and the amount of N-iodosuccinimide is 0.20 mmol. The dosage is 100 mg, and the dosage of tetrahydrofuran is 1.0 mL.

[0023] In the above method, the metal-centered chiral cobalt(III) anionic catalyst can be prepared using the methods reported in Angew. Chem. Int. Ed. 2015, 54, 11209; Angew. Chem. Int. Ed. 2017, 56, 11931; ZL201510426983.X. In the above reaction, the enantiomeric excess percentage (ee) of the obtained chiral thioimine ester compound can reach up to 97%.

[0024] This invention discloses a method for preparing chiral thioimine esters, involving an asymmetric S-esterification reaction catalyzed by a metal-centered chiral cobalt(III) anion and sulfenamide. The method is simple, the reaction conditions are mild, the raw materials are economical and readily available, and the prepared product has high optical purity (ee value up to 97%). The chiral thioimine esters prepared by this invention are expected to have wide applications in asymmetric synthesis and in the research and development of pharmaceuticals and pesticides.

[0025] Other features and advantages of the present invention will be described in detail in the following detailed description section. Attached Figure Description

[0026] The accompanying drawings are provided to further illustrate the invention and form part of the specification. They are used together with the following detailed description to explain the invention, but do not constitute a limitation thereof. In the drawings:

[0027] Figure 1 This is the liquid phase spectrum of compound 4a obtained in Example 1. Detailed Implementation

[0028] The following provides a detailed description of specific embodiments of the present invention. It should be understood that the specific embodiments described herein are for illustrative and explanatory purposes only and are not intended to limit the invention. In the embodiments, the reaction yield refers to the separation yield, and ee refers to the percentage of enantiomer excess in the reaction.

[0029] Unless otherwise specified, all reagents used in the examples were purchased from Anengji, Aladdin, and Shanghai Guoyao Company. All solvents used in the examples were purchased from UPT Co., Ltd. Unless otherwise specified, all thin-layer chromatography silica gels used in the examples were purchased from Qingdao Haiyang Chemical Co., Ltd.

[0030] Example 1: Synthesis and characterization of compound 4a

[0031]

[0032] Step 1: At room temperature, add sulfenamide 2a (0.10 mmol) and isobutanol 3a (0.20 mmol) to a 10 mL dry reaction tube. (100 mg), chiral cobalt(III) with a metal center and anion Λ-(S,S)-1a (0.01 mmol); ultra-dry tetrahydrofuran (1.0 mL) was added to the reaction tube, and the mixture was stirred at -40 °C for 30 minutes. Then, N-iodosuccinimide (0.20 mmol) was added to the reaction tube in one go, and the entire system was reacted at -40 °C for 36 hours. The reaction was quenched by adding an aqueous solution of Na2S2O3 and then separating the organic layer from the aqueous phase. After quenching the reaction, the aqueous phase was extracted with ethyl acetate (3 × 5.0 mL), the organic layer was dried over anhydrous sodium sulfate, the resulting mixture was filtered, concentrated by vacuum distillation, and then dissolved and diluted with 1.0 mL of dichloromethane. Thin-layer chromatography silica gel was added to a standard glass column, and the dissolved mixture was subjected to nitrogen-pressurized column chromatography (15 cm column length, 3 drops / second flow rate) with petroleum ether:ethyl acetate = 10:1 (volume ratio) as the eluent. Purification was achieved directly by rapid column chromatography, finally separating the axially chiral thioimine compound 4a with a yield of 94% and ee = 93%. Compounds 4a-4ca in the following examples were obtained similarly. Chiral thioimine esters were obtained through separation and purification.

[0033] The structure of compound 4a is as follows:

[0034]

[0035] Characterization data of compound 4a:

[0036] isobutyl(R)-N-benzoyl-4-(tert-butyl)benzenesulfinimidate 4a: yield: 94% (33.7mg); flash column chromatography eluent, petroleum ether / ethyl acetate=10:1; colorless oil; [α] D 20 = -108.9 (c 0.73CH2Cl2); 1 H NMR (600MHz, CDCl3) δ8.29 (d, J=7.5Hz, 2H), 7.96 (d, J=8.4Hz, 2H), 7.61 (d, J=8.4Hz, 2H), 7.50 (t, J=7.2Hz, 1H), 7.43 (t, J= 7.5Hz, 2H), 4.06 (dd, J=9.5, 6.7Hz, 1H), 3.70 (dd, J=9.5, 6.7Hz, 1H), 2.01-1.88 (m, 1H), 1.37 (s, 9H), 0.89 (t, J=6.6Hz, 6H); 13 C NMR (151MHz, CDCl3) δ178.5, 156.6, 136.2, 133.8, 131.8, 129.6, 128.0, 127.7, 126.6, 74.2, 35.3, 31.2, 28.9, 19.1; HRMS (ESI) m / z: [M+H] + Calculated for C 21 H 28 NO2S: 358.1835, found: 358.1937; Enantiomeric excess: 93%, determined by HPLC (Daicel Chiralpak IF, isopropanol / hexane=20 / 80, flow rate=1.0mL / min, T=30°C, λ=254nm): t R =6.06min (major), t R = 6.60min (minor).

[0037] Example 2: Synthesis and characterization of compound 4b

[0038]

[0039] Using the same method as in Example 1, product 4b was finally separated with a yield of 98% and ee = 93%.

[0040] The structure of compound 4b is as follows:

[0041]

[0042] Characterization data of compound 4b:

[0043] methyl(R)-N-benzoyl-4-(tert-butyl)benzenesulfinimidate 4b: yield: 98% (31.0mg); flash column chromatography eluent, petroleum ether / ethyl acetate=10:1; colorless oil; [α] D 20 = -200.9 (c 0.23CH2Cl2); 1 H NMR (600MHz, CDCl3) δ8.30 (d, J=8.0Hz, 2H), 7.98 (d, J=8.4Hz, 2H), 7.63 (d, J=8. 4Hz, 2H), 7.52 (t, J=7.3Hz, 1H), 7.44 (t, J=7.5Hz, 2H), 3.67 (s, 3H), 1.37 (s, 9H); 13 C NMR (151MHz, CDCl3) δ178.6, 157.0, 136.0, 132.8, 131.9, 129.6, 128.1, 127.9, 126.7, 52.8, 35.4, 31.3; HRMS (ESI) m / z: [M+H] + Calculated for C 18 H 22 NO2S: 316.1366, found: 316.1368; Enantiomeric excess: 93%, determined by HPLC (Daicel Chiralpak IF, isopropanol / hexane=5 / 95, flow rate=1.0mL / min, T=30°C, λ=254nm): t R =21.39min (major), t R= 23.34min (minor).

[0044] Example 3: Synthesis and characterization of compound 4c

[0045]

[0046] Using the same method as in Example 1, product 4c was finally separated with a yield of 92% and ee = 95%.

[0047] The structure of compound 4c is as follows:

[0048]

[0049] Characterization data of compound 4c:

[0050] thyl(R)-N-benzoyl-4-(tert-butyl)benzenesulfinimidate 4c: yield: 92% (30.2mg); flash column chromatography eluent, petroleum ether / ethyl acetate=10:1; colorless oil; [α] D 20 = -198.2 (c 0.17CH2Cl2); 1 H NMR (600MHz, CDCl3) δ8.29 (d, J=7.9Hz, 2H), 7.97 (d, J=8.3Hz, 2H), 7.62 (d, J=8.3Hz, 2H), 7.51 (t, J=7.2Hz, 1H), 7. 43 (t, J=7.6Hz, 2H), 4.35 (dq, J=14.3, 7.1Hz, 1H), 4.07 (dq, J=14.5, 7.1Hz, 1H), 1.37 (s, 9H), 1.32 (t, J=7.1Hz, 3H); 13 C NMR (151MHz, CDCl3) δ178.6, 156.7, 136.1, 133.7, 131.9, 129.6, 128.1, 127.7, 126.6, 64.8, 35.3, 31.3, 15.8; HRMS (ESI) m / z: [M+H] + Calculated for C 19 H 24NO2S: 330.1522, found: 330.1530; Enantiomeric excess: 95%, determined by HPLC (Daicel Chiralpak IF, isopropanol / hexane=5 / 95, flow rate=1.0mL / min, T=30°C, λ=254nm): t R =16.54min (major), t R = 19.35min (minor).

[0051] Example 4: Synthesis and characterization of compound 4d

[0052]

[0053] Using the same method as in Example 1, the final product 4d was obtained with a yield of 94% and ee = 90%.

[0054] The structure of compound 4d is as follows:

[0055]

[0056] Characterization data of compound 4d:

[0057] propyl(R)-N-benzoyl-4-(tert-butyl)benzenesulfinimidate 4d: yield: 94% (32.4mg); flash column chromatography eluent, petroleum ether / ethyl acetate=10:1; colorless oil; [α] D 20 = -198.2 (c 0.29CH2Cl2); 1 H NMR (600MHz, CDCl3) δ8.32-8.26 (m, 2H), 7.97 (d, J=8.4Hz, 2H), 7.62 (d, J=8.4Hz, 2H), 7.51 (t, J=7.3Hz, 1H), 7.43 (t, J=7.6Hz, 2H), 4.24 (dt, J=9.7, 6.7Hz, 1H), 3.92 (dt, J=9.8, 6.7Hz, 1H), 1.69 (dt, J=14.1, 7.2Hz, 2H), 1.37 (s, 9H), 0.90 (t, J=7.4Hz, 3H); 13C NMR (151MHz, CDCl3) δ178.6, 156.7, 136.2, 133.8, 131.8, 129.6, 128.1, 127.7, 126.6, 70.1, 35.3, 31.3, 23.3, 10.4; HRMS (ESI) m / z: [M+Na] + Calculated for C 20 H 25 NNaO2S: 366.1498, found: 366.1504; Enantiomericexcess: 90%, determined by HPLC (Daicel Chiralpak IF, isopropanol / hexane=10 / 90, flow rate=1.0mL / min, T=30°C, λ=254nm): t R =10.14min (major), t R = 11.25min (minor).

[0058] Example 5: Synthesis and characterization of compound 4e

[0059]

[0060] Using the same method as in Example 1, product 4e was finally separated with a yield of 95% and ee = 89%.

[0061] The structure of compound 4e is as follows:

[0062]

[0063] Characterization data of compound 4e:

[0064] hexyl(R)-N-benzoyl-4-(tert-butyl)benzenesulfinimidate 4e: yield: 95% (36.7mg); flash column chromatography eluent, petroleum ether / ethyl acetate=10:1; colorless oil; [α] D 20 = -52.0 (c 0.03CH2Cl2); 1H NMR (600MHz, CDCl3) δ8.29 (d, J=7.9Hz, 2H), 7.96 (d, J=8.4Hz, 2H), 7.61 (d, J=8.4Hz, 2H), 7.50 (t, J=7.3Hz, 1H), 7.43 (t, J=7.6Hz, 2H), 4.27 (d t, J=9.7, 6.7Hz, 1H), 3.95 (dt, J=9.7, 6.7Hz, 1H), 1.67-1.63 (m, 2H), 1. 37(s, 9H), 1.33-1.28(m, 2H), 1.27-1.21(m, 4H), 0.83(t, J=6.9Hz, 3H); 13 C NMR (151MHz, CDCl3) δ178.6, 156.7, 136.2, 133.8, 131.8, 129.6, 128.1, 127.7 , 126.6, 68.5, 35.3, 31.4, 31.3, 29.9, 25.4, 22.6, 14.1; HRMS (ESI) m / z: [M+Na] + Calculated for C 23 H 31 NNaO2S: 408.1968, found: 408.1975; Enantiomeric excess: 89%, determined by HPLC (Daicel Chiralpak OD, isopropanol / hexane=5 / 95, flow rate=1.0mL / min, T=30°C, λ=254nm): t R =7.37min (major), t R = 8.13min (minor).

[0065] Example 6: Synthesis and characterization of compound 4f

[0066]

[0067] Using the same method as in Example 1, product 4f was finally obtained with a yield of 96% and ee = 86%.

[0068] The structure of compound 4f is as follows:

[0069]

[0070] Characterization data of compound 4f:

[0071] octyl(R)-N-benzoyl-4-(tert-butyl)benzenesulfinimidate 4f: yield:96%(39.7mg);flash column chromatography eluent,petroleum ether / ethyl acetate=10:1;colorless oil;[α] D 20 =-172.1(c 0.19CH2Cl2); 1 H NMR(600MHz,CDCl3)δ8.30(dd,J=8.0,1.0Hz,2H),7.97(d,J=8.6Hz,2H),7.61(d,J=8.6Hz,2H),7.53-7.48(m,1H),7.43(t,J=7.6Hz,2H),4.27(dt,J=9.9,6.6Hz,1H),3.94(dt,J=9.9,6.6Hz,1H),1.67-1.62(m,2H),1.37(s,9H),1.32-1.27(m,2H),1.26-1.18(m,8H),0.85(t,J=7.1Hz,3H); 13 C NMR(151MHz,CDCl3)δ178.5,156.6,136.1,133.7,131.8,129.6,128.0,127.7,126.6,68.4,35.3,31.8,31.2,29.9,29.2,29.2,25.7,22.7,14.2;HRMS(ESI)m / z:[M+Na] + calculatedfor C 25 H 35 NNaO2S:436.2281,found:436.2286;Enantiomeric excess:86%,determined byHPLC(Daicel Chiralpak AD,isopropanol / hexane=10 / 90,flow rate=1.0mL / min,T=30℃,λ=254nm):t R =6.93min(major),t R =6.16min(minor).

[0072] Example 7: Synthesis and characterization of compound 4g

[0073]

[0074] Using the same method as in Example 1, 4g of product was finally separated, with a yield of 92% and ee = 92%.

[0075] The structure of compound 4g is as follows:

[0076]

[0077] Characterization data of compound 4g:

[0078] isopropyl(R)-N-benzoyl-4-(tert-butyl)benzenesulfinimidate 4g: yield: 92% (31.5mg); flash column chromatography eluent, petroleum ether / ethyl acetate=10:1; colorless oil; [α] D 20 = -215.9 (c 0.04CH2Cl2); 1 H NMR (600MHz, CDCl3) δ8.28 (d, J=7.4Hz, 2H), 7.96 (d, J=8.4Hz, 2H), 7.60 (d, J=8.4Hz, 2H), 7.49 (t, J=7.3Hz, 1H) , 7.42 (t, J=7.5Hz, 2H), 5.07 (dt, J=12.5, 6.3Hz, 1H), 1.46 (d, J=6.1Hz, 3H), 1.37 (s, 9H), 1.28 (d, J=6.2Hz, 3H); 13 C NMR (151MHz, CDCl3) δ178.8, 156.5, 136.1, 134.6, 131.8, 129.6, 128.1, 127.5, 126.6, 76.3, 35.3, 31.3, 23.9, 23.5; HRMS (ESI) m / z: [M+Na] + calculated for C 20 H 25 NNaO2S: 366.1498, found: 366.1505; Enantiomeric excess: 92%, determined by HPLC (Daicel Chiralpak IF, isopropanol / hexane=5 / 95, flow rate=1.0mL / min, T=30°C, λ=254nm): t R =12.14min (major), t R = 14.58min (minor).

[0079] Example 8: Synthesis and characterization of compound 4h

[0080]

[0081] Using the same method as in Example 1, the final product 4h was obtained with a yield of 92% and ee = 87%.

[0082] The structure of compound 4h is as follows:

[0083]

[0084] Characterization data of compound 4h:

[0085] pentan-3-yl(R)-N-benzoyl-4-(tert-butyl)benzenesulfinimidate 4h: yield: 92% (34.1mg); flash column chromatography eluent, petroleum ether / ethyl acetate=10:1; colorless oil; [α] D 20 = -124.9 (c 0.29CH2Cl2); 1 H NMR (600MHz, CDCl3) δ8.27 (d, J=7.1Hz, 2H), 7.97 (d, J=8.5Hz, 2H), 7.60 (d, J=8.5Hz, 2H), 7.49 (t, J=7.3Hz, 1H), 7.42 (t, J=7. 4Hz, 2H), 4.82-4.74 (m, 1H), 1.84-1.75 (m, 2H), 1.65-1.52 (m, 2H), 1.36 (s, 9H), 0.99 (t, J=7.4Hz, 3H), 0.87 (t, J=7.4Hz, 3H); 13 C NMR (151MHz, CDCl3) δ178.7, 156.4, 136.3, 135.0, 131.7, 129.5, 128.0, 127.4, 126.5, 86.2, 35.3, 31.3, 27.9, 27.2, 9.6, 9.4; HRMS (ESI) m / z: [M+H] + Calculated for C 27 H 30NO2S: 372.1992, found: 372.1928; Enantiomeric excess: 87%, determined by HPLC (Daicel Chiralpak IF, isopropanol / hexane=5 / 95 flow rate=1.0mL / min, T=30°C, λ=254nm): t R = 9.79min (major), t R = 11.46 min (minor).

[0086] Example 9: Synthesis and characterization of compound 4i

[0087]

[0088] Using the same method as in Example 1, product 4i was finally separated with a yield of 95% and ee = 92%.

[0089] The structure of compound 4i is as follows:

[0090]

[0091] Characterization data of compound 4i:

[0092] cyclobutyl(R)-N-benzoyl-4-(tert-butyl)benzenesulfinimidate 4i: yield: 95% (33.7mg); flash column chromatography eluent, petroleum ether / ethyl acetate=10:1; colorless oil; [α] D 20 = -209.3 (c 0.27CH2Cl2); 1 H NMR (600MHz, CDCl3) δ8.28 (d, J=7.1Hz, 2H), 7.97 (d, J=8.5Hz, 2H), 7.61 (d, J=8.5Hz, 2H), 7.50 (t, J=7.3Hz, 1H), 7.42 (t, J=7.6Hz, 2H), 5.00 (p , J=7.6Hz, 1H), 2.43-2.36(m, 1H), 2.25-2.18(m, 1H), 2.18-2.12(m, 1H) , 2.12-2.05(m, 1H), 1.76-1.69(m, 1H), 1.54-1.48(m, 1H), 1.37(s, 9H); 13C NMR (151MHz, CDCl3) δ178.5, 156.7, 136.2, 134.0, 131.8, 129.6, 128.1, 127.7, 126.6, 73.3, 35.3, 32.4, 31.9, 31.3, 13.3; HRMS (ESI) m / z: [M+H] + Calculated for C 21 H 26 NO2S: 356.1679, found: 356.1683; HRMS (ESI) m / z: [M+H] + Calculated for C 27 H 30 NO2S: 372.1992, found: 372.1928; Enantiomeric excess: 92%, determined by HPLC (Daicel ChiralpakIF, isopropanol / hexane=20 / 80, flow rate=1.0mL / min, T=30°C, λ=254nm): t R = 8.53min (major), t R = 9.45min (minor).

[0093] Example 10: Synthesis and characterization of compound 4j

[0094]

[0095] Using the same method as in Example 1, product 4j was finally separated, with a yield of 91% and ee = 86%.

[0096] The structure of compound 4j is as follows:

[0097]

[0098] Characterization data for compound 4.j:

[0099] cyclohexyl(R)-N-benzoyl-4-(tert-butyl)benzenesulfinimidate 4j: yield: 91% (34.8mg); flash column chromatography eluent, petroleum ether / ethyl acetate=10:1; colorless oil; [α] D 20 = -147.1 (c 0.05CH2Cl2); 1H NMR (600MHz, CDCl3) δ8.32-8.25 (m, 2H), 7.95 (dd, J=8.6, 1.9Hz, 2H), 7.60 (dd, J=8 .6, 1.8Hz, 2H), 7.51-7.46 (m, 1H), 7.44-7.39 (m, 2H), 4.81 (dd, J=10.9, 7.3Hz, 1H), 2.19-2.11(m, 1H), 1.94-1.87(m, 1H), 1.82-1.68(m, 2H), 1.63(dd, J=21.7, 10.5Hz , 1H), 1.54-1.49(m, 1H), 1.49-1.41(m, 2H), 1.40-1.34(m, 10H), 1.28-1.21(m, 1H); 13 C NMR (151MHz, CDCl3) δ178.6, 156.4, 136.2, 134.8, 131.7, 129.5, 128.0, 127.4 , 126.5, 81.1, 53.6, 35.2, 33.6, 33.1, 31.1, 25.2, 23.8; HRMS (ESI) m / z: [M+Na] + Calculated for C 23 H 29 NNaO2S: 406.1811, found: 406.1818; Enantiomeric excess: 86%, determined by HPLC (Daicel Chiralpak IF, isopropanol / hexane=5 / 95, flow rate=1.0mL / min, T=30°C, λ=254nm): t R =12.88min(major), t R = 14.01 min (minor).

[0100] Example 11: Synthesis and characterization of compound 4k

[0101]

[0102] Using the same method as in Example 1, product 4k was finally separated, with a yield of 97% and ee = 91%.

[0103] The structure of compound 4k is as follows:

[0104]

[0105] Characterization data of compound 4k:

[0106] cyclopropylmethyl(R)-N-benzoyl-4-(tert-butyl)benzenesulfinimidate 4k:yield:97%(34.6mg);flash column chromatography eluent,petroleum ether / ethylacetate=10:1;colorless oil;[α] D 20 =-174.0(c 0.32CH2Cl2); 1 H NMR(600MHz,CDCl3)δ8.28(d,J=7.7Hz,2H),7.99(d,J=8.5Hz,2H),7.61(d,J=8.5Hz,2H),7.50(t,J=7.3Hz,1H),7.42(t,J=7.6Hz,2H),4.15(dd,J=10.8,7.7Hz,1H),3.90(dd,J=10.8,7.2Hz,1H),1.37(s,9H),1.21-1.13(m,1H),0.64-0.54(m,2H),0.39-0.32(m,1H),0.28-0.22(m,1H); 13 CNMR(151MHz,CDCl3)δ178.6,156.6,136.1,134.0,131.8,129.6,128.1,127.7,126.6,74.3,35.3,31.3,11.2,4.2,3.8;HRMS(ESI)m / z:[M+H] + calculated for C 21 H 26 NO2S:356.1679,found:356.1684;Enantiomeric excess:91%,determined by HPLC(Daicel ChiralpakIF,isopropanol / hexane=20 / 80,flow rate=1.0mL / min,T=30℃,λ=254nm):t R =8.81min(major),t R =9.75min(minor).

[0107] Example 12: Synthesis and characterization of compound 4l

[0108]

[0109] Using the same method as in Example 1, product 4l was finally separated, with a yield of 90% and ee = 85%.

[0110] The structure of compound 4l is as follows:

[0111]

[0112] Characterization data of compound 4l:

[0113] 2-cyclopentylethyl(R)-N-benzoyl-4-(tert-butyl)benzenesulfinimidate4l: yield: 90% (35.9mg); flash column chromatography eluent, petroleum ether / ethyl acetate=10:1; colorless oil; [α] D 20 = -155.9 (c 0.37CH2Cl2); 1 H NMR (600MHz, CDCl3) δ8.29 (d, J=7.6Hz, 2H), 7.97 (dd, J=8.4, 1.6Hz, 2H), 7.61 (dd, J=8.4, 1.6Hz, 2H), 7.50 (dd, J=7.4, 5.9Hz, 1H), 7.43 (t, J=6.8Hz, 2H), 4 .32-4.23(m, 1H), 3.99-3.89(m, 1H), 1.82-1.76(m, 1H), 1.73-1.62(m, 4H), 1. 57-1.51 (m, 2H), 1.49-1.42 (m, 2H), 1.36 (d, J=1.9Hz, 9H), 1.07-0.96 (m, 2H); 13 C NMR (151MHz, CDCl3) δ178.5, 156.7, 136.2, 133.8, 131.8, 129.6, 128.0, 127.7, 1 26.6, 67.8, 36.5, 36.0, 35.3, 32.6, 32.5, 31.2, 25.1, 25.1; HRMS (ESI) m / z: [M+H] + Calculated for C 24 H 32NO2S: 398.2148, found: 398.2156; Enantiomericexcess: 85%, determined by HPLC (Daicel Chiralpak AD, isopropanol / hexane=30 / 70, flow rate=1.0mL / min, T=30°C, λ=254nm): t R = 5.32min (major), t R = 4.90min (minor).

[0114] Example 13: Synthesis and characterization of compound 4m

[0115]

[0116] Using the same method as in Example 1, the final product 4m was obtained with a yield of 98% and ee = 84%.

[0117] The structure of compound 4m is as follows:

[0118]

[0119] Characterization data of compound 4m:

[0120] 2-cyclohexylethyl(R)-N-benzoyl-4-(tert-butyl)benzenesulfinimidate 4m: yield: 98% (40.4mg); flash column chromatography eluent, petroleum ether / ethylacetate=10:1; colorless oil; [α] D 20 = -153.9 (c 0.33CH2Cl2); 1 H NMR (600MHz, CDCl3) δ8.33-8.26 (m, 2H), 7.97 (d, J=8.5Hz, 2H), 7.61 (d, J=8.5Hz, 2H), 7.50 (t, J=7.3Hz, 1H), 7.43 (t, J=7.6Hz, 2H), 4.29 (dt , J=10.0, 6.7Hz, 1H), 3.96 (dt, J=10.0, 6.7Hz, 1H), 1.66-1.51 (m, 7H), 1.37(s, 9H), 1.34-1.30(m, 1H), 1.20-1.05(m, 3H), 0.89-0.78(m, 2H); 13C NMR (126MHz, CDCl3) δ178.5, 156.7, 136.2, 133.7, 131.8, 129.6, 128.0, 127.7, 126. 6, 66.2, 37.2, 35.3, 34.1, 33.2, 33.1, 31.3, 26.5, 26.2, 26.2; HRMS (ESI) m / z: [M+Na] + calculated for C 25 H 33 NNaO2S: 434.2124, found: 434.2128; Enantiomeric excess: 84%, determined by HPLC (Daicel Chiralpak AD, isopropanol / hexane=30 / 70, flow rate=1.0mL / min, T=30°C, λ=254nm): t R = 5.18min (major), t R = 4.65min (minor).

[0121] Example 14: Synthesis and characterization of compound 4n

[0122]

[0123] Using the same method as in Example 1, product 4n was finally separated with a yield of 94% and ee = 94%.

[0124] The structure of compound 4n is as follows:

[0125]

[0126] Characterization data of compound 4n:

[0127] benzyl(R)-N-benzoyl-4-(tert-butyl)benzenesulfinimidate 4n: yield: 94% (36.8mg); flash column chromatography eluent, petroleum ether / ethyl acetate=10:1; colorless oil; [α] D 20 = -160.0 (c 0.22CH2Cl2); 1H NMR (600MHz, CDCl3) δ8.33 (dd, J=8.0, 1.0Hz, 2H), 7.94 (d, J=8.7Hz, 2H), 7.59 (d, J=8.6Hz, 2H), 7.55-7.51 (m , 1H), 7.46 (t, J=7.5Hz, 2H), 7.41-7.25 (m, 5H), 5.36 (d, J=11.5Hz, 1H), 4.98 (d, J=11.5Hz, 1H), 1.36 (s, 9H); 13 C NMR (151MHz, CDCl3) δ178.7, 156.8, 136.0, 135.7, 133.5, 131.9, 129.6, 129. 0, 128.8, 128.7, 128.1, 127.8, 126.6, 70.1, 35.3, 31.3; HRMS (ESI) m / z: [M+H] + Calculated for C 24 H 26 NO2S: 392.1679, found: 392.1688; Enantiomeric excess: 94%, determined by HPLC (Daicel Chiralpak IG, isopropanol / hexane=30 / 70, flow rate=1.0mL / min, T=30°C, λ=254nm): t R =10.51min (major), t R = 12.89min (minor).

[0128] Example 15: Synthesis and characterization of compound 4o

[0129]

[0130] Using the same method as in Example 1, product 4o was finally separated, with a yield of 94% and ee = 94%.

[0131] The structure of compound 4o is as follows:

[0132]

[0133] Characterization data of compound 4o:

[0134] phenethyl(R)-N-benzoyl-4-(tert-butyl)benzenesulfinimidate 4o:yield:94%(38.0mg);flash column chromatography eluent,petroleum ether / ethyl acetate=10:1;colorless oil;[α] D 20 =-203.8(c 0.28CH2Cl2); 1 H NMR(600MHz,CDCl3)δ8.31(d,J=8.1Hz,2H),7.81(d,J=8.3Hz,2H),7.56-7.50(m,3H),7.44(t,J=7.6Hz,2H),7.27(dd,J=11.0,4.1Hz,2H),7.22(dd,J=10.6,3.9Hz,1H),7.16(d,J=7.6Hz,2H),4.50(dt,J=10.0,7.0Hz,1H),4.17(dt,J=10.1,7.0Hz,1H),3.01-2.94(m,2H),1.36(s,9H); 13 C NMR(151MHz,CDCl3)δ178.6,156.6,137.2,136.0,133.3,131.9,129.6,129.2,128.6,128.0,127.7,126.7,126.5,68.8,36.4,35.2,31.2;HRMS(ESI)m / z:[M+Na] + calculated forC 25 H 27 NNaO2S:428.1655,found:428.1655;Enantiomeric excess:94%,determined byHPLC(Daicel Chiralpak IF,isopropanol / hexane=5 / 95,flow rate=1.0mL / min,T=30℃,λ=254nm):t R =21.16min(major),t R =23.75min(minor).

[0135] Example 16: Synthesis and characterization of compound 4p

[0136]

[0137] Using the same method as in Example 1, product 4p was finally separated, with a yield of 98% and ee = 91%.

[0138] The structure of compound 4p is as follows:

[0139]

[0140] Characterization data of compound 4p:

[0141] 3-phenylpropyl(R)-N-benzoyl-4-(tert-butyl)benzenesulfinimidate 4p: yield: 98% (41.3mg); flash column chromatography eluent, petroleum ether / ethylacetate=10:1; colorless oil; [α] D 20 = -173.0 (c 0.24CH2Cl2); 1 H NMR (600MHz, CDCl3) δ8.31 (d, J=7.4Hz, 2H), 7.98 (d, J=8.3Hz, 2H), 7.62 (d, J=8.4Hz, 2H), 7.52 (t, J=7.3Hz, 1H), 7.44 (t, J=7.5Hz, 2H), 7.21 (t, J=7. 4Hz, 2H), 7.15 (t, J=7.3Hz, 1H), 7.10 (d, J=7.4Hz, 2H), 4.31-4.25 (m, 1H), 3.97-3.91(m, 1H), 2.66(t, J=7.6Hz, 2H), 2.00-1.94(m, 2H), 1.38(s, 9H); 13 C NMR (151MHz, CDCl3) δ178.5, 156.8, 141.0, 136.1, 133.5, 131.9, 129.6, 128.54, 128. 48, 128.1, 127.7, 126.6, 126.1, 67.0, 35.3, 31.9, 31.5, 31.3; HRMS (ESI) m / z: [M+Na] + Calculated for C 26 H 29NNaO2S: 442.1811, found: 442.1815; Enantiomeric excess: 91%, determined by HPLC (Daicel Chiralpak IF, isopropanol / hexane=5 / 95, flow rate=1.0mL / min, T=30°C, λ=254nm): t R =21.84min(major), t R = 23.96min (minor).

[0142] Example 17: Synthesis and characterization of compound 4q

[0143]

[0144] Using the same method as in Example 1, product 4q was finally separated with a yield of 90% and ee = 93%.

[0145] The structure of compound 4q is as follows:

[0146]

[0147] Characterization data of compound 4q:

[0148] 2-phenoxyethyl(R)-N-benzoyl-4-(tert-butyl)benzenesulfinimidate 4q: yield: 90% (37.8mg); flash column chromatography eluent, petroleum ether / ethylacetate=10:1; colorless oil; [α] D 20 = -258.1 (c 0.04CH2Cl2); 1 H NMR (600MHz, CDCl3) δ8.29 (d, J=7.8Hz, 2H), 8.01 (d, J=8.5Hz, 2H), 7.59 (d, J=8.5Hz, 2H), 7.51 (t, J=7.1Hz, 1H), 7.44 (t, J=7.5Hz, 2H), 7.26 (t, J= 7.9Hz, 2H), 6.95 (t, J=7.3Hz, 1H), 6.86 (d, J=8.1Hz, 2H), 4.77-4.71 (m, 1 H), 4.40-4.33(m, 1H), 4.26-4.20(m, 1H), 4.19-4.13(m, 1H), 1.36(s, 9H); 13C NMR (126MHz, CDCl3) δ178.8, 158.4, 156.9, 135.9, 133.5, 132.0, 129.6, 128. 1, 127.8, 126.6, 121.3, 114.7, 67.3, 66.7, 35.3, 31.2; HRMS (ESI) m / z: [M+Na] + Calculated for C 25 H 27 NNaO3S: 444.1604, found: 444.1609; Enantiomeric excess: 93%, determined by HPLC (Daicel Chiralpak OJ, isopropanol / hexane=30 / 70, flow rate=1.0mL / min, T=30°C, λ=254nm): t R = 10.73min (major), t R = 9.10min (minor).

[0149] Example 18: Synthesis and characterization of compound 4r

[0150]

[0151] Using the same method as in Example 1, product 4r was finally separated with a yield of 95% and ee = 93%.

[0152] The structure of compound 4r is as follows:

[0153]

[0154] Characterization data of compound 4r:

[0155] 4-fluorobenzyl(R)-N-benzoyl-4-(tert-butyl)benzenesulfinimidate 4r: yield: 95% (38.9mg); flash column chromatography eluent, petroleum ether / ethylacetate=10:1; colorless oil; [α] D 20 = -191.5 (c 0.06CH2Cl2); 1H NMR (600MHz, CDCl3) δ8.32 (d, J=7.4Hz, 2H), 7.93 (d, J=8.4Hz, 2H), 7.60 (d, J=8.5Hz, 2H), 7.53 (t, J=7.3Hz, 1H), 7.46 (t, J= 7.6Hz, 2H), 7.31 (dd, J=8.3, 5.5Hz, 2H), 7.00 (t, J=8.6Hz, 2H), 5.30 (d, J=11.5Hz, 1H), 4.95 (d, J=11.5Hz, 1H), 1.36 (s, 9H); 13 C NMR (151MHz, CDCl3) δ178.7, 163.0 (d, J=247.7Hz), 156.9, 135.9, 133.4, 132.0, 131.6 (d, J=3.4Hz), 131. 0 (d, J=8.5Hz), 129.6, 128.2, 127.8, 126.7, 115.7 (d, J=21.6Hz), 69.2, 35.3, 31.3; HRMS (ESI) m / z: [M+Na] + Calculated for C 24 H 24 FNO2S: 432.1404, found: 432.1411; 19 F NMR (565MHz, CDCl3) δ-112.80; Enantiomeric excess: 93%, determined by HPLC (Daicel Chiralpak ID, isopropanol / hexane=30 / 70, flow rate=1.0mL / min, T=30°C, λ=254nm): t R = 8.75min (major), t R = 8.24min (minor).

[0156] Example 19: Synthesis and characterization of compound 4S

[0157]

[0158] Using the same method as in Example 1, product 4s was finally separated, with a yield of 93% and ee = 91%.

[0159] The structure of compound 4S is as follows:

[0160]

[0161] Characterization data of compound 4s:

[0162] 4-chlorobenzyl(R)-N-benzoyl-4-(tert-butyl)benzenesulfinimidate 4s: yield: 93% (39.5mg); flash column chromatography eluent, petroleum ether / ethylacetate=10:1; colorless oil; [α] D 20 = -191.0 (c 0.11CH2Cl2); 1 H NMR (600MHz, CDCl3) δ8.31 (d, J=7.9Hz, 2H), 7.93 (d, J=8.3Hz, 2H), 7.60 (d, J=8.4Hz, 2H), 7.52 (dd, J=10.7, 3.8H z, 1H), 7.45 (t, J=7.6Hz, 2H), 7.27 (q, J=8.3Hz, 4H), 5.28 (d, J=11.7Hz, 1H), 4.93 (d, J=11.7Hz, 1H), 1.36 (s, 9H); 13 C NMR (151MHz, CDCl3) δ178.7, 157.0, 135.8, 134.7, 134.3, 133.3, 132.0, 130.3 , 129.6, 128.9, 128.2, 127.8, 126.7, 68.9, 35.3, 31.2; HRMS (ESI) m / z: [M+Na] + Calculated for C 20 H 24 ClNNaO2S: 448.1108, found: 448.1110; Enantiomeric excess: 91%, determined by HPLC (Daicel Chiralpak ID, isopropanol / hexane=30 / 70, flow rate=1.0mL / min, T=30°C, λ=254nm): t R = 9.49min (major), t R = 8.82min (minor).

[0163] Example 20: Synthesis and characterization of compound 4t

[0164]

[0165] Using the same method as in Example 1, 4 tons of product were finally separated, with a yield of 97% and ee = 94%.

[0166] The structure of compound 4t is as follows:

[0167]

[0168] Characterization data of compound 4t:

[0169] 4-bromobenzyl(R)-N-benzoyl-4-(tert-butyl)benzenesulfinimidate 4t: yield: 97% (45.7mg); flash column chromatography eluent, petroleum ether / ethylacetate=10:1; colorless oil; [α] D 20 = -16.3 (c 2.1CH2Cl2); 1 H NMR (600MHz, CDCl3) δ8.31 (d, J=7.3Hz, 2H), 7.94 (d, J=8.3Hz, 2H), 7.60 (d, J=8.3Hz, 2H), 7.52 (t, J=7.2Hz, 1H), 7.45 (dd, J=13.3, 7.7Hz, 4H), 7.19 (d, J=8.0Hz, 2H), 5.27 (d, J=11.8Hz, 1H), 4.92 (d, J=11.8Hz, 1H), 1.37 (s, 9H); 13 C NMR (151MHz, CDCl3) δ178.6, 156.9, 135.8, 134.7, 133.2, 132.0, 131.8, 130.5 , 129.6, 128.1, 127.7, 126.6, 122.8, 68.8, 35.3, 31.2; HRMS (ESI) m / z: [M+Na] + Calculated for C 24 H 24 BrNNaO2S: 492.0603, found: 492.0602; Enantiomeric excess: 94%, determined by HPLC (Daicel Chiralpak AD, isopropanol / hexane=30 / 70, flow rate=1.0mL / min, T=30°C, λ=254nm): t R = 8.29min (major), t R = 7.78min (minor).

[0170] Example 21: Synthesis and characterization of compound 4u

[0171]

[0172] Using the same method as in Example 1, product 4u was finally separated, with a yield of 96% and ee = 94%.

[0173] The structure of compound 4u is as follows:

[0174]

[0175] Characterization data of compound 4u:

[0176] 4-(trifluoromethyl)benzyl(R)-N-benzoyl-4-(tert-butyl)benzenesulfinimidate 4u: yield: 96% (44.0mg); flash column chromatographyeluent, petroleum ether / ethyl acetate=10:1; colorless oil; [α] D 20 = -31.1 (c0.27CH2Cl2); 1 H NMR (600MHz, CDCl3) δ8.35-8.27 (m, 2H), 7.97 (d, J=8.5Hz, 2H), 7.61 (d, J=8.5Hz, 2H), 7.59-7.51 ( m, 3H), 7.44 (dd, J=17.6, 8.0Hz, 4H), 5.35 (d, J=12.1Hz, 1H), 5.02 (d, J=12.1Hz, 1H), 1.37 (s, 9H); 13 C NMR (151MHz, CDCl3) δ178.8, 157.2, 139.8, 135.7, 133.2, 132.1, 129.7, 128.8, 128.2, 127.8, 126.8, 125.6 (q, J=3.9Hz), 68.4, 35.4, 31.2; 19 FNMR (565MHz, CDCl3) δ-62.69; HRMS (ESI) m / z: [M+Na] + Calculated for C 25 H 24F3NNaO2S: 482.1372, found: 482.1377; Enantiomeric excess: 94%, determined by HPLC (DaicelChiralpak ID, isopropanol / hexane=30 / 70, flow rate=1.0mL / min, T=30°C, λ=254nm): t R =7.47min (major), t R = 6.86min (minor).

[0177] Example 22: Synthesis and characterization of compound 4v

[0178]

[0179] Using the same method as in Example 1, product 4V was finally separated with a yield of 94% and ee = 92%.

[0180] The structure of compound 4v is as follows:

[0181]

[0182] Characterization data of compound 4v:

[0183] 3-methylbenzyl(R)-N-benzoyl-4-(tert-butyl)benzenesulfinimidate 4v: yield: 94% (38.1mg); flash column chromatography eluent, petroleum ether / ethylacetate=10:1; colorless oil; [α] D 20 = -122.4 (c 0.09CH2Cl2); 1 H NMR (600MHz, CDCl3) δ8.32 (d, J=7.7Hz, 2H), 7.93 (d, J=8.3Hz, 2H), 7.59 (d, J=8.3Hz, 2H), 7.52 (t, J=7.3Hz, 1H), 7.45 (t, J=7.6 Hz, 2H), 7.22 (t, J=7.4Hz, 1H), 7.12 (d, J=8.3Hz, 3H), 5.31 (d, J=11.4Hz, 1H), 4.93 (d, J=11.4Hz, 1H), 2.31 (s, 3H), 1.36 (s, 9H); 13C NMR (151MHz, CDCl3) δ178.7, 156.8, 138.4, 136.1, 135.6, 133.7, 131.9, 129.8, 129.7, 1 29.6, 128.7, 128.1, 127.9, 126.6, 126.1, 70.3, 35.3, 31.3, 21.5; HRMS (ESI) m / z: [M+Na] + Calculated for C 25 H 27 NNaO2S: 428.1655, found: 428.1656; Enantiomeric excess: 92%, determined by HPLC (Daicel Chiralpak IG, isopropanol / hexane=30 / 70, flow rate=1.0mL / min, T=30°C, λ=254nm): t R = 9.74min (major), t R = 12.85min (minor).

[0184] Example 23: Synthesis and characterization of compound 4w

[0185]

[0186] Using the same method as in Example 1, product 4w was finally separated, with a yield of 92% and ee = 93%.

[0187] The structure of compound 4w is as follows:

[0188]

[0189] Characterization data of compound 4w:

[0190] 3,5-dimethylbenzyl(R)-N-benzoyl-4-(tert-butyl)benzenesulfinimidate4w: yield: 92% (38.6mg); flash column chromatography eluent, petroleum ether / ethyl acetate=10:1; colorless oil; [α] D 20 = -105.1 (c 0.07CH2Cl2); 1H NMR (600MHz, CDCl3) δ 8.37-8.30 (m, 2H), 7.95 (d, J = 8.5Hz, 2H), 7.60 (d, J = 8.5Hz, 2H), 7.55-7.51 (m, 1H), 7.46 (t , J=7.7Hz, 2H), 6.94 (d, J=5.5Hz, 3H), 5.27 (d, J=11.3Hz, 1H), 4.90 (d, J=11.3Hz, 1H), 2.27 (s, 6H), 1.37 (s, 9H); 13 C NMR (151MHz, CDCl3) δ178.6, 156.7, 138.3, 136.1, 135.4, 133.5, 131.9, 130.5, 1 29.6, 128.1, 127.8, 126.9, 126.6, 70.2, 35.3, 31.2, 21.3; HRMS (ESI) m / z: [M+Na] + Calculated for C 26 H29NNaO2S: 442.1811, found: 442.1816; Enantiomeric excess: 93%, determined by HPLC (Daicel Chiralpak IG, isopropanol / hexane=30 / 70, flow rate=1.0mL / min, T=30°C, λ=254nm): t R = 9.04min (major), t R = 10.82min (minor).

[0191] Example 24: Synthesis and characterization of compound 4x

[0192]

[0193] Using the same method as in Example 1, product 4x was finally obtained with a yield of 78% and ee = 92%.

[0194] The structure of compound 4x is as follows:

[0195]

[0196] Characterization data of compound 4x:

[0197] naphthalen-1-ylmethyl(R)-N-benzoyl-4-(tert-butyl)benzenesulfinimidate4x:yield:78%(34.4mg);flash column chromatography eluent,petroleum ether / ethyl acetate=10:1;colorless oil;[α] D 20 =-108.2(c 0.2CH2Cl2); 1 H NMR(600MHz,CDCl3)δ8.38(dd,J=8.3,1.3Hz,2H),8.02(dd,J=5.4,4.3Hz,1H),7.88-7.81(m,4H),7.56-7.47(m,8H),7.41(dd,J=8.2,7.1Hz,1H),5.81(d,J=11.6Hz,1H),5.50(d,J=11.6Hz,1H),1.33(s,9H); 13 C NMR(151MHz,CDCl3)δ178.8,156.7,136.1,133.9,133.5,132.0,131.8,131.4,130.1,129.7,128.8,128.7,128.2,127.8,126.8,126.5,126.2,125.3,124.0,68.8,35.3,31.2;HRMS(ESI)m / z:[M+Na] + calculated for C 28 H 27 NNaO2S:464.1655,found:464.1658;Enantiomeric excess:92%,determined by HPLC(DaicelChiralpak ID,isopropanol / hexane=30 / 70,flow rate=1.0mL / min,T=30℃,λ=254nm):t R =9.34min(major),t R =10.37min(minor).

[0198] Example 25: Synthesis and characterization of compound 4y

[0199]

[0200] Using the same method as in Example 1, product 4y was finally separated, with a yield of 89% and ee = 92%.

[0201] The structure of compound 4y is as follows:

[0202]

[0203] Characterization data of compound 4y:

[0204] 4-nitrophenethyl(R)-N-benzoyl-4-(tert-butyl)benzenesulfinimidate 4y: yield: 89% (40.0mg); flash column chromatography eluent, petroleum ether / ethylacetate=10:1; colorless oil; [α] D 20 = -155.3 (c 0.4CH2Cl2); 1 H NMR (600MHz, CDCl3) δ8.24 (d, J=8.1Hz, 2H), 8.07 (d, J=8.2Hz, 2H), 7.83 (d, J=8.3Hz, 2H), 7.56 (d, J=8.3Hz, 2H), 7.54-7.49 (m, 1H), 7.43 (t, J=7.6Hz, 2H), 7.30 (d, J=8.4Hz, 2H), 4.48 (dt, J=10.6, 6.4Hz, 1H), 4.20 (dt, J=10.6, 6.4Hz, 1H), 3.04 (t, J=6.4Hz, 2H), 1.36 (s, 9H); 13 H MS(ESI)m / z:[M+Na] + Calculated for C 25 H 26 N2NaO4S: 473.1505, found: 473.1508; Enantiomeric excess: 92%, determined by HPLC (Daicel Chiralpak IF, isopropanol / hexane=20 / 80, flow rate=1.0mL / min, T=30°C, λ=254nm): tR = 17.13min (major), t R = 16.01min (minor).

[0205] Example 26: Synthesis and characterization of compound 4z

[0206]

[0207] Using the same method as in Example 1, product 4z was finally separated with a yield of 75% and ee = 97%.

[0208] The structure of compound 4z is as follows:

[0209]

[0210] Characterization data of compound 4z:

[0211] 3,3,3-trifluoropropyl(R)-N-benzoyl-4-(tert-butyl)benzenesulfinimidate4z: yield: 75% (29.8mg); flash column chromatography eluent, petroleum ether / ethyl acetate=10:1; colorless oil; [α] D 20 = -64.2 (c 0.04CH2Cl2); 1 H NMR (600MHz, CDCl3) δ8.28 (d, J=7.1Hz, 2H), 7.98 (d, J=8.6Hz, 2H), 7.63 (d, J=8.6Hz, 2H), 7.52 (t, J=7.3Hz, 1H), 7 .44 (t, J=7.6Hz, 2H), 4.50 (dt, J=11.2, 6.4Hz, 1H), 4.21 (dt, J=11.2, 6.4Hz, 1H), 2.57-2.44 (m, 2H), 1.37 (s, 9H); 13 C NMR (151MHz, CDCl3) δ178.8, 157.2, 135.6, 132.9, 132.2, 129.6, 128.2, 127.7, 1 26.8, 126.5 (q, J=236.1Hz), 61.0 (q, J=3.6Hz), 35.4, 34.6 (q, J=29.1Hz), 31.2; 19 F NMR(565MHz, CDCl3)δ-64.62; HRMs(EsI)m / z: [M+Na] +Calculated for C 20 H 22 F3NNaO3S: 420.1216, found: 420.1219; Enantiomericexcess: 97%, determined by HPLC (Daicel Chiralpak IC, isopropanol / hexane=10 / 90, flow rate=1.0mL / min, T=30°C, λ=254nm): t R = 8.78min (major), t R = 9.77min (minor).

[0212] Example 27: Synthesis and characterization of compound 4aa

[0213]

[0214] Using the same method as in Example 1, product 4aa was finally separated, with a yield of 87% and ee = 93%.

[0215] The structure of compound 4aa is as follows:

[0216]

[0217] Characterization data of compound 4aa:

[0218] 4-fluorobutyl(R)-N-benzoyl-4-(tert-butyl)benzenesulfinimidate 4aa: yield: 87% (31.3mg); flash column chromatography eluent, petroleum ether / ethylacetate=10:1; colorless oil; [α] D 20 = -570.6 (c 0.02CH2Cl2); 1H NMR (600MHz, CDCl3) δ8.29 (d, J=7.3Hz, 2H), 7.98 (d, J=8.5Hz, 2H), 7.63 (d, J=8.5Hz, 2H), 7.51 (t, J=7.3Hz, 1H), 7.44 (t, J=7.6Hz, 2H), 4.55-4 .50 (m, 1H), 4.48-4.43 (m, 1H), 4.39 (dt, J=10.3, 6.2Hz, 1H), 4.06 (dt, J=10.4, 6.1Hz, 1H), 2.10-1.98(m, 2H), 1.37(s, 9H), 1.35-1.24(m, 2H); 13 C NMR (151MHz, CDCl3) δ178.6, 156.9, 135.9, 133.3, 131.9, 129.6, 128.1, 127.7, 126.7, 80.3 (d, J = 165.4Hz), 63.5 (d, J = 5.1Hz), 35.3, 31.2.30.9 (d, J = 20.0Hz); 19 F NMR(376MHz, CDCl3)δ-222.36--222.81(m); HRMS(ESI)m / z: [M+Na] + Calculated for C 20 H 24 FNNaO2S: 384.1404, found: 384.1412; Enantiomeric excess: 93%, determined by HPLC (Daicel Chiralpak OD, isopropanol / hexane=5 / 95, flow rate=1.0mL / min, T=30°C, λ=254nm): t R =12.18min (major), t R = 13.36min (minor).

[0219] Example 28: Synthesis and characterization of compound 4ab

[0220]

[0221] Using the same method as in Example 1, product 4ab was finally separated with a yield of 98% and ee = 93%.

[0222] The structure of compound 4ab is as follows:

[0223]

[0224] Characterization data of compound 4ab:

[0225] 3-chloropropyl(R)-N-benzoyl-4-(tert-butyl)benzenesulfinimidate 4ab: yield: 98% (37.2mg); flash column chromatography eluent, petroleum ether / ethylacetate=10:1; colorless oil; [α] D 20 = -193.8 (c 0.06CH2Cl2); 1 H NMR (600MHz, CDCl3) δ8.32-8.24 (m, 2H), 8.02-7.95 (m, 2H), 7.65-7.62 (m, 2H), 7.53-7.50 (m, 1H), 7.44 (t, J=7.6 Hz, 2H), 4.40 (dt, J=10.4, 5.9Hz, 1H), 4.11-4.04 (m, 1H), 3.57 (t, J=6.3Hz, 2H), 2.11-2.06 (m, 2H), 1.37 (s, 9H); 13 C NMR (151MHz, CDCl3) δ178.6, 157.0, 135.9, 133.2, 132.0, 129.6, 128.1, 127.7, 126.7, 64.1, 41.0, 35.4, 32.6, 31.3; HRMS (ESI) m / z: [M+H] + Calculated for C 20 H 25 ClNO2S: 378.1289, found: 378.1298; Enantiomeric excess: 93%, determined by HPLC (Daicel Chiralpak OD, isopropanol / hexane=5 / 95, flow rate=1.0mL / min, T=30°C, λ=254nm): t R =12.80min (major), t R = 14.25min (minor).

[0226] Example 29: Synthesis and characterization of compound 4ac

[0227]

[0228] Using the same method as in Example 1, product 4ac was finally separated, with a yield of 96% and ee = 91%.

[0229] The structure of compound 4ac is as follows:

[0230]

[0231] Characterization data of compound 4ac:

[0232] but-3-yn-1-yl(R)-N-benzoyl-4-(tert-butyl)benzenesulfinimidate 4ac: yield: 96% (34.1mg); flash column chromatography eluent, petroleum ether / ethylacetate=10:1; colorless oil; [α] D 20 = -214.1 (c 0.29CH2Cl2); 1 H NMR (600MHz, CDCl3) δ8.30-8.26 (m, 2H), 8.04-8.00 (m, 2H), 7.65-7.61 (m, 2H), 7.52 (t, J=7.3Hz, 1H), 7.44 (t, J=7.6Hz, 2H), 4.45 (dt, J=10.1, 6.8Hz, 1H), 4.10 (dt, J=10.1, 6.6Hz, 1H), 2.64-2.53 (m, 2H), 2.00 (t, J=2.6Hz, 1H), 1.37 (s, 9H); 13 C NMR (151MHz, CDCl3) δ178.7, 156.9, 135.8, 133.3, 132.0, 129.6, 128.1, 127.8, 126.7, 79.9, 70.6, 66.3, 35.3, 31.3, 20.4; HRMS (ESI) m / z: [M+Na] + Calculated for C 21 H 23 NNaO2S: 376.1342, found: 376.1346; Enantiomericexcess: 91%, determined by HPLC (Daicel Chiralpak IF, isopropanol / hexane=20 / 80, flow rate=1.0mL / min, T=30°C, λ=254nm): t R =7.29min (major), t R = 8.04min (minor).

[0233] Example 30: Synthesis and characterization of compound 4ad

[0234]

[0235] Using the same method as in Example 1, product 4ad was finally separated with a yield of 93% and ee = 95%.

[0236] The structure of compound 4ad is as follows:

[0237]

[0238] Characterization data of compound 4ad:

[0239] pent-4-yn-1-yl(R)-N-benzoyl-4-(tert-butyl)benzenesulfinimidate 4ad: yield: 93% (34.1mg); flash column chromatography eluent, petroleum ether / ethylacetate=10:1; colorless oil; [α] D 20 = -127.1 (c 0.37CH2Cl2); 1 H NMR (600MHz, CDCl3) δ8.29 (d, J=7.1Hz, 2H), 7.98 (d, J=8.5Hz, 2H), 7.62 (d, J=8.5Hz, 2H), 7.51 (t, J=7.3Hz, 1H), 7.43 (t, J=7.7H z, 2H), 4.38 (dt, J=10.2, 6.2Hz, 1H), 4.05 (dt, J=10.2, 6.0Hz, 1H), 2.26 (td, J=7.0, 2.6Hz, 2H), 1.94-1.80 (m, 3H), 1.37 (s, 9H); 13 C NMR (151MHz, CDCl3) δ178.7, 156.9, 135.8, 133.3, 132.0, 129.6, 128.1, 127.8, 126.7, 79.9, 70.6, 66.3, 35.3, 31.3, 20.4; HRMS (ESI) m / z: [M+Na] + Calculated for C 22 H 25NNaO2S: 390.1498, found: 390.1503; Enantiomeric excess: 95%, determined by HPLC (Daicel Chiralpak OD, isopropanol / hexane=5 / 95, flow rate=0.5mL / min, T=30°C, λ=254nm): t R =22.19min (major), t R = 25.51min (minor).

[0240] Example 31: Synthesis and characterization of compound 4ae

[0241]

[0242] Using the same method as in Example 1, product 4ae was finally separated, with a yield of 74% and ee = 87%.

[0243] The structure of compound 4ae is as follows:

[0244]

[0245] Characterization data of compound 4ae:

[0246] but-2-yn-1-yl(R)-N-benzoyl-4-(tert-butyl)benzenesulfinimidate 4ae: yield: 74% (26.1mg); flash column chromatography eluent, petroleum ether / ethylacetate=10:1; colorless oil; [α] D 20 = -156.0 (c 0.03CH2Cl2); 1 H NMR (600MHz, CDCl3) δ8.28 (d, J=7.4Hz, 2H), 8.02 (d, J=8.5Hz, 2H), 7.62 (d, J=8.5Hz, 2H), 7.51 (t, J=7.3 Hz, 1H), 7.43 (t, J=7.6Hz, 2H), 5.05-5.00 (m, 1H), 4.66-4.61 (m, 1H), 1.83 (t, J=2.2Hz, 3H), 1.37 (s, 9H); 13C NMR (151MHz, CDCl3) δ178.7, 156.9, 135.8, 133.3, 132.0, 129.6, 128.1, 127.9, 126.6, 85.8, 76.8, 73.8, 57.6, 35.3, 31.3, 4.0; HRMS (ESI) m / z: [M+H] + calculated for C 21 H 24 NO2S: 354.1528, found: 354.1530; Enantiomeric excess: 87%, determined by HPLC (Daicel Chiralpak IF, isopropanol / hexane=10 / 90, flow rate=1.0mL / min, T=30°C, λ=254nm): t R =13.09min (major), t R = 14.04min (minor).

[0247] Example 32: Synthesis and characterization of compound 4af

[0248]

[0249] Using the same method as in Example 1, product 4af was finally separated, with a yield of 92%.

[0250] The structure of compound 4af is as follows:

[0251]

[0252] Characterization data of compound 4af:

[0253] (3S,5S,8R,9S,10S,13R,14S,17R)-10,13-dimethyl-17-((R)-6-methylheptan-2-yl)hexadecahydro-1H-cyclopenta[a]phenanthren-3-yl(R)-N-benzoyl-4-(tert-butyl)benzenesulfinimidate 4af: yield: 92% (59.2mg); >95: 5dr (determined by 1 HNMR); flash column chromatography eluent, petroleum ether / ethyl acetate=10:1; colorless oil; [α] D20 = -45.0 (c 0.59CH2Cl2); 1 H NMR (600MHz, CDCl3) δ8.28 (d, J=7.1Hz, 2H), 7.95 (d, J=8.6Hz, 2H), 7.59 (d, J=8.6Hz, 2H), 7.49 (t, J=7.3Hz, 1H), 7.42 (t, J=7.5Hz, 2H), 4.80-4.73 (m, 1H), 2.21-2.14 (m, 1 H), 1.99-1.93 (m, 1H), 1.86-1.42 (m, 10H), 1.36 (s, 9H), 1.34-0.93 (m, 19H), 0.90 (d, J=6.5Hz, 3H), 0.87 (d, J=2.7Hz, 3H), 0.86 (d, J=2.7Hz, 3H), 0.79 (s, 3H), 0.64 (s, 3H); 13 C NMR (151MHz, CDCl3) δ178.7, 156.4, 136.3, 134.9, 131.7, 129.6, 128.0, 127.5, 126.5, 82.3, 56.5, 56.4, 54.3, 45.0, 42.7, 40.1, 39.6, 37. 1, 36.3, 35.9, 35.6, 35.5, 35.3, 32.0, 31.3, 30.0, 28.7, 28.4, 28.1, 24.3, 23.9, 23.0, 22.7, 21.4, 18.8, 12.4, 12.2; HRMS (ESI) m / z: [M+Na] + Calculated for C 42 H 61 NNaO2S: 666.4321, found: 666.4313.

[0254] Example 33: Synthesis and characterization of compound 4ag

[0255]

[0256] Using the same method as in Example 1, 4 ag of product was finally separated, with a yield of 83% and ee = 86%.

[0257] The structure of compound 4ag is as follows:

[0258]

[0259] Characterization data of compound 4ag:

[0260] isobutyl(S)-N-bennzoyl-4-fluorobenzenesulfinimidate 4ag:yield:83%(26.5mg);flash column chromatography eluent,petroleum ether / ethyl acetate=10:1;colorless oil;[α] D 20 =-197.0(c 0.27CH2Cl2); 1 H NMR(600MHz,CDCl3)δ8.30-8.25(m,2H),8.09-8.05(m,2H),7.54-7.49(m,1H),7.44(t,J=7.6Hz,2H),7.30(dd,J=12.6,4.4Hz,2H),4.06-4.01(m,1H),3.69-3.64(m,1H),1.96-1.88(m,1H),0.91-0.84(m,6H); 13 CNMR(151MHz,CDCl3)δ178.5,165.5(d,J=255.3Hz),135.9,132.7(d,J=2.4Hz),132.0,130.5(d,J=9.1Hz),129.6,128.2,116.9(d,J=22.1Hz),74.2,28.9,19.1; 19 F NMR(565MHz,CDCl3)δ-105.46;HRMS(ESI)m / z:[M+H] + calculated for C 17 H 19 FNO2S:320.115,found:320.1119;Enantiomeric excess:86%,determined by HPLC(Daicel ChiralpakIF,isopropanol / hexane=20 / 80,flow rate=1.0mL / min,T=30℃,λ=254nm):t R =6.53min(major),t R =7.73min(minor).

[0261] Example 34: Synthesis and characterization of compound 4ah

[0262]

[0263] Using the same method as in Example 1, the final product 4ah was obtained by separation, with a yield of 73% and ee = 92%.

[0264] The structure of compound 4ah is as follows:

[0265]

[0266] Characterization data of compound 4ah:

[0267] isobutyl(R)-N-benzoyl-4-chlorobenzenesulfinimidate 4ah: yield: 73% (24.6mg); flash column chromatography eluent, petroleum ether / ethyl acetate=10:1; colorless oil; [α] D 20 = -210.5 (c 0.25CH2Cl2); 1 H NMR (600MHz, CDCl3) δ8.27 (dd, J=8.1, 0.9Hz, 2H), 7.99 (d, J=8.6Hz, 2H), 7.58 (d, J=8.6Hz, 2H), 7.52 (t, J=7.3Hz, 1H), 7 .44 (t, J=7.6Hz, 2H), 4.04 (dd, J=9.6, 6.5Hz, 1H), 3.66 (dd, J=9.6, 6.6Hz, 1H), 2.00-1.86 (m, 1H), 0.88 (t, J=6.4Hz, 6H); 13 C NMR (151MHz, CDCl3) δ178.5, 139.4, 135.8, 135.5, 132.0, 129.8, 129.6, 129.3, 128.1, 74.3, 28.9, 19.0; HRMS (ESI) m / z: [M+H] + calculated for C 17 H 19 ClNO2S: 336.0820, found: 336.0822; Enantiomeric excess: 92%, determined by HPLC (Daicel Chiralpak IF, isopropanol / hexane=20 / 80, flow rate=1.0mL / min, T=30°C, λ=254nm): t R = 6.85min (major), t R = 8.04min (minor).

[0268] Example 35: Synthesis and characterization of compound 4ai

[0269]

[0270] Using the same method as in Example 1, product 4ai was finally separated with a yield of 88% and ee = 95%.

[0271] The structure of compound 4ai is as follows:

[0272]

[0273] Characterization data of compound 4ai:

[0274] isobutyl(R)-N-benzoyl-4-bromobenzenesulfinimidate 4ai: yield: 88% (33.5mg); flash column chromatography eluent, petroleum ether / ethyl acetate=10:1; colorless oil; [α] D 20 = -185.5 (c 0.23CH2Cl2); 1 H NMR (600MHz, CDCl3) δ8.27 (d, J=8.1Hz, 2H), 7.94-7.87 (m, 2H), 7.77-7.72 (m, 2H), 7.56-7.49 (m, 1H), 7.44 (t, J=7.6Hz, 2H), 4.07-4.01 (m, 1H), 3.66 (dd, J=9.5, 6.7Hz, 1H), 1.98-1.88 (m, 1H), 0.88 (t, J=6.2Hz, 6H); 13 C NMR (151MHz, CDCl3) δ178.5, 136.1, 135.8, 132.8, 132.1, 129.6, 129.5, 128.2, 127.8, 74.4, 28.9, 19.0; HRMS (ESI) m / z: [M+H] + Calculated for C 17 H 19BrNO2S: 380.0314, found: 380.0324; Enantiomeric excess: 95%, determined by HPLC (Daicel ChiralpakIF, isopropanol / hexane=20 / 80, flow rate=1.0mL / min, T=30°C, λ=254nm): t R =7.29min (major), t R = 8.57min (minor).

[0275] Example 36: Synthesis and characterization of compound 4aj

[0276]

[0277] Using the same method as in Example 1, product 4aj was finally separated, with a yield of 71% and ee = 95%.

[0278] The structure of compound 4aj is as follows:

[0279]

[0280] Characterization data of compound 4aj:

[0281] isobutyl(R)-N-benzoyl-4-(trifluoromethyl)benzenesulfinimidate 4aj: yield: 71% (26.4mg); flash column chromatography eluent, petroleum ether / ethylacetate=10:1; colorless oil; [α] D 20 = -195.1 (c 0.23CH2Cl2); 1 H NMR (600MHz, CDCl3) δ8.28 (d, J=7.5Hz, 2H), 8.18 (d, J=8.2Hz, 2H), 7.87 (d, J=8.2Hz, 2H), 7.53 (dd, J=10.7, 4.0Hz, 1H) , 7.45 (t, J=7.5Hz, 2H), 4.10 (dd, J=9.5, 6.6Hz, 1H), 3.73 (dd, J=9.5, 6.6Hz, 1H), 2.01-1.92 (m, 1H), 0.92-0.89 (m, 6H); 13C NMR (151MHz, CDCl3) δ178.6, 141.2, 135.6, 134.6 (q, J=32.7Hz), 132.2, 129.6, 128.5, 128.2, 126.5 (q, J=3.6Hz), 123.5 (q, J=272.7Hz), 77.3, 77.1, 76.8, 75.0, 29.0, 19.0; 19 F NMR (565MHz, CDCl3) δ-63.05; HRMS (ESI) m / z: [M+Na] + Calculated for C 18 H 18 F3NNaO2S: 392.0903, found: 392.0904; Enantiomericexcess: 95%, determined by HPLC (Daicel Chiralpak IF, isopropanol / hexane=20 / 80, flow rate=1.0mL / min, T=30°C, λ=254nm): t R = 5.71min (major), t R = 6.08min (minor).

[0282] Example 37: Synthesis and characterization of compound 4ak

[0283]

[0284] Using the same method as in Example 1, product 4ak was finally separated, with a yield of 44% and ee = 87%.

[0285] The structure of compound 4ak is as follows:

[0286]

[0287] Characterization data of compound 4ak:

[0288] isobutyl(R)-N-benzoyl-4-cyanobenzenesulfinimidate 4ak: yield: 44% (14.2mg); flash column chromatography eluent, petroleum ether / ethyl acetate=10:1; colorless oil; [α] D 20 = -114.1 (c 0.14CH2Cl2); 1H NMR (600MHz, CDCl3) δ8.25 (d, J=7.1Hz, 2H), 8.17 (d, J=8.2Hz, 2H), 7.89 (d, J=8.1Hz, 2H), 7.53 (t, J=7.3H z, 1H), 7.45 (t, J=7.5Hz, 2H), 4.15-4.06 (m, 1H), 3.82-3.72 (m, 1H), 2.02-1.93 (m, 1H), 0.94-0.87 (m, 6H); 13 C NMR (151MHz, CDCl3) δ178.6, 142.2, 135.4, 133.1, 132.3, 129.6, 128.7, 128.3, 117.6, 116.5, 75.4, 29.0, 19.0; HRMS (ESI) m / z: [M+Na] + Calculated for C 18 H 18 N2NaO2S: 349.0987, found: 349.0988; Enantiomeric excess: 87%, determined by HPLC (DaicelChiralpak IF, isopropanol / hexane=20 / 80, flow rate=1.0mL / min, T=30°C, λ=254nm): t R = 9.59min (major), t R = 11.74 min (minor).

[0289] Example 38: Synthesis and characterization of compound 4al

[0290]

[0291] Using the same method as in Example 1, product 4al was finally separated, with a yield of 66% and ee = 84%.

[0292] The structure of compound 4al is as follows:

[0293]

[0294] Characterization data of compound 4al:

[0295] isobutyl(R)-N-benzoyl-4-nitrobenzenesulfinimidate 4al: yield: 66% (22.8mg); flash column chromatography eluent, petroleum ether / ethyl acetate=10:1; colorless oil; [α] D 20 = -137.7 (c 0.23CH2Cl2); 1 H NMR (600MHz, CDCl3) δ8.44 (d, J=8.6Hz, 2H), 8.36-8.19 (m, 4H), 7.54 (t, J=7.3Hz, 1H), 7.45 (t, J=7.5Hz, 2H), 4.12 ( dd, J=9.5, 6.6Hz, 1H), 3.79 (dd, J=9.4, 6.7Hz, 1H), 2.05-1.94 (m, 1H), 0.92 (d, J=5.3Hz, 3H), 0.91 (d, J=6.1Hz, 3H); 13 C NMR (151MHz, CDCl3) δ178.6, 150.4, 143.8, 135.3, 132.4, 129.6, 129.2, 128.3, 124.6, 75.5, 29.0, 19.0; HRMS (ESI) m / z: [M+Na] + Calculated for C 17 H18N2NaO4S: 369.0885, found: 369.0885; Enantiomeric excess: 84%, determined by HPLC (Daicel Chiralpak IF, isopropanol / hexane=20 / 80, flow rate=1.0mL / min, T=30°C, λ=254nm): t R =10.38min (major), t R = 13.03min (minor).

[0296] Example 39: Synthesis and characterization of compound 4am

[0297]

[0298] Using the same method as in Example 1, the final product 4am was obtained with a yield of 62% and ee = 85%.

[0299] The structure of compound 4am is as follows:

[0300]

[0301] Characterization data of compound 4am:

[0302] methyl (R)-4-(N-benzoyl-isobutoxysulfinimidoyl)benzoate 4am: yield: 62% (22.2 mg); flash column chromatography eluent, petroleum ether / ethyl acetate = 10:1; colorless oil; [α] D 20 = -107.7 (c 0.22 CH2Cl2); 1 1H NMR (600 MHz, CDCl3) δ 8.31 - 8.23 (m, 4H), 8.12 (d, J = 8.5 Hz, 2H), 7.52 (t, J = 6.7 Hz, 1H), 7.44 (t, J = 7.5 Hz, 2H), 4.07 (dd, J = 9.6, 6.5 Hz, 1H), 3.98 (s, 3H), 3.70 (dd, J = 9.5, 6.6 Hz, 1H), 1.99 - 1.90 (m, 1H), 0.89 (t, J = 6.5 Hz, 6H); 13 = 13 C NMR (151 MHz, CDCl3) δ 178.6, 165.9, 141.5, 135.7, 134.1, 132.1, 130.6, 129.6, 128.2, 128.0, 74.7, 52.8, 29.0, 19.0; HRMS (ESI) m / z: [M+Na] + calculated for C 19 H 21 NNaO4S: 382.1089, found: 382.1090; Enantiomeric excess: 85%, determined by HPLC (Daicel Chiralpak IF, isopropanol / hexane = 20 / 80, flow rate = 1.0 mL / min, T = 30 °C, λ = 254 nm): t R = 8.69 min (major), t R = 10.64 min (minor).

[0303] Example 40: Synthesis and characterization of compound 4an

[0304]

[0305] Using the same method as in Example 1, product 4an was finally separated, with a yield of 97% and ee = 84%.

[0306] The structure of compound 4an is as follows:

[0307]

[0308] Characterization data of compound 4an:

[0309] isobutyl(R)-N-benzoylbenzenesulfinimidate 4an: yield: 97% (29.1mg); flash column chromatography eluent, petroleum ether / ethyl acetate=10:1; colorless oil; [α] D 20 = -237.3 (c 0.24CH2Cl2); 1 H NMR (600MHz, CDCl3) δ8.32-8.28 (m, 2H), 8.05 (dd, J=8.0, 1.3Hz, 2H), 7.65-7.59 (m, 3H), 7.51 (t, J=7.3Hz, 1H), 7.44 (dd , J=11.4, 4.0Hz, 2H), 4.05 (dd, J=9.6, 6.6Hz, 1H), 3.66 (dd, J=9.6, 6.7Hz, 1H), 1.98-1.88 (m, 1H), 0.88 (t, J=7.0Hz, 6H); 13 C NMR (151MHz, CDCl3) δ178.5, 137.0, 136.1, 132.8, 131.9, 129.6, 129.5, 128.1, 127.9, 74.1, 28.9, 19.1; HRMS (ESI) m / z: [M+Na] + Calculated for C 17 H 19 NNaO2S: 324.1029, found: 3324.1034; Enantiomeric excess: 84%, determined by HPLC (Daicel Chiralpak IF, isopropanol / hexane=10 / 90, flow rate=1.0mL / min, T=30°C, λ=254nm): t R =10.15min (major), t R = 12.23min (minor).

[0310] Example 41: Synthesis and characterization of compound 4ao

[0311]

[0312] Using the same method as in Example 1, product 4ao was finally separated, with a yield of 97% and ee = 86%.

[0313] The structure of compound 4ao is as follows:

[0314]

[0315] Characterization data of compound 4ao:

[0316] isobutyl(R)-N-benzoyl-4-methylbenzenesulfinimidate 4ao: yield: 97% (29.1mg); flash column chromatography eluent, petroleum ether / ethyl acetate=10:1; colorless oil; [α] D 20 = -189.3 (c 0.20CH2Cl2); 1 H NMR (600MHz, CDCl3) δ8.29 (d, J=7.7Hz, 2H), 7.93 (d, J=7.2Hz, 2H), 7.50 (t, J=6.9Hz, 1H), 7.43 (t, J=7.2Hz, 2H), 7.39 ( d, J=7.6Hz, 2H), 4.02 (dd, J=8.0, 7.2Hz, 1H), 3.70-3.58 (m, 1H), 2.46 (s, 3H), 1.97-1.86 (m, 1H), 0.87 (t, J=6.4Hz, 6H); 13 C NMR (151MHz, CDCl3) δ178.5, 143.7, 136.2, 133.8, 131.8, 130.2, 129.6, 128.1, 127.9, 73.8, 28.9, 21.7, 19.1; HRMS (ESI) m / z: [M+Na] + calculated for C 18 H 21NNaNO2S: 338.1185, found: 338.1186; Enantiomeric excess: 86%, determined by HPLC (Daicel Chiralpak IF, isopropanol / hexane=20 / 80, flow rate=1.0mL / min, T=30°C, λ=254nm): t R =7.40min (major), t R = 9.30min (minor).

[0317] Example 42: Synthesis and characterization of compound 4ap

[0318]

[0319] Using the same method as in Example 1, product 4ap was finally separated, with a yield of 81% and ee = 78%.

[0320] The structure of compound 4ap is as follows:

[0321]

[0322] Characterization data of compound 4ap:

[0323] isobutyl(R)-N-benzoyl-4-isopropylbenzenesulfinimidate 4ap: yield: 81% (27.8mg); flash column chromatography eluent, petroleum ether / ethyl acetate=10:1; colorless oil; [α] D 20 = -114.1 (c 0.18CH2Cl2); 1 H NMR (600MHz, CDCl3) δ8.29 (d, J=7.7Hz, 2H), 7.96 (d, J=8.2Hz, 2H), 7.50 (t, J=7.3Hz, 1H), 7.44 (dd, J=14.4, 7.7Hz, 4H), 4.05 (dd, J =9.6, 6.6Hz, 1H), 3.68 (dd, J=9.5, 6.7Hz, 1H), 3.09-2.93 (m, 1H), 2.01-1.87 (m, 1H), 1.30 (d, J=6.9Hz, 6H), 0.88 (t, J=6.8Hz, 6H); 13C NMR (151MHz, CDCl3) δ178.5, 154.4, 136.1, 134.0, 131.8, 129.6, 128.1, 128.0, 127.7, 74.1, 34.3, 28.9, 23.86, 23.85, 19.1;; HRMS (ESI) m / z: [M+Na] + Calculated for C 20 H 25 NNaO2S: 366.1498, found: 36.1504; Enantiomeric excess: 78%, determined by HPLC (Daicel Chiralpak IF, isopropanol / hexane=20 / 80, flow rate=1.0mL / min, T=30°C, λ=254nm): t R = 6.53min (major), t R = 7.43min (minor).

[0324] Example 43: Synthesis and characterization of compound 4aq

[0325]

[0326] Using the same method as in Example 1, the final product 4aq was obtained with a yield of 96% and ee = 81%.

[0327] The structure of compound 4aq is as follows:

[0328]

[0329] Characterization data of compound 4aq:

[0330] isobutyl(R)-N-benzoyl-4-methoxybenzenesulfinimidate 4aq: yield: 96% (31.9mg); flash column chromatography eluent, petroleum ether / ethyl acetate=10:1; colorless oil; [α] D 20 = -175.2 (c 0.28CH2Cl2); 1H NMR (600MHz, CDCl3) δ8.33-8.23 (m, 2H), 8.00 (d, J=8.9Hz, 2H), 7.53-7.48 (m, 1H), 7.43 (t, J=7.5Hz, 2H), 7.09 (dd, J=9.4, 2.5 Hz, 2H), 4.00 (dd, J=9.6, 6.6Hz, 1H), 3.90 (s, 3H), 3.61 (dd, J=9.6, 6.7Hz, 1H), 1.93-1.86 (m, 1H), 0.86 (dd, J=8.1, 6.8Hz, 6H); 13 C NMR (151MHz, CDCl3) δ178.3, 163.3, 136.3, 131.8, 129.9, 129.6, 128.1, 128.0, 114.9, 73.5, 55.8, 28.9, 19.1; HRMS (ESI) m / z: [M+H] + Calculated for C 18 H 22 NO3S: 332.1315, found: 332.1223; Enantiomeric excess: 81%, determined by HPLC (Daicel Chiralpak AD, isopropanol / hexane=30 / 70, flowrate=1.0mL / min, T=30°C, λ=254nm): t R =7.40min (major), t R = 9.76min (minor).

[0331] Example 44: Synthesis and characterization of compound 4ar

[0332]

[0333] Using the same method as in Example 1, product 4ar was finally separated, with a yield of 74% and ee = 84%.

[0334] The structure of compound 4ar is as follows:

[0335]

[0336] Characterization data of compound 4ar:

[0337] isobutyl(R)-N-benzoyl-3-rt-uorobenzenesulfinimidate 4ar:yield:74%(23.7mg);flash column chromatography eluent,petroleum ether / ethyl acetate=10:1;colorless oil;[α] D 20 =-201.4(c 0.19CH2Cl2); 1 H NMR(600MHz,CDCl3)δ8.28(d,J=7.8Hz,2H),7.85(d,J=8.4Hz,1H),7.78(d,J=7.8Hz,1H),7.59(td,J=8.0,5.5Hz,1H),7.53(t,J=7.1Hz,1H),7.45(t,J=7.6Hz,2H),7.33(td,J=8.2,2.5Hz,1H),4.06(dd,J=9.4,6.6Hz,1H),3.68(dd,J=9.5,6.7Hz,1H),2.03-1.89(m,1H),0.90(t,J=6.1Hz,6H); 13 CNMR(151MHz,CDCl3)δ178.5,165.5(d,J=255.3Hz),135.9,132.7(d,J=2.4Hz),132.0,130.5(d,J=9.1Hz),129.6,128.2,116.9(d,J=22.1Hz),74.2,28.9,19.1; 19 F NMR(565MHz,CDCl3)δ-109.13;HRMS(ESI)m / z:[M+H] + calculated for C 17 H 19 FNO2S:320.1121,found:320.1129;Enantiomeric excess:84%,determined by HPLC(Daicel ChiralpakIF,isopropanol / hexane=20 / 80,flow rate=1.0mL / min,T=30℃,λ=254nm):t R =6.37min(major),t R =6.79min(minor).

[0338] Example 45: Synthesis and characterization of compound 4as

[0339]

[0340] Using the same method as in Example 1, product 4as was finally separated, with a yield of 72% and ee = 87%.

[0341] The structure of compound 4as is as follows:

[0342]

[0343] Characterization data of compound 4as:

[0344] isobutyl(R)-N-benzoyl-3-chlorobenzenesulfinimidate 4as: yield: 72% (24.2mg); flash column chromatography eluent, petroleum ether / ethyl acetate=10:1; colorless oil; [α] D 20 = -154.0 (c 0.25CH2Cl2); 1 H NMR (600MHz, CDCl3) δ8.30-8.26 (m, 2H), 8.07 (d, J=1.3Hz, 1H), 7.89 (dd, J=7.8, 0.9Hz, 1H), 7.59 (dd, J=8.0, 0.9Hz, 1H), 7.56-7.51 (m , 2H), 7.45 (t, J=7.6Hz, 2H), 4.05 (dd, J=9.5, 6.6Hz, 1H), 3.68 (dd, J=9.5, 6.7Hz, 1H), 1.99-1.90 (m, 1H), 0.89 (dd, J=6.5, 4.9Hz, 6H); 13 C NMR (151MHz, CDCl3) δ178.5, 138.8, 135.70, 135.65, 133.0, 132.1, 130.7, 129.6, 128.2, 127.8, 126.2, 74.4, 28.9, 19.0HRMS (ESI) m / z: [M+H] + Calculated for C 17 H 19ClNO2S: 336.0820, found: 336.0825; Enantiomeric excess: 87%, determined by HPLC (Daicel Chiralpak IF, isopropanol / hexane=20 / 80, flow rate=1.0mL / min, T=30°C, λ=254nm): t R = 6.64min (major), t R = 7.13min (minor).

[0345] Example 46: Synthesis and characterization of compound 4at

[0346]

[0347] Using the same method as in Example 1, the final product was 4at, with a yield of 73% and ee = 85%.

[0348] The structure of compound 4at is as follows:

[0349]

[0350] Characterization data of compound 4at:

[0351] isobutyl(R)-N-benzoyl-3-bromobenzenesulfinimidate 4at: yield: 73% (27.6mg); flash column chromatography eluent, petroleum ether / ethyl acetate=10:1; colorless oil; [α] D 20 = -156.3 (c 0.34CH2Cl2); 1 H NMR (600MHz, CDCl3) δ8-30-8.25 (m, 2H), 8.21 (t, J=1.6Hz, 1H), 7.94 (d, J=7.9Hz, 1H), 7.76 (dd, J=8.0, 0.7Hz, 1H), 7.53 (t, J=7.3H z, 1H), 7.50-7.43 (m, 3H), 4.05 (dd, J=9.6, 6.5Hz, 1H), 3.68 (dd, J=9.6, 6.7Hz, 1H), 1.99-1.91 (m, 1H), 0.90 (dd, J=6.7, 4.4Hz, 6H); 13C NMR (151MHz, CDCl3) δ178.5, 139.1, 135.9, 135.7, 132.1, 131.0, 130.7, 129.6, 128.2, 126.7, 123.5, 74.5, 28.9, 19.1; HRMS (ESI) m / z: [M+H] + Calculated for C 17 H 19 BrNO2S: 380.0314, found: 380.0319; Enantiomeric excess: 85%, determined by HPLC (Daicel Chiralpak IF, isopropanol / hexane=20 / 80, flow rate=1.0mL / min, T=30°C, λ=254nm): t R = 6.84min (major), t R = 7.42 min (minor).

[0352] Example 47: Synthesis and characterization of compound 4au

[0353]

[0354] Using the same method as in Example 1, the final product 4au was obtained, with a yield of 71% and ee = 82%.

[0355] The structure of compound 4au is as follows:

[0356]

[0357] Characterization data of compound 4au:

[0358] isobutyl(R)-N-benzoyl-3-(trifluoromethyl)benzenesulfinimidate 4au: yield: 71% (26.1mg); flash column chromatography eluent, petroleum ether / ethylacetate=10:1; colorless oil; [α] D 20 = -174.5 (c 0.20CH2Cl2); 1H NMR (600MHz, CDCl3) δ8.32 (s, 1H), 8.29-8.26 (m, 2H), 8.23 ​​(d, J=7.9Hz, 1H), 7.89 (d, J=7.7Hz, 1H), 7.77 (t, J=7.8Hz, 1H), 7.54 (dd, J=10.6, 4.1Hz, 1H), 7.46 (t, J=7.5Hz, 2H), 4.10 (dd, J=9.6, 6.5Hz, 1H), 3.73 (dd, J=9.5, 6.7Hz, 1H), 2.04-1.88 (m, 1H), 0.91 (dd, J=6.6, 4.7Hz, 6H); 13 C NMR (151MHz, CDCl3) δ178.6, 138.7, 135.6, 132.2, 131.3, 132.2 (q, J=33.2Hz), 130.2, 129. 6, 129.5 (q, J = 3.5Hz), 128.2, 125.0 (q, J = 3.8Hz), 123.4 (q, J = 272.4Hz), 75.0, 29.0, 19.0; 19 F NMR (565MHz, CDCl3) δ-62.81; HRMS (ESI) m / z: [M+Na] + Calculated for C 18 H 18 F3NNaO2S: 392.0903, found: 392.0904; Enantiomeric excess: 82%, determined by HPLC (Daicel Chiralpak IF, isopropanol / hexane=5 / 95, flow rate=1.0mL / min, T=30°C, λ=254nm): t R =10.05min (major), t R = 10.72 min (minor).

[0359] Example 48: Synthesis and characterization of compound 4av

[0360]

[0361] Using the same method as in Example 1, product 4av was finally separated with a yield of 90% and ee = 79%.

[0362] The structure of compound 4av is as follows:

[0363]

[0364] Characterization data of compound 4av:

[0365] isobutyl(R)-N-benzoyl-3-methylbenzenesulfinimidate 4av: yield: 90% (28.5mg); flash column chromatography eluent, petroleum ether / ethyl acetate=10:1; colorless oil; [α] D 20 = -35.5 (c 0.06CH2Cl2); 1 H NMR (600MHz, CDCl3) δ8.29 (d, J=7.4Hz, 2H), 7.84 (s, 2H), 7.53-7.47 (m, 2H), 7.46-7.41 (m, 3H), 4.04 (dd , J=9.6, 6.6Hz, 1H), 3.66 (dd, J=9.5, 6.7Hz, 1H), 2.49 (s, 3H), 1.98-1.89 (m, 1H), 0.88 (t, J=6.4Hz, 6H); 13 C NMR (151MHz, CDCl3) δ178.6, 139.7, 136.7, 136.1, 133.7, 131.8, 129.6, 129.4, 128.1, 128.1, 125.1, 74.1, 28.9, 21.7, 19.1; HRMS (ESI) m / z: [M+Na] + Calculated for C 18 H 22 NO2S: 316.1366, found: 316.1363; Enantiomeric excess: 79%, determined by HPLC (DaicelChiralpak IF, isopropanol / hexane=20 / 80, flow rate=1.0mL / min, T=30°C, λ=254nm): t R = 6.63min (major), t R = 7.44min (minor).

[0366] Example 49: Synthesis and characterization of compound 4aw

[0367]

[0368] Using the same method as in Example 1, the final product 4aw was obtained by separation, with a yield of 76% and ee = 70%.

[0369] The structure of compound 4aw is as follows:

[0370]

[0371] Characterization data of compound 4aw:

[0372] isobutyl(R)-N-benzoyl-2-methylbenzenesulfinimidate 4aw: yield: 76% (24.0mg); flash column chromatography eluent, petroleum ether / ethyl acetate=10:1; colorless oil; [α] D 20 = -122.2 (c 0.19CH2Cl2); 1 H NMR (600MHz, CDCl3) δ8.50 (d, J=7.9Hz, 1H), 8.29 (d, J=8.0Hz, 2H), 7.53-7.49 (m, 2H), 7.48-7.42 (m, 3H), 7.34 (d, J=7.4Hz, 1H), 3.98 (dd, J=9.4, 6.5Hz, 1H), 3.59 (dd, J=9.4, 6.8Hz, 1H), 2.64 (s, 3H), 1.92-1.82 (m, 1H), 0.84 (dd, J=12.0, 6.7Hz, 6H); 13 C NMR (151MHz, CDCl3) δ178.3, 138.6, 136.3, 134.8, 133.0, 131.8, 131.7, 129. 6, 128.1, 127.4, 126.9, 73.7, 28.8, 19.2, 19.03, 19.0; HRMS (ESI) m / z: [M+Na] + Calculated for C 18 H 22 NO2S: 316.1366, found: 316.1364; Enantiomeric excess: 70%, determined by HPLC (Daicel Chiralpak IF, isopropanol / hexane=20 / 80, flow rate=1.0mL / min, T=30°C, λ=254nm): t R = 6.54min (major), t R = 7.13min (minor).

[0373] Example 50: Synthesis and characterization of compound 4ax

[0374]

[0375] Using the same method as in Example 1, product 4ax was finally separated with a yield of 84% and ee = 89%.

[0376] The structure of compound 4ax is as follows:

[0377]

[0378] Characterization data of compound 4ax:

[0379] isobutyl(R)-N-benzoyl-3, 4-dirt-uorobenzenesulfinimidate 4ax: yield: 84% (28.2mg); flash column chromatography eluent, petroleum ether / ethyl acetate=10:1; colorless oil; [α] D 20 = -210.0 (c 0.22CH2Cl2); 1 H NMR (600MHz, CDCl3) δ8.28-8.23 (m, 2H), 8.02-7.96 (m, 1H), 7.81-7.75 (m, 1H), 7.55-7.51 (m, 1H), 7.47-7.3 9 (m, 3H), 4.05 (dd, J=9.5, 6.6Hz, 1H), 3.67 (dd, J=9.5, 6.7Hz, 1H), 1.98-1.90 (m, 1H), 0.89 (t, J=6.0Hz, 6H); 13 C NMR (151MHz, CDCl3) δ178.4, 153.3 (dd, J=257.0, 12.7Hz), 150.8 (dd, J=254.4, 13.2Hz), 135.6, 133.8-133.7 (m ), 132.2, 129.6, 128.2, 125.0 (dd, J=7.3, 3.8Hz), 118.6 (d, J=18.1Hz), 117.6 (d, J=20.3Hz), 74.5, 28.9, 19.0; 19 F NMR (565MHz, CDCl3) δ-129.58 (d, J=20.2Hz), -133.04 (d, J=20.2Hz); HRMS (ESI) m / z: [M+Na] + Calculated for C 17 H 17F2NNaO2S: 360.0840, found: 360.0846; Enantiomeric excess: 89%, determined by HPLC (Daicel Chiralpak IF, isopropanol / hexane=5 / 95, flow rate=1.0mL / min, T=30°C, λ=254nm): t R =11.88min (major), t R = 13.23min (minor).

[0380] Example 51: Synthesis and characterization of compound 4ay

[0381]

[0382] Using the same method as in Example 1, product 4ay was finally separated, with a yield of 85% and ee = 87%.

[0383] The structure of compound 4ay is as follows:

[0384]

[0385] Characterization data of compound 4ay:

[0386] isobutyl(R)-N-benzoylthiophene-2-sulfinimidate 4ay: yield: 85% (26.1mg); flash column chromatography eluent, petroleum ether / ethyl acetate=10:1; colorless oil; [α] D 20 = -51.5 (c 0.18CH2Cl2); 1 H NMR (600MHz, CDCl3) δ8.26 (dd, J=8.2, 1.3Hz, 2H), 7.76 (dd, J=5.0, 1.2Hz, 1H), 7.68 (dd, J=3.8, 1.2Hz, 1H), 7.54-7.49 (m, 1H), 7.44 (t ; 13C NMR (151MHz, CCDCl3) δ178.1, 135.4, 133.6, 132.5, 132.0, 129.6, 128.7, 128.1, 72.1, 28.7, 19.1; HRMS (ESI) m / z: [M+Na] + Calculated for C 15 H 17 NNaO2S2: 330.0593, found: 330.0597; Enantiomericexcess: 87%, determined by HPLC (Daicel Chiralpak AD, isopropanol / hexane=30 / 70, flow rate=1.0mL / min, T=30°C, λ=254nm): t R = 6.82min (major), t R = 8.50min (minor)

[0387] Example 52: Synthesis and characterization of compound 4az

[0388]

[0389] Using the same method as in Example 1, product 4az was finally separated with a yield of 95% and ee = 81%.

[0390] The structure of compound 4az is as follows:

[0391]

[0392] Characterization data of compound 4az:

[0393] isobutyl(R)-N-benzoylcyclohexan-sulfinimidate 4az: yield: 95% (29.2mg); flash column chromatography eluent, petroleum ether / ethyl acetate=10:1; colorless oil; [α] D 20 = -198.8 (c 0.27CH2Cl2); 1H NMR (600MHz, CDCl3) δ8.18 (d, J=7.4Hz, 2H), 7.47 (t, J=7.3Hz, 1H), 7.39 (t, J=7 .5Hz, 2H), 4.13-4.05(m, 2H), 3.14(t, J=11.4Hz, 1H), 2.21(s, 2H), 2.02-1.96(m , 1H), 1.94-1.87 (m, 2H), 1.73 (d, J=13.4Hz, 1H), 1.58 (dt, J=16.2, 12.0Hz, 2H) , 1.40 (dd, J=25.1, 12.4Hz, 2H), 1.34-1.28 (m, 1H), 0.94 (dd, J=6.6, 3.5Hz, 6H); 13 C NMR (151MHz, CDCl3) δ179.3, 136.3, 131.6, 129.5, 128.0, 78.8, 59.3, 29.4, 26.4, 25.6, 25.4, 19.1; HRMS (ESI) m / z: [M+Na] + Calculated for C 17 H 25 NNaO2S2: 330.1498, found: 330.1497; Enantiomeric excess: 81%, determined by HPLC (Daicel Chiralpak AD, isopropanol / hexane=5 / 95, flow rate=1.0mL / min, T=30°C, λ=254nm): t R =13.23(minor)min,t R = 14.31min (major).

[0394] Example 53: Synthesis and characterization of compound 4ba

[0395]

[0396] Using the same method as in Example 1, product 4ba was finally separated with a yield of 90% and ee = 70%.

[0397] The structure of compound 4ba is as follows:

[0398]

[0399] Characterization data of compound 4ba:

[0400] isobutyl(R)-N-benzoylpentasulfinimidate 4ba: yield: 90% (25.3mg); flashcolumn chromatography eluent, petroleum ether / ethyl acetate=10:1; colorlessoil; [α] D 20 = -160.6 (c 0.23CH2Cl2); 1 H NMR (600MHz, CDCl3) δ8.21-8.13 (m, 2H), 7.47 (t, J=7.3Hz, 1H), 7.40 (t, J=7.6Hz, 2H), 4.09 (d, J=6.6Hz, 2H), 3.24-3.18 (m, 1H), 3.16-3.10 (m, 1H), 2.02-1.93 (m, 1H), 1.84-1.78 (m, 2H), 1.56-1.49 (m, 2H), 0.99 (t, J=7.4Hz, 3H), 0.94 (dd, J=6.7, 3.0Hz, 6H); 13 C NMR (151MHz, CDCl3) δ179.1, 135.9, 131.7, 129.5, 128.1, 78.6, 50.6, 29.3, 25.2, 21.9, 19.00, 18.97, 13.8; HRMS (ESI) m / z: [M+Na] + Calculated for C 15 H 23 NNaO2S: 304.1342, found: 304.1343; Enantiomeric excess: 70%, determined by HPLC (Daicel Chiralpak AD, isopropanol / hexane=5 / 95, flow rate=1.0mL / min, T=30°C, λ=254nm): t R =11.76(minor)min,t R = 14.30min (major).

[0401] Example 54: Synthesis and characterization of compound 4bb

[0402]

[0403] Using the same method as in Example 1, product 4bb was finally obtained by separation, with a yield of 95% and ee = 69%.

[0404] The structure of compound 4bb is as follows:

[0405]

[0406] Characterization data of compound 4bb:

[0407] isobutyl (R)-N-benzoyl-2-phenylacesulfinimidate 4bb: yield: 95% (30.0 mg); flash column chromatography eluent, petroleum ether / ethyl acetate = 10:1; colorless oil; [α] D 20 = -198.3 (c 0.28 CH2Cl2); 1 1H NMR (600 MHz, CDCl3) δ 8.16 (d, J = 7.1 Hz, 2H), 7.58 - 7.33 (m, 8H), 4.49 (dd, J = 13.3, 1.8 Hz, 1H), 4.42 - 4.33 (m, 1H), 4.09 - 4.02 (m, 1H), 4.00 - 3.92 (m, 1H), 1.91 - 1.80 (m, 1H), 0.82 (d, J = 6.0 Hz, 6H); 13 13C NMR (151 MHz, CDCl3) δ 179.0, 135.8, 131.8, 131.0, 129.5, 129.09, 129.06, 129.05, 128.1, 79.1, 57.3, 29.2, 18.9; HRMS (ESI) m / z: [M+Na]<00005**00**> calculated for C<00005**01**>H<00005**02**>NNaO2S: 338.1185, found: 338.1185; Enantiomeric excess: 69%, determined by HPLC (Daicel Chiralpak AD, isopropanol / hexane = 30 / 70, flow rate = 1.0 mL / min, T = 30 °C, λ = 254 nm): t<00005**03**>= 6.46 (minor) min, t<00005**04**>= 11.35 min (major).

[0408] Example 55: Synthesis and characterization of compound 4bc

[0409]

[0410] It seems there might be some minor formatting issues in the original text (like the repeated use of + , 18 , 21 , R , R which might be a typo). I've translated it as is while keeping those tags intact. If you have any further clarifications or corrections regarding the original text, feel free to let me know.Using the same method as in Example 1, product 4bc was finally separated, with a yield of 88% and ee = 79%.

[0411] The structure of compound 4bc is as follows:

[0412]

[0413] Characterization data of compound 4bc:

[0414] isobutyl(R)-N-benzoyl-2-(m-tolyl)acesulfinimidate 4ay: yield: 88% (29.1mg); flash column chromatography eluent, petroleum ether / ethyl acetate=10:1; colorless oil; [α] D 20 = -79.5 (c 0.14CH2Cl2); 1 H NMR (600MHz, CDCl3) δ8.16 (dd, J=5.1, 3.3Hz, 2H), 7.48 (ddd, J=8.6, 2.5, 1.2Hz, 1H), 7.40 (dd, J=10.5, 4.6Hz, 2H), 7.30-7.25 (m, 2H), 7.23 (d, J=7.6Hz, 1H), 7.18 (d, J=7. 5Hz, 1H), 4.46 (d, J=13.2Hz, 1H), 4.35 (d, J=13.2Hz, 1H), 4.06 (dd, J=9.8, 6.6Hz, 1H) , 3.96 (dd, J=9.8, 6.5Hz, 1H), 2.37 (s, 3H), 1.90-1.81 (m, 1H), 0.84 (d, J=6.7Hz, 6H); 13 C NMR (151MHz, CDCl3) δ178.9, 138.8, 135.8, 131.8, 129.8, 129.5, 128.9, 128.8, 128.1, 128.0, 79.1, 57.2, 29.3, 21.4, 18.9; HRMS (ESI) m / z: [M+Na] + Calculated for C 19 H 23NNaO2S: 352.1342, found: 352.1347; Enantiomeric excess: 79%, determined by HPLC (Daicel Chiralpak AD, isopropanol / hexane=30 / 70, flow rate=1.0mL / min, T=30°C, λ=254nm): t R =6.05(minor)min,t R = 11.70 min (major).

[0415] Example 56: Synthesis and characterization of compound 4bd

[0416]

[0417] Using the same method as in Example 1, product 4bd was finally obtained by separation, with a yield of 86% and ee = 92%.

[0418] The structure of compound 4bd is as follows:

[0419]

[0420] Characterization data of compound 4bd:

[0421] isobutyl(R)-4-(tert-butyl)-N-(4-fluorobenzoyl)benzenesulfinimidate4bd: yield: 86% (32.4mg); flash column chromatography eluent, petroleum ether / ethyl acetate=10:1; colorless oil; [α] D 20 = -152.5 (c 0.12CH2Cl2); 1 H NMR (600MHz, CDCl3) δ8.29 (dd, J=8.2, 5.9Hz, 2H), 7.94 (d, J=8.4Hz, 2H), 7.61 (d, J=8.4Hz, 2H), 7.08 (t, J=8.6Hz, 2 H), 4.05 (dd, J=9.5, 6.6Hz, 1H), 3.70 (dd, J=9.5, 6.7Hz, 1H), 1.99-1.89 (m, 1H), 1.37 (s, 9H), 0.89 (t, J=6.5Hz, 6H); 13C NMR (151MHz, CDCl3) δ177.4, 165.3 (d, J = 251.6Hz), 156.8, 133.6, 132.5 (d, J = 2.1Hz), 132.0 (d, J=8.9Hz), 127.7, 126.6, 115.0 (d, J=21.6Hz), 74.4, 35.3, 31.3, 29.0, 19.1; 19 F NMR (565MHz, CDCl3) δ-108.57; HRMS (ESI) m / z: [M+H] + Calculated for C 21 H 27 FNO2S: 376.1741, found: 376.1746; Enantiomericexcess: 92%, determined by HPLC (Daicel Chiralpak IF, isopropanol / hexane=10 / 90, flow rate=1.0mL / min, T=30°C, λ=254nm): t R = 7.25min (major), t R = 8.02min (minor).

[0422] Example 57: Synthesis and characterization of compound 4be

[0423]

[0424] Using the same method as in Example 1, product 4be was finally separated, with a yield of 78% and ee = 92%.

[0425] The structure of compound 4be is as follows:

[0426]

[0427] Characterization data of compound 4be:

[0428] isobutyl(R)-4-(tert-butyl)-N-(4-chlorobenzoyl)benzenesulfinimidate4be: yield: 78% (30.5mg); flash column chromatography eluent, petroleum ether / ethyl acetate=10:1; colorless oil; [α] D 20 = -168.4 (c 0.04CH2Cl2); 1H NMR (600MHz, CDCl3) δ8.21 (d, J=8.5Hz, 2H), 7.94 (d, J=8.5Hz, 2H), 7.61 (d, J=8.5Hz, 2H), 7.39 (d, J=8.5Hz, 2H), 4.04 (dd, J=9.6, 6.6Hz, 1H), 3.69 (dd, J=9.6, 6.6Hz, 1H), 1.98-1.89 (m, 1H), 1.37 (s, 9H), 0.89 (t, J=6.5Hz, 6H); 13 C NMR (126MHz, CDCl3) δ177.5, 156.8, 138.0, 134.7, 133.5, 131.0, 128.3, 127.6, 126.6, 74.4, 35.3, 31.2, 28.9, 19.1, 19.0; HRMS (ESI) m / z: [M+H] + Calculated for C 21 H 27 ClNO2S: 392.1446, found: 392.1447; Enantiomeric excess: 92%, determined by HPLC (Daicel Chiralpak IF, isopropanol / hexane=5 / 95, flowrate=1.0mL / min, T=30°C, λ=254nm): t R =13.03min (major), t R = 14.04min (minor).

[0429] Example 58: Synthesis and characterization of compound 4bf

[0430]

[0431] Using the same method as in Example 1, product 4bf was finally obtained by separation, with a yield of 75% and ee = 92%.

[0432] The structure of compound 4bf is as follows:

[0433]

[0434] Characterization data of compound 4bf:

[0435] isobutyl(R)-N-(4-bromobenzoyl)-4-(tert-butyl)benzenesulfinimidate4bf: yield: 75% (32.6mg); flash column chromatography eluent, petroleum ether / ethyl acetate=10:1; colorless oil; [α] D 20 = -88.9 (c 0.06CH2Cl2); 1 H NMR (600MHz, CDCl3) δ8.14 (d, J=8.5Hz, 2H), 7.94 (d, J=8.6Hz, 2H), 7.61 (d, J=8.6Hz, 2H), 7.55 (d, J=8.5Hz, 2H), 4.04 (dd, J=9.6, 6.6Hz, 1H), 3.69 (dd, J=9.6, 6.6Hz, 1H), 1.98-1.88 (m, 1H), 1.37 (s, 9H), 0.88 (t, J=6.5Hz, 6H); 13 C NMR (151MHz, CDCl3) δ177.6, 156.9, 135.1, 133.5, 131.3, 131.2, 127.7, 126.7, 126.6, 74.4, 35.3, 31.2, 28.9, 19.1, 19.0; HRMS (ESI) m / z: [M+H] + Calculated for C 21 H 27 BrNO2S: 436.0940, found: 436.0945; Enantiomeric excess: 92%, determined by HPLC (Daicel Chiralpak AD, isopropanol / hexane=30 / 70, flowrate=1.0mL / min, T=30°C, λ=254nm): t R =6.24min (minor), t R = 6.94min (major).

[0436] Example 59: Synthesis and characterization of compound 4bg

[0437]

[0438] Using the same method as in Example 1, 4bg of product was finally separated, with a yield of 77% and ee = 91%.

[0439] The structure of compound 4bg is as follows:

[0440]

[0441] Characterization data of compound 4bg:

[0442] isobutyl(R)-4-(tert-butyl)-N-(4-(trifluoromethyl)benzenesulfinimidate4bg: yield: 77% (32.9mg); flash column chromatography eluent, petroleum ether / ethyl acetate=10:1; colorless oil; [α] D 20 = -186.2 (c 0.05CH2Cl2); 1 H NMR (600MHz, CDCl3) δ8.38 (d, J=8.1Hz, 2H), 7.95 (d, J=8.5Hz, 2H), 7.68 (d, J=8.2Hz, 2H), 7.63 (d, J=8.5Hz, 2H), 4.05 (dd, J=9.6, 6.6Hz, 1H), 3.71 (dd, J=9.6, 6.6Hz, 1H), 1.98-1.90 (m, 1H), 1.37 (s, 9H), 0.89 (t, J=6.5Hz, 6H); 13 C NMR (151MHz, CDCl3) δ177.1, 157.0, 139.5133.2 (q, J=32.3Hz), 129.9, 127.7, 126.7 , δ125.1 (q, J=3.8Hz), 124.2 (q, J=272.3Hz).74.6, 35.4, 31.2, 28.9, 19.03, 19.02; 19 F NMR (565MHz, CDCl3) δ-62.75; HRMS (ESI) m / z: [M+H] + Calculated for C 22 H 27 F3NO2S: 426.1709, found: 426.1704; Enantiomeric excess: 91%, determined by HPLC (Daicel Chiralpak IF, isopropanol / hexane=5 / 95, flow rate=1.0mL / min, T=30°C, λ=254nm): t R = 8.29min (major), tR = 9.17min (minor).

[0443] Example 60: Synthesis and characterization of compound 4bh

[0444]

[0445] Using the same method as in Example 1, product 4bh was finally obtained by separation, with a yield of 99% and ee = 91%.

[0446] The structure of compound 4bh is as follows:

[0447]

[0448] Characterization data of compound 4bh:

[0449] isobutyl(R)-4-(tert-butyl)-N-(4-cyanobenzoyl)benzenesulfinimidate4bh: yield: 99% (38.0mg); flash column chromatography eluent, petroleum ether / ethyl acetate=10:1; colorless oil; [α] D 20 = -144.4 (c 0.24CH2Cl2); 1 H NMR (600MHz, CDCl3) δ8.35 (d, J=8.3Hz, 2H), 7.94 (d, J=8.5Hz, 2H), 7.72 (d, J=8.3Hz, 2H), 7.63 (d, J=8.5Hz, 2H), 4.04 (dd, J=9.5, 6.6Hz, 1H), 3.70 (dd, J=9.5, 6.6Hz, 1H), 2.00-1.89 (m, 1H), 1.37 (s, 9H), 0.88 (t, J=6.5Hz, 6H); 13 C NMR (151MHz, CDCl3) δ176.5, 157.2, 140.2, 133.1, 132.0, 130.0, 127.6, 126. 8, 118.8, 115.0, 74.8, 35.4, 31.2, 28.9, 19.02, 19.00; HRMS (ESI) m / z: [M+H] + Calculated for C 22 H 27N2NO2S: 383.1788, found: 383.1786; Enantiomericexcess: 91%, determined by HPLC (Daicel Chiralpak IC, isopropanol / hexane=30 / 70, flow rate=1.0mL / min, T=30°C, λ=254nm): t R =11.16min (major), t R = 12.19min (minor).

[0450] Example 61: Synthesis and characterization of compound 4bi

[0451]

[0452] Using the same method as in Example 1, the final product 4bi was obtained by separation, with a yield of 85% and ee = 90%.

[0453] The structure of compound 4bi is as follows:

[0454]

[0455] Characterization data of compound 4bi:

[0456] isobutyl(R)-4-(tert-butyl)-N-(4-nitrobenzoyl)benzenesulfinimidate4bi: yield: 85% (34.1mg); flash column chromatography eluent, petroleum ether / ethyl acetate=10:1; colorless oil; [α] D 20 = -97.1 (c 0.06CH2Cl2); 1 H NMR (600MHz, CDCl3) δ8.41 (d, J=8.9Hz, 2H), 8.25 (d, J=8.9Hz, 2H), 7.95 (d, J=8.6Hz, 2H), 7.64 (d, J=8.6Hz, 2H), 4.05 (dd, J=9.6, 6.5Hz, 1H), 3.72 (dd, J=9.6, 6.6Hz, 1H), 1.99-1.91 (m, 1H), 1.37 (s, 9H), 0.89 (t, J=6.5Hz, 6H); 13C NMR (151MHz, CDCl3) δ176.3, 157.2, 149.9, 141.8, 133.0, 130.5, 127.7, 126.8, 123.3, 74.9, 35.4, 31.2, 28.9, 19.01, 18.99; HRMS (ESI) m / z: [M+H] + Calculated for C 21 H 27 N2O4S: 403.1686, found: 403.1690; Enantiomeric excess: 90%, determined by HPLC (Daicel Chiralpak IF, isopropanol / hexane=10 / 90, flowrate=1.0mL / min, T=30°C, λ=254nm): t R =11.90min (major), t R = 15.59min (minor).

[0457] Example 62: Synthesis and characterization of compound 4bj

[0458]

[0459] Using the same method as in Example 1, product 4bj was finally separated, with a yield of 87% and ee = 91%.

[0460] The structure of compound 4bj is as follows:

[0461]

[0462] Characterization data of compound 4bj:

[0463] methyl(R)-4-(((4-(tert-butyl)benzene)(isobutoxy)-λ 4 -sulfaneylidene)car bamoyl)benzoate 4bj: yield: 87% (36.1mg); flash column chromatographyeluent, petroleum ether / ethyl acetate=10:1; colorless oil; [α] D 20 = -227.2 (c0.31CH2Cl2); 1H NMR (600MHz, CDCl3) δ8.32 (d, J=8.1Hz, 2H), 8.09 (d, J=8.1Hz, 2H), 7.96 (d, J=8.4Hz, 2H), 7.63 (d, J=8.4Hz, 2H), 4.06 ( dd, J=9.4, 6.7Hz, 1H), 3.94 (s, 3H), 3.71 (dd, J=9.4, 6.7Hz, 1H), 1.98-1.91 (m, 1H), 1.37 (s, 9H), 0.89 (t, J=6.5Hz, 6H); 13 C NMR (151MHz, CDCl3) δ177.6, 166.9, 156.9, 140.2, 133.4, 132.8, 129.5, 129.4 , 127.7, 126.7, 74.6, 52.4, 35.3, 31.3, 28.9, 19.1, 19.0; HRMS (ESI) m / z: [M+H] + Calculated for C 23 H 30 NO4S: 416.1890, found: 416.1896; Enantiomeric excess: 91%, determined by HPLC (Daicel Chiralpak AD, isopropanol / hexane=10 / 90, flow rate=1.0mL / min, T=30°C, λ=254nm): t R =13.79min (major), t R = 14.59min (minor).

[0464] Example 63: Synthesis and characterization of compound 4bk

[0465]

[0466] Using the same method as in Example 1, product 4bk was finally separated with a yield of 83% and ee = 87%.

[0467] The structure of compound 4bk is as follows:

[0468]

[0469] Characterization data of compound 4bk:

[0470] isobutyl(R)-4-(tert-butyl)-N-(4-benzoyl-benzoyl)benzenesulfinimidate4b k:yield:83%(38.2mg);flash column chromatographyeluent,petroleum ether / ethyl acetate=10:1;colorless oil;[α] D 20 =-55.2(c0.38CH2Cl2); 1 H NMR(600MHz,CDCl3)δ8.37(d,J=8.0Hz,2H),7.96(d,J=8.3Hz,2H),7.83(d,J=8.0Hz,2H),7.81(d,J=7.7Hz,2H),7.62(d,J=8.3Hz,2H),7.59(t,J=7.4Hz,1H),7.48(t,J=7.6Hz,2H),4.06(dd,J=9.3,6.8Hz,1H),3.72(dd,J=9.3,6.9Hz,1H),1.99-1.90(m,1H),1.36(s,8H),0.89(t,J=6.8Hz,6H); 13 C NMR(151MHz,CDCl3)δ196.6,196.5,177.5,156.9,140.1,139.5,137.5,133.3,132.7,130.2,129.7,129.4,128.4,127.6,126.6,74.4,35.3,31.2,28.9,19.0,19.0;HRMS(ESI)m / z:[M+H] + calculated forC 28 H 32 NO3S:462.2103,found:462.2108;Enantiomeric excess:87%,determined by HPLC(Daicel Chiralpak AD,isopropanol / hexane=10 / 90,flow rate=1.0mL / min,T=30℃,λ=254nm):t R =15.95min(major),t R =17.96min(minor).

[0471] Example 64: Synthesis and characterization of compound 4bl

[0472]

[0473] Using the same method as in Example 1, 4bl of product was finally separated, with a yield of 70% and ee = 96%.

[0474] The structure of compound 4bl is as follows:

[0475]

[0476] Characterization data of compound 4bl:

[0477] isobutyl(R)-N-4-(tert-butyl)-N-(4-methylbenzoyl)benzenesulfinimidate4bl: yield: 70% (26.0mg); flash column chromatography eluent, petroleum ether / ethyl acetate=10:1; colorless oil; [α]D20=-146.9(c 0.24CH2Cl2); 1 H NMR (600MHz, CDCl3) δ8.18 (d, J=7.8Hz, 2H), 7.96 (d, J=8.4Hz, 2H), 7.61 (d, J=8.4Hz, 2H), 7.23 (d, J=7.7Hz, 2H), 4.05 ( dd, J=9.5, 6.6Hz, 1H), 3.69 (dd, J=9.5, 6.7Hz, 1H), 2.41 (s, 3H), 1.98-1.89 (m, 1H), 1.37 (s, 9H), 0.89 (t, J=6.4Hz, 6H); 13 C NMR (151MHz, CDCl3) δ178.6, 156.6, 142.2, 133.9, 133.5, 129.7, 128.8, 127.7, 126.6, 74.2, 35.3, 31.3, 29.0, 21.7, 19.1; HRMS (ESI) m / z: [M+H] + Calculated for C 22 H 30 NO2S: 372.1992, found: 372.1997; Enantiomeric excess: 96%, determined by HPLC (Daicel Chiralpak AD, isopropanol / hexane=30 / 70, flow rate=1.0mL / min, T=30°C, λ=254nm): t R =6.17min (minor), tR = 6.74min (major).

[0478] Example 65: Synthesis and characterization of compound 4bm

[0479]

[0480] Using the same method as in Example 1, the final product was 4 bm, with a yield of 61% and ee = 93%.

[0481] The structure of compound 4bm is as follows:

[0482]

[0483] Characterization data of compound 4bm:

[0484] isobutyl(R)-N-4-(tert-butyl)-N-(4-methoxybenzoyl)benzenesulfinimidate4bm: yield: 61% (23.7mg); flash column chromatography eluent, petroleum ether / emyl acetate=10:1; colorless oil; [α]D20=-179.2(c 0.13CH2Cl2); 1 H NMR (600MHz, CDCl3) δ8.25 (d, J=8.6Hz, 2H), 7.95 (d, J=8.4Hz, 2H), 7.60 (d, J=8.4Hz, 2H), 6.92 (d, J=8.6Hz, 2 H), 4.10-3.97 (m, 1H), 3.86 (s, 3H), 3.74-3.64 (m, 1H), 1.98-1.89 (m, 1H), 1.37 (s, 9H), 0.89 (t, J=6.4Hz, 6H); 13 C NMR (151MHz, CDCl3) δ178.0, 162.6, 156.5, 133.9, 131.5, 127.6, 126.5, 126.2, 113.2, 73.9, 55.4, 53.6, 35.2, 31.2, 28.9, 19.0; HRMS (ESI) m / z: [M+H] + Calculated for C 22 H 30NO3S: 388.1941, found: 388.1950; Enantiomeric excess: 93%, determined by HPLC (Daicel Chiralpak AD, isopropanol / hexane=30 / 70, flow rate=1.0mL / min, T=30°C, λ=254nm): t R =6.38min (minor), t R = 7.66min (major).

[0485] Example 66: Synthesis and characterization of compound 4bn

[0486]

[0487] Using the same method as in Example 1, product 4bn was finally separated, with a yield of 87% and ee = 92%.

[0488] The structure of compound 4bn is as follows:

[0489]

[0490] Characterization data of compound 4bn:

[0491] isobutyl(R)-4-(tert-butyl)-N-(3-rt-uorobenzoyl)benzenesulfinimidate4bn: yield: 87% (32.7mg); flash column chromatography eluent, petroleum ether / ethyl acetate=10:1; colorless oil; [α] D 20 = -102.9 (c 0.02CH2Cl2); 1 H NMR (600MHz, CDCl3) δ8.06 (d, J=7.6Hz, 1H), 7.99-7.93 (m, 3H), 7.62 (d, J=8.5Hz, 2H), 7.39 (dd, J=13.6, 7.7Hz, 1H), 7.19 (t, J =8.0Hz, 1H), 4.04 (dd, J=9.1, 7.0Hz, 1H), 3.69 (dd, J=9.2, 7.0Hz, 1H), 1.99-1.89 (m, 1H), 1.37 (s, 9H), 0.89 (t, J=6.7Hz, 6H); 13C NMR (151MHz, CDCl3) δ177.2 (d, J=2.3Hz), 162.7 (d, J=245.4Hz), 156.9, 138.6 (d, J=7.1Hz), 133.4, 129.6 (d, J=7.7Hz ), 127.7, 126.7, 125.2 (d, J = 3.0Hz), 118.7 (d, J = 21.5Hz), 116.4 (d, J = 22.7Hz), 74.4, 35.3, 31.2, 28.9, 19.05, 19.04; 19 F NMR (565MHz, CDCl3) δ-113.63; HRMS (ESI) m / z: [M+Na] + Calculated for C 18 H 26 FNaNO2S: 398.1560, found: 398.1561; Enantiomeric excess: 92%, determined by HPLC (Daicel Chiralpak IF, isopropanol / hexane=5 / 95, flow rate=1.0mL / min, T=30°C, λ=254nm): t R = 9.81min (major), t R = 11.22min (minor).

[0492] Example 67: Synthesis and characterization of compound 4bo

[0493]

[0494] Using the same method as in Example 1, product 4bo was finally separated, with a yield of 77% and ee = 92%.

[0495] The structure of compound 4bo is as follows:

[0496]

[0497] Characterization data of compound 4bo:

[0498] isobutyl(R)-4-(tert-butyl)-N-(3-chlorobenzoyl)benzenesulfinimidate4bo: yield: 77% (30.2mg); flash column chromatography eluent, petroleum ether / ethyl acetate=10:1; colorless oil; [α] D20 = -633.3 (c 0.02CH2Cl2); 1 H NMR (600MHz, CDCl3) δ8.26 (s, 1H), 8.15 (d, J=7.7Hz, 1H), 7.95 (d, J=8.4Hz, 2H), 7.62 (d, J=8.4Hz, 2H), 7.46 (dd, J=7.9, 0.8Hz, 1H), 7 .36 (t, J=7.8Hz, 1H), 4.04 (dd, J=9.5, 6.6Hz, 1H), 3.69 (dd, J=9.5, 6.6Hz, 1H), 2.00-1.87 (m, 1H), 1.37 (s, 9H), 0.89 (t, J=6.7Hz, 6H); 13 CNMR (151MHz, CDCl3) δ177.1, 156.9, 138.1, 134.1, 133.3, 131.7, 129.7, 129.4, 1 27.7, 127.6, 126.7, 74.4, 35.3, 31.2, 28.9, 19.04, 19.03; HRMS (ESI) m / z: [M+Na] + calculated for C 18 H 26 ClNaNO2S: 414.1265found: 414.1266; Enantiomeric excess: 92%, determined by HPLC (Daicel Chiralpak IF, isopropanol / hexane=5 / 95, flow rate=1.0mL / min, T=30°C, λ=254nm): t R =10.59min (major), t R = 11.89min (minor).

[0499] Example 68: Synthesis and characterization of compound 4bp

[0500]

[0501] Using the same method as in Example 1, the final product 4bp was obtained with a yield of 73% and ee = 94%.

[0502] The structure of compound 4bp is as follows:

[0503]

[0504] Characterization data of compound 4bp:

[0505] isobutyl(R)-N-(3-bromobenzoyl)-4-(tert-butyl)benzenesulfinimidate4bp: yield: 73% (31.8mg); flash column chromatography eluent, petroleum ether / ethyl acetate=10:1; colorless oil; [α] D 20 = -153.9 (c 0.34CH2Cl2); 1 H NMR (600MHz, CDCl3) δ8.42 (s, 1H), 8.19 (d, J=7.6Hz, 1H), 7.94 (d, J=8.1Hz, 2H), 7.67-7.58 (m, 3H), 7.30 (t, J=7 .7Hz, 1H), 4.03 (t, J=8.0Hz, 1H), 3.69 (t, J=8.0Hz, 1H), 1.99-1.89 (m, 1H), 1.37 (s, 9H), 0.89 (t, J=6.3Hz, 6H); 13 C NMR (151MHz, CDCl3) δ177.0, 156.9, 138.3, 134.6, 133.4, 132.6, 129.7, 128.1, 127.7, 126.7, 122.3, 74.4, 35.4, 31.3, 28.9, 19.1, 19.0; HRMS (ESI) m / z: [M+H] + Calculated for C 21 H 27 BrNO2S: 436.0940, found: 436.0949; Enantiomeric excess: 94%, determined by HPLC (Daicel Chiralpak IF, isopropanol / hexane=10 / 90, flow rate=1.0mL / min, T=30°C, λ=254nm): t R =7.80min (minor), t R = 8.46min (major).

[0506] Example 69: Synthesis and characterization of compound 4bq

[0507]

[0508] Using the same method as in Example 1, the final product 4bq was obtained with a yield of 98% and ee = 93%.

[0509] The structure of compound 4bq is as follows:

[0510]

[0511] Characterization data of compound 4bq:

[0512] isobutyl(R)-N-4-(tert-butyl)-N-(3-methoxybenzoyl)benzenesulfinimidate4bq: yield: 98% (37.8mg); flash column chromatography eluent, petroleum ether / ethyl acetate=10:1; colorless oil; [α]D20=-167.7(c 0.30CH2Cl2); 1 H NMR (600MHz, CDCl3) δ7.95 (d, J=8.6Hz, 2H), 7.91 (d, J=7.6Hz, 1H), 7.83-7.81 (m, 1H), 7.61 (d, J=8.6Hz, 2H), 7.34 (t, J=7.9Hz, 1H), 7.08- 7.03 (m, 1H), 4.05 (dd, J=9.6, 6.6Hz, 1H), 3.87 (d, 3H), 3.70 (dd, J=9.6, 6.6Hz, 1H), 1.99-1.90 (m, 1H), 1.37 (s, 9H), 0.89 (t, J=6.7Hz, 6H); 13 C NMR (151MHz, CDCl3) δ178.4, 159.5, 156.7, 137.7, 133.7, 129.1, 127.7, 126.6, 122.2, 118.3, 114.0, 74.3, 55.5, 35.3, 31.3, 29.0, 19.1; HRMS (ESI) m / z: [M+H] + Calculated for C 22 H 30 NO3S: 388.1941, found: 388.1940; Enantiomeric excess: 93%, determined by HPLC (Daicel Chiralpak AD, isopropanol / hexane=30 / 70, flow rate=1.0mL / min, T=30°C, λ=254nm): t R = 4.92min (major), t R = 5.40 min (minor).

[0513] Example 70: Synthesis and characterization of compound 4br

[0514]

[0515] Using the same method as in Example 1, the final product 4br was obtained with a yield of 98% and ee = 88%.

[0516] The structure of compound 4br is as follows:

[0517]

[0518] Characterization data of compound 4br:

[0519] isobutyl(R)-4-(tert-butyl)-N-(3,5-dichlorobenzoyl)benzenesulfinimidate 4br: yield: 98% (41.7mg); flash column chromatographyeluent, petroleum ether / ethyl acetate=10:1; colorless oil; [α] D 20 = -128.3 (c0.43CH2Cl2); 1 H NMR (600MHz, CDCl3) δ8.17-8.10(m, 2H), 7.96-7.91(m, 2H), 7.68-7.62(m, 2H), 7.50-7.44(m, 1H), 4. 05-3.99 (m, 1H), 3.70-3.66 (m, 1H), 1.98-1.89 (m, 1H), 1.38 (d, J = 1.5Hz, 9H), 0.89 (t, J = 6.7Hz, 6H); 13 C NMR (151MHz, CDCl3) δ175.8, 157.2, 139.2, 134.8, 133.0, 131.5, 128.0, 127.7, 126.8, 74.6, 35.4, 31.3, 28.9, 19.03, 19.01; HRMS (ESI) m / z: [M+H] + Calculated for C 21 H 26Cl2NO2S: 426.1056, found: 426.1054; Enantiomeric excess: 88%, determined by HPLC (Daicel Chiralpak IF, isopropanol / hexane=5 / 95, flowrate=1.0mL / min, T=30°C, λ=254nm): t R =7.98min (major), t R = 8.46min (minor).

[0520] Example 71: Synthesis and characterization of compound 4bs

[0521]

[0522] Using the same method as in Example 1, the final product 4bs was obtained, with a yield of 71% and ee = 94%.

[0523] The structure of compound 4bs is as follows:

[0524]

[0525] Characterization data of compound 4bs:

[0526] isobutyl(R)-N-(2-naphthoyl)-4-(tert-butyl)benzenesulfinimidate 4bs: yield: 71% (28.9mg); flash column chromatography eluent, petroleum ether / ethylacetate=10:1; colorless oil; [α] D 20 = -177.3 (c 0.15CH2Cl2); 1 H NMR (600MHz, CDCl3) δ8.85 (s, 1H), 8.34 (dd, J=8.5, 1.3Hz, 1H), 8.02 (d, J=8.4Hz, 2H), 7.99 (d, J=8.0Hz, 1H), 7.88 (d, J=8.5Hz, 2H), 7.65 (d, J= 8.5Hz, 2H), 7.58-7.49 (m, 2H), 4.11 (dd, J=9.6, 6.6Hz, 1H), 3.75 (dd, J=9.6, 6.7Hz, 1H), 2.01-1.91 (m, 1H), 1.39 (s, 9H), 0.91 (t, J=6.3Hz, 6H); 13C NMR (151MHz, CDCl3) δ178.6, 156.7, 135.3, 133.7, 133.5, 132.9, 130.4, 129.5, 127.8, 127.74, 1 27.67, 127.5, 126.7, 126.2, 126.1, 74.4, 35.3, 31.3, 29.0, 19.12, 19.10; HRMS (ESI) m / z: [M+H] + Calculated for C 25 H 30 NO2S: 408.1992, found: 408.1992; Enantiomeric excess: 94%, determined by HPLC (Daicel Chiralpak AD, isopropanol / hexane=30 / 70, flow rate=1.0mL / min, T=30°C, λ=254nm): t R =6.91min (minor), t R = 9.24min (major).

[0527] Example 72: Synthesis and characterization of compound 4bt

[0528]

[0529] Using the same method as in Example 1, the final product 4bt was obtained with a yield of 80% and ee = 90%.

[0530] The structure of compound 4bt is as follows:

[0531]

[0532] Characterization data of compound 4bt:

[0533] isobutyl(R)-4-(tert-butyl)-N-(thiophene-2-carbonyl)benzenesulfinimidate 4bt: yield: 80% (29.2mg); flash column chromatographyeluent, petroleum ether / ethyl acetate=10:1; colorless oil; [α] D 20 =v-365.4(c0.11CH2Cl2); 1H NMR (600MHz, CDCl3) δ7.93 (d, J=8.6Hz, 2H), 7.87 (dd, J=3.6, 1.2Hz, 1H), 7.60 (d, J=8.6Hz, 2H), 7.47 (dd, J=4.9, 1.1Hz, 1H), 7.09 (dd ; 13 C NMR (151MHz, CDCl3) δ173.4, 156.7, 141.6, 133.3, 131.6, 131.1, 127.7, 126.6, 74.1, 35.3, 31.2, 28.9, 19.1; HRMS (ESI) m / z: [M+H] + Calculated for C 19 H 26 NO2S2: 364.1399, found: 364.1408; Enantiomeric excess: 90%, determined by HPLC (Daicel Chiralpak IF, isopropanol / hexane=20 / 80, flow rate=1.0mL / min, T=30°C, λ=254nm): t R = 6.65min (major), t R = 7.30min (minor).

[0534] Example 73: Synthesis and characterization of compound 4bu

[0535]

[0536] Using the same method as in Example 1, 4bu of product was finally separated, with a yield of 80% and ee = 90%.

[0537] The structure of compound 4bu is as follows:

[0538]

[0539] Characterization data of compound 4bu:

[0540] isobutyl(R)-N-(4-bromothiophene-2-carbonyl)-4-(tert-butyl)benzenesulfinimidate 4bu: yield: 80% (35.4mg); flash column chromatography eluent, petroleum ether / ethyl acetate=10:1; colorless oil; [α] D 20 = -132.9 (c 0.34CH2Cl2); 1 H NMR (600MHz, CDCl3) δ7.91 (d, J=8.3Hz, 2H), 7.75 (d, J=1.2Hz, 1H), 7.61 (d, J=8.3Hz, 2H), 7.36 (d, J=1.2Hz, 1H), 4.05-4.00(m, 1H), 3.67-3.62(m, 1H), 1.97-1.88(m, 1H), 1.37(d, J=0.4Hz, 9H), 0.89(t, J=6.9Hz, 6H); 13 C NMR (151MHz, CDCl3) δ172.0, 157.0, 142.6, 133.6, 132.9, 128.3, 127.7, 126.7, 110.2, 74.3, 35.4, 31.3, 28.9, 19.0; HRMS (ESI) m / z: [M+H] + Calculated for C 19 H 25 BrNO2S2: 442.0505, found: 442.0510; Enantiomeric excess: 90%, determined by HPLC (Daicel Chiralpak IF, isopropanol / hexane=5 / 95, flowrate=1.0mL / min, T=30°C, λ=254nm): t R =17.0min (major), t R = 17.51 ​​min (minor).

[0541] Example 74: Synthesis and characterization of compound 4bv

[0542]

[0543] Using the same method as in Example 1, product 4bv was finally obtained with a yield of 98% and ee = 94%.

[0544] The structure of compound 4bv is as follows:

[0545]

[0546] Characterization data of compound 4bv:

[0547] isobutyl(R)-4-(tert-butyl)-N-butyrylbenzenesulfinimidate 4bv: yield: 98% (31.7mg); flash column chromatography eluent, petroleum ether / ethyl acetate=10:1; colorless oil; [α] D 20 = -151.3 (c 0.04CH2Cl2); 1 H NMR (600MHz, CDCl3) δ7.81 (d, J=8.5Hz, 2H), 7.55 (d, J=8.5Hz, 2H), 3.96 (dd, J=9.6, 6.7Hz, 1H), 3.65 (dd, J=9.6, 6.7Hz, 1H), 2.51-2.44(m, 2H), 1.95-1.88(m, 1H), 1.77-1.68(m, 2H), 1.33(s, 9H), 0.97(t, J=7.4Hz, 3H), 0.88(t, J=6.7Hz, 6H); 13 C NMR (151MHz, CDCl3) δ187.5, 156.5, 133.7, 127.5, 126.5, 74.5, 41.0, 35.2, 31.2, 28.9, 19.7, 19.1, 19.0, 14.1; HRMS (ESI) m / z: [M+H] + Calculated for C 18 H 30 NO2S: 324.1992, found: 324.1990; Enantiomeric excess: 94%, determined by HPLC (Daicel Chiralpak AD, isopropanol / hexane=10 / 90, flow rate=1.0mL / min, T=30°C, λ=254nm): t R = 5.99min (major), t R = 6.73min (minor).

[0548] Example 75: Synthesis and characterization of compound 4bw

[0549]

[0550] Using the same method as in Example 1, product 4bw was finally obtained by separation, with a yield of 88% and ee = 95%.

[0551] The structure of compound 4bw is as follows:

[0552]

[0553] Characterization data of compound 4bw:

[0554] isobutyl(R)-4-(tert-butyl)-N-isobutyrylbenzenesulfinimidate 4bw: yield: 88% (28.5mg); flash column chromatography eluent, petroleum ether / ethylacetate=10:1; colorless oil; [α] D 20 = -165.7 (c 0.03CH2Cl2); 1 H NMR (600MHz, CDCl3) δ7.82 (dd, J=8.8, 2.0Hz, 2H), 7.55 (dd, J=8.8, 2.0Hz, 2H), 3.97 (dd, J=9.7, 6.5Hz, 1H), 3.64 (dd, J= 9.7, 6.6Hz, 1H), 2.77-2.69 (m, 1H), 1.95-1.87 (m, 1H), 1.33 (s, 9H), 1.22 (dd, J=6.9, 3.8Hz, 6H), 0.88 (t, J=6.7Hz, 6H); 13 C NMR (151MHz, CDCl3) δ191.3, 156.4, 133.9, 127.5, 126.5, 74.3, 37.7, 35.2, 31.2, 29.0, 20.2, 19.06, 19.05; HRMS (ESI) m / z: [M+H] + Calculated for C 18 H 30 NO2S: 324.1992, found: 324.1986; Enantiomeric excess: 95%, determined by HPLC (Daicel Chiralpak AD, idopropanol / hexane=10 / 90, flow rate=1.0mL / min, T=30°C, λ=254nm): tR = 5.49min (major), t R = 6.14min (minor).

[0555] Example 76: Synthesis and characterization of compound 4bx

[0556]

[0557] Using the same method as in Example 1, product 4bx was finally separated with a yield of 73% and ee = 88%.

[0558] The structure of compound 4bx is as follows:

[0559]

[0560] Characterization data of compound 4bx:

[0561] isobutyl(R)-4-(tert-butyl)-N-pivaloylbenzenesulfinimidate 4bx: yield: 73% (24.5mg); flash column chromatography eluent, petroleum ether / ethyl acetate=10:1; colorless oil; [α] D 20 = -124.0 (c 0.05CH2Cl2); 1 H NMR (600MHz, CDCl3) δ7.84 (d, J=8.3Hz, 2H), 7.56 (d, J=8.4Hz, 2H), 3.96 (dd, J=9.6, 6.6Hz, 1H), 3.59 (dd, J=9.6, 6.6Hz, 1H), 1.93-1.86 (m, 1H), 1.35 (s, 9H), 1.29 (s, 9H), 0.88 (t, J=7.0Hz, 6H); 13 C NMR (151MHz, CDCl3) δ192.9, 156.3, 134.1, 127.7, 126.4, 73.7, 41.1, 35.2, 31.3, 28.9, 28.4, 19.1; HRMS (ESI) m / z: [M+H] + Calculated for C 19 H 31NO2S: 338.2148, found: 338.2144; Enantiomeric excess: 88%, determined by HPLC (Daicel Chiralpak AD, isopropanol / hexane=10 / 90, rt-ow rate=1.0mL / min, T=30°C, λ=254nm): t R = 4.86min (major), t R = 5.61min (minor).

[0562] Example 77: Synthesis and characterization of compound 4by

[0563]

[0564] Using the same method as in Example 1, product 4by was finally separated, with a yield of 87% and ee = 93%.

[0565] The structure of compound 4by is as follows:

[0566]

[0567] Characterization data of compound 4by:

[0568] isobutyl(R)-4-(tert-butyl)-N-(cyclopropanecarbonyl)benzenesulfinimidate 4by: yield: 87% (28.2mg); flash column chromatographyeluent, petroleum ether / ethyl acetate=10:1; colorless oil; [α] D 20 = -252.3 (c0.18CH2Cl2); 1 H NMR (600MHz, CDCl3) δ7.82 (d, J=8.6Hz, 2H), 7.54 (d, J=8.6Hz, 2H), 3.95 (dd, J=9.7, 6.6Hz, 1H), 3.64 (dd, J=9.7, 6.6Hz, 1 H), 1.94-1.85 (m, 2H), 1.32 (s, 9H), 1.10-1.05 (m, 1H), 1.02-0.98 (m, 1H), 0.86 (dd, J=7.8, 6.9Hz, 6H), 0.82-0.77 (m, 2H); 13CNMR (151MHz, CDCl3) δ187.6, 156.5, 133.8, 127.5, 126.5, 74.5, 35.2, 31.2, 28.9, 19.02, 18.99, 17.4, 9.4, 8.7; HRMS (ESI) m / z: [M+H] + Calculated for C 18 H 28 NO2S: 322.1835, found: 322.1835; Enantiomeric excess: 93%, determined by HPLC (Daicel ChiralpakAD, isopropanol / hexane=10 / 90, flow rate=1.0mL / min, T=30°C, λ=254nm): t R = 6.56min (major), t R = 7.10min (minor).

[0569] Example 78: Synthesis and characterization of compound 4bz

[0570]

[0571] Using the same method as in Example 1, product 4bz was finally separated, with a yield of 97% and ee = 94%.

[0572] The structure of compound 4bz is as follows:

[0573]

[0574] Characterization data of compound 4bz:

[0575] isobutyl(R)-4-(tert-butyl)-N-(cyclohexanecarbonyl)benzenesulfinimidate 4bz: yield: 97% (35.1mg); flash column chromatographyeluent, petroleum ether / ethyl acetate=10:1; colorless oil; [α] D 20 = -182.9 (c0.28CH2Cl2); 1H NMR (600MHz, CDCl3) δ7.82 (d, J=8.5Hz, 2H), 7.55 (d, J=8.5Hz, 2H), 3.96 (dd, J=9.7, 6.6Hz, 1H), 3.64 (dd, J=9.7, 6.6Hz, 1H), 2.04-1.96 (m, 2 H), 1.94-1.87(m, 1H), 1.81-1.73(m, 2H), 1.69-1.62(m, 1H), 1.56-1.4 8(m, 2H), 1.37-1.32(m, 9H), 1.30-1.23(m, 4H), 0.88(t, J=6.7Hz, 6H); 13 C NMR (151MHz, CDCl3) δ190.3, 156.4, 134.0, 127.5, 126.5, 74.3, 47.4, 35.2, 31. 3, 30.33, 30.31, 29.0, 26.2, 26.12, 26.07, 19.09, 19.07; HRMS(ESI)m / z: [M+H] + Calculated for C 21 H 34 NO2S: 364.2305, found: 364.2303; Enantiomeric excess: 94%, determined by HPLC (Daicel Chiralpak AD, isopropanol / hexane=10 / 90, flow rate=1.0mL / min, T=30°C, λ=254nm): t R =6.07min (major), t R = 7.17min (minor).

[0576] Example 79: Synthesis and characterization of compound 4ca

[0577]

[0578] Using the same method as in Example 1, the final product 4ca was obtained by separation, with a yield of 84% and ee = 63%.

[0579] The structure of compound 4ca is as follows:

[0580]

[0581] Characterization data of compound 4ca:

[0582] isobutyl(R)-4-(tert-butyl)-N-(p-tolylcarbamoyl)benzenesulfinimidate4ca: yield: 84% (32.3mg); flash column chromatographyeluent, petroleum ether / ethyl acetate=10:1; colorless oil; [α] D 20 = -38.1 (c0.32CH2Cl2); 1 H NMR (600MHz, CDCl3) δ7.82 (d, J=8.4Hz, 2H), 7.55 (d, J=8.4Hz, 2H), 7.38 (d, J=7.7Hz, 2H), 7.28 (s, 1H), 7.08 (d, J=8.0Hz, 2H), 4.01 (dd, J=9.5, 6.6Hz, 1H), 3.78-3.66 (m, 1H), 2.29 (s, 3H), 2.02-1.90 (m, 1H), 1.34 (s, 9H), 0.91 (t, J=6.5Hz, 6H); 13 C NMR (151MHz, CDCl3) δ163.3, 156.2, 137.1, 134.3, 132.0, 129.4, 127.2, 126.5, 118.9, 73.9, 35.2, 31.2, 29.0, 20.8, 19.1; HRMS (ESI) m / z: [M+H] + Calculated for C 22 H 31 N2O2S: 387.2106, found: 387.2108; Enantiomeric excess: 63%, determined by HPLC (DaicelChiralpak IF, isopropanol / hexane=10 / 90, flow rate=1.0mL / min, T=30°C, λ=254nm): t R =21.78min (major), t R = 23.93min (minor).

[0583] Table 1 Synthesis of chiral thioimine esters in this invention

[0584]

[0585]

[0586]

[0587]

[0588]

[0589] The preferred embodiments of the present invention have been described in detail above. However, the present invention is not limited to the specific details in the above embodiments. Within the scope of the technical concept of the present invention, various simple modifications can be made to the technical solution of the present invention, and these simple modifications all fall within the protection scope of the present invention.

[0590] It should also be noted that the various specific technical features described in the above specific embodiments can be combined in any suitable manner without contradiction. In order to avoid unnecessary repetition, the present invention will not describe the various possible combinations separately.

[0591] Furthermore, various different embodiments of the present invention can be combined in any way, as long as they do not violate the spirit of the present invention, they should also be regarded as the content disclosed by the present invention.

Claims

1. A method for preparing a chiral thioimine ester compound, characterized in that, The preparation method includes: 1) The sulfenamide shown in Formula 2, the alcohol shown in Formula 3, MS, the metal-centered chiral cobalt(III) anion shown in Formula 1a, and ultra-dry tetrahydrofuran were mixed and reacted at -45℃ to -35℃ for 25-35 min. 2) Then N-iodosuccinimide was added, and the whole system was reacted at -45℃ to -35℃ for 35-37h. Na2S2O3 aqueous solution was added to separate the organic layer from the aqueous phase to quench the reaction. The chiral thioimide ester compound shown in Formula 4 was obtained by separation and purification. The structural formula shown in Equation 4 is: Among them, R 1 C 1-8 Straight-chain or branched alkyl groups, cycloalkyl groups, alkynyl groups, C3 halogenated straight-chain alkyl groups, C 6-9 One of the aryl or substituted aryl or naphthyl groups; The substituted aryl group is C. 1-3 One of the following: alkyl-substituted aryl, C2-oxoalkyl-substituted aryl, nitro-substituted phenethyl, trifluoromethyl-substituted benzyl, or halobenzyl; R 2 It is n-butyl or cyclohexyl, C 6-9 One of aryl, benzyl or substituted aryl, substituted benzyl or thiophene; The substituted aryl group is one of methyl or isopropyl substituted aryl, cyano substituted aryl, methyl formate substituted aryl, nitro substituted aryl, methoxy substituted aryl, trifluoromethyl substituted aryl, or haloaryl; the substituted benzyl group is methyl substituted benzyl. R 3 C 3 / 4 / 6 Straight-chain or branched alkyl / cycloalkyl, C 6-8 One of the substituted aryl, naphthyl, thiophene, or 4-methylaniline groups; The substituted aryl group is one of cyano-substituted aryl, trifluoromethyl-substituted aryl, nitro-substituted aryl, methyl formate-substituted aryl, benzoyl-substituted aryl, methyl-substituted aryl, methoxy-substituted aryl, or haloaryl.

2. The preparation method according to claim 1, wherein, R 1 The alkyl group is one of methyl, ethyl, n-propyl, isopropyl, isobutyl, 3-pentyl, n-hexyl, n-octyl, or β-cholestyl; The cycloalkyl group is one of cyclopropylmethyl, cyclobutyl, cyclohexyl, cyclopentylethyl, or cyclohexylethyl; The alkynyl group is one of 2-butynyl, 3-butynyl or 4-pentynyl; the halogen is one of fluorine, chlorine or bromine.

3. The preparation method according to claim 1, wherein, R 2 Halogens are one of fluorine, chlorine, or bromine.

4. The preparation method according to claim 1, wherein, R 3 The alkyl group is one of n-propyl, isopropyl, or tert-butyl; The cycloalkyl group is one of cyclopropyl or cyclohexyl; Halogens are one of fluorine, chlorine, or bromine.

5. The preparation method according to claim 1, wherein, In step (2), after the reaction is quenched, the aqueous phase is extracted with ethyl acetate, the organic layer is dried with Na2SO4, concentrated under reduced pressure, and purified by column chromatography using a mixture of petroleum ether / ethyl acetate as the eluent to obtain chiral thioimine ester compounds.

6. The preparation method according to claim 1, wherein, The amounts of isobutanol (0.15–0.25 mmol), the chiral cobalt(III) anion (0.005–0.015 mmol), and the N-iodosuccinimide (0.15–0.25 mmol) are relative to 0.10 mmol of sulfenamide. The dosage of MS is 95–105 mg, and the dosage of tetrahydrofuran is 0.05–0.15 mL.

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