CN112624963B - Silver-catalyzed serial cyclization reaction for constructing chiral 4-amino tetrahydrocarbazole - Google Patents

Silver-catalyzed serial cyclization reaction for constructing chiral 4-amino tetrahydrocarbazole Download PDF

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CN112624963B
CN112624963B CN201910903213.8A CN201910903213A CN112624963B CN 112624963 B CN112624963 B CN 112624963B CN 201910903213 A CN201910903213 A CN 201910903213A CN 112624963 B CN112624963 B CN 112624963B
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sulfinamide
carbazol
tetrahydro
methylpropan
methyl
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CN112624963A (en
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汪清民
宋红健
国忠林
刘玉秀
张静静
李永强
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Nankai University
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D209/56—Ring systems containing three or more rings
    • C07D209/80—[b, c]- or [b, d]-condensed
    • C07D209/82—Carbazoles; Hydrogenated carbazoles
    • C07D209/88—Carbazoles; Hydrogenated carbazoles with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to carbon atoms of the ring system
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
    • C07D409/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings
    • C07D409/12—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings linked by a chain containing hetero atoms as chain links
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B2200/00—Indexing scheme relating to specific properties of organic compounds
    • C07B2200/07—Optical isomers

Abstract

The invention belongs to the technical field of fine chemicals, and particularly relates to a chiral 4-aminotetrazole derivative and a preparation method thereof, wherein the chiral 4-aminotetrazole derivative is a compound shown in a formula (I).

Description

Silver-catalyzed serial cyclization reaction for constructing chiral 4-amino tetrahydrocarbazole
Technical Field
The invention belongs to the technical field of fine chemicals, and particularly relates to a chiral 4-amino tetrahydrocarbazole derivative and a preparation method thereof.
Background
Heterocyclic compounds are very important in nature and are widely distributed in nature. Heterocyclic drug discovery is one of the main areas of research in pharmaceutical chemistry. At present, a large number of heterocyclic compounds with pharmacological activity are already used clinically, such as vincristine, morphine, chloroquine, pethidine, sulfadiazine and the like. Tetrahydrocarbazole is a typical aza-cycle compound, and as early as the beginning of the last century, researchers have synthesized tetrahydrocarbazole using Fischer-tropsch, and have found that some tetrahydrocarbazole compounds exhibit good biological activities, such as antiviral, antifungal, anticancer. In particular, it has recently been found to exhibit excellent efficacy in the treatment of human migraine and human papillomaviruses. Chiral 4-aminotetrazole is found in a variety of natural products, such as ileine, (+) -leucomycin a, (+) -Kopsihainanine a, alsilobanine C, brucine alkaloid brucine (strychnine), tubifolidine, quebrachine (Aspidospermidine), cattail-line ((-) -Kopsinine) and indian picrinine ((-) -Venalstonine), and the like. Therefore, development of a novel and efficient method for constructing a 4-aminotetrazole skeleton is of great significance for the total synthesis of various natural products.
The series reaction saves the cost and time of experiments, lightens the workload of experimenters and realizes green chemistry and atomic economy. The tandem cyclization reaction can be used for efficiently constructing a ring structure: and a fused ring structure, a condensed ring structure, a spiro ring structure, etc.
Disclosure of Invention
The invention aims to provide a chiral 4-aminotetrazole derivative and a preparation method thereof.
The invention provides a chiral 4-aminotetrazole derivative and a preparation method thereof, wherein the chiral 4-aminotetrazole derivative is a compound shown in a formula (I):
wherein R is 1 、R 2 、R 3 And R is 4 Each independently selected from one or more of hydrogen, halogen, phenyl, C1-C6 hydrocarbyl, C1-C6 alkoxy;
r is C1-C12 alkyl, substituted or unsubstituted phenyl, sulfur-containing heterocycle containing 1-10 carbon atoms; the substituent groups of the substituted phenyl groups are each independently selected from one or more of halogen, cyano, C1-C6 hydrocarbyl and C1-C6 alkoxy;
the chirality of the 4-amino group is R-type or S-type, and the chirality of the sulfinyl group is R-type or S-type.
The invention provides a preparation method of the chiral 4-aminotetrahydro carbazole derivative, which comprises the following steps: in the presence of a catalyst and an additive, in an organic solvent, carrying out a serial cyclization reaction on 6-phenyl-5-hexyne imine shown in a formula (II) to obtain a compound shown in the formula (I);
Detailed Description
The invention provides a chiral 4-aminotetrazole derivative and a preparation method thereof, wherein the chiral 4-aminotetrazole derivative is a compound shown in a formula (I):
wherein R is 1 、R 2 、R 3 And R is 4 Each independently selected from one or more of hydrogen, halogen, phenyl, C1-C6 hydrocarbyl, C1-C6 alkoxy;
r is C1-C12 alkyl, substituted or unsubstituted phenyl, sulfur-containing heterocycle containing 1-10 carbon atoms; the substituent groups of the substituted phenyl groups are each independently selected from one or more of halogen, cyano, C1-C6 hydrocarbyl and C1-C6 alkoxy;
the chirality of the 4-amino is R type or S type, and the chirality of the sulfinyl is R type or S type;
in the present invention, specific examples of the C1-C12 alkyl group may be, for example: methyl, ethyl, n-propyl, isopropyl, cyclopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl and the like.
The C1-C6 hydrocarbon group may be selected from the specific examples of the alkyl groups described above and is subject to the corresponding limitations.
The C1-C6 alkoxy group may be an alkoxy group formed by the specific examples of the alkyl groups satisfying the definition of 1 to 6 carbon atoms described above.
The sulfur-containing heterocyclic ring having 1 to 10 carbon atoms may be an unsaturated sulfur heterocyclic ring or a saturated sulfur heterocyclic ring, provided that sulfur is a structural atom in the ring structure of the heterocyclic ring and the heterocyclic ring has 1 to 10 carbon atoms, and may be, for example, unsubstituted or C1-C6 alkyl-substituted thiophene, unsubstituted or C1-C6 alkyl-substituted hydrogenated thiophene, unsubstituted or C1-C7 alkyl-substituted thiazole, unsubstituted or C1-C7 alkyl-substituted hydrogenated thiazole, or the like.
Preferably, R 1 、R 2 、R 3 And R is 4 Each independently selected from one or more of hydrogen, F, cl, br, I, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, n-pentoxy, phenyl;
preferably, R is a C1-C6 alkyl, a substituted or unsubstituted phenyl, a sulfur-containing heterocycle having from 2 to 6 carbon atoms; the substituents of the substituted phenyl are each independently selected from one or more of hydrogen, F, cl, br, I, cyano, methyl, ethyl, n-propyl, isopropyl, cyclopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, n-pentoxy;
the chirality of the 4-amino group is R-type or S-type, and the chirality of the sulfinyl group is R-type or S-type.
In a preferred embodiment of the present invention, the compound represented by formula (I) is selected from one of the compounds represented by the following formulas:
(R) -2-methyl-N- ((S) 9-p-toluenesulfonyl-2, 3,4, 9-tetrahydro-1H-carbazol-4-yl) propane-2-sulfinamide (I-a 1);
(R) -2-methyl-N- ((R) 9-p-toluenesulfonyl-2, 3,4, 9-tetrahydro-1H-carbazol-4-yl) propane-2-sulfinamide (I-a 2);
(S) -2-methyl-N- ((S) 9-p-toluenesulfonyl-2, 3,4, 9-tetrahydro-1H-carbazol-4-yl) propane-2-sulfinamide (I-a 3);
(S) -2-methyl-N- ((R) 9-p-toluenesulfonyl-2, 3,4, 9-tetrahydro-1H-carbazol-4-yl) propane-2-sulfinamide (I-a 4);
(R) -2-methyl-N- ((S) 9- (benzenesulfonyl) -2,3,4, 9-tetrahydro-1H-carbazol-4-yl) propane-2-sulfinamide (I-b 1);
(R) -2-methyl-N- ((R) 9- (benzenesulfonyl) -2,3,4, 9-tetrahydro-1H-carbazol-4-yl) propane-2-sulfinamide (I-b 2);
(R) -N- ((S) 9- ((4-tert-butylbenzenesulfonyl) -2,3,4, 9-tetrahydro-1H-carbazol-4-yl) -2-methylpropan-2-sulfinamide (I-c 1);
(R) -N- ((R) 9- ((4-tert-butylbenzenesulfonyl) -2,3,4, 9-tetrahydro-1H-carbazol-4-yl) -2-methylpropan-2-sulfinamide (I-c 2);
(R) -N- ((S) 9- (4-methoxybenzenesulfonyl) -2,3,4, 9-tetrahydro-1H-carbazol-4-yl) -2-methylpropan-2-sulfinamide (I-d 1);
(R) -N- ((R) 9- (4-methoxybenzenesulfonyl) -2,3,4, 9-tetrahydro-1H-carbazol-4-yl) -2-methylpropan-2-sulfinamide (I-d 2);
(R) -N- ((S) 9- (4-fluorobenzenesulfonyl) -2,3,4, 9-tetrahydro-1H-carbazol-4-yl) -2-methylpropan-2-sulfinamide (I-e 1);
(R) -N- ((R) 9- (4-fluorobenzenesulfonyl) -2,3,4, 9-tetrahydro-1H-carbazol-4-yl) -2-methylpropan-2-sulfinamide (I-e 2);
(R) -N- ((S) 9- (4-chlorobenzenesulfonyl) -2,3,4, 9-tetrahydro-1H-carbazol-4-yl) -2-methylpropan-2-sulfinamide (I-f 1);
(R) -N- ((R) 9- (4-chlorobenzenesulfonyl) -2,3,4, 9-tetrahydro-1H-carbazol-4-yl) -2-methylpropan-2-sulfinamide (I-f 2);
(R) -N- ((S) 9- (4-bromobenzenesulfonyl) -2,3,4, 9-tetrahydro-1H-carbazol-4-yl) -2-methylpropan-2-sulfinamide (I-g 1);
(R) -N- ((R) 9- (4-bromobenzenesulfonyl) -2,3,4, 9-tetrahydro-1H-carbazol-4-yl) -2-methylpropan-2-sulfinamide (I-g 2);
(R) -N- ((S) 9- (4-cyanobenzenesulfonyl) -2,3,4, 9-tetrahydro-1H-carbazol-4-yl) -2-methylpropan-2-sulfinamide (I-H1);
(R) -N- ((R) 9- (4-cyanobenzenesulfonyl) -2,3,4, 9-tetrahydro-1H-carbazol-4-yl) -2-methylpropan-2-sulfinamide (I-H2);
(R) -2-methyl-N- ((S) 9-methanesulfonyl-2, 3,4, 9-tetrahydro-1H-carbazol-4-yl) propane-2-sulfinamide (I-I1);
(R) -2-methyl-N- ((R) 9-methanesulfonyl-2, 3,4, 9-tetrahydro-1H-carbazol-4-yl) propane-2-sulfinamide (I-I2);
(R) -N- ((S) 9-cyclopropylsulfonyl-2, 3,4, 9-tetrahydro-1H-carbazol-4-yl) -2-methylpropan-2-sulfinamide (I-j 1);
(R) -N- ((R) 9-cyclopropylsulfonyl-2, 3,4, 9-tetrahydro-1H-carbazol-4-yl) -2-methylpropan-2-sulfinamide (I-j 2);
(R) -2-methyl-N- ((S) 9- (thiophene-2-sulfonyl) -2,3,4, 9-tetrahydro-1H-carbazol-4-yl) propane-2-sulfinamide (I-k 1);
(R) -2-methyl-N- ((R) 9- (thiophene-2-sulfonyl) -2,3,4, 9-tetrahydro-1H-carbazol-4-yl) propane-2-sulfinamide (I-k 2);
(R) -2-methyl-N- ((S) 6-methyl-9-p-toluenesulfonyl-2, 3,4, 9-tetrahydro-1H-carbazol-4-yl) propane-2-sulfinamide (I-l 1);
(R) -2-methyl-N- ((R) 6-methyl-9-p-toluenesulfonyl-2, 3,4, 9-tetrahydro-1H-carbazol-4-yl) propane-2-sulfinamide (1-l 2);
(R) -2-methyl-N- ((S) 6-phenyl-9-p-toluenesulfonyl-2, 3,4, 9-tetrahydro-1H-carbazol-4-yl) propane-2-sulfinamide (I-m 1);
(R) -2-methyl-N- ((R) 6-phenyl-9-p-toluenesulfonyl-2, 3,4, 9-tetrahydro-1H-carbazol-4-yl) propane-2-sulfinamide (I-m 2);
(R) -N- ((S) 6-tert-butyl-9-p-toluenesulfonyl-2, 3,4, 9-tetrahydro-1H-carbazol-4-yl) -2-methylpropan-2-sulfinamide (I-N1);
(R) -N- ((R) 6-tert-butyl-9-p-toluenesulfonyl-2, 3,4, 9-tetrahydro-1H-carbazol-4-yl) -2-methylpropan-2-sulfinamide (I-N2);
(R) -N- ((S) 6-isopropyl-9-p-toluenesulfonyl-2, 3,4, 9-tetrahydro-1H-carbazol-4-yl) -2-methylpropan-2-sulfinamide (I-o 1);
(R) -N- ((R) 6-isopropyl-9-p-toluenesulfonyl-2, 3,4, 9-tetrahydro-1H-carbazol-4-yl) -2-methylpropan-2-sulfinamide (I-o 2);
(R) -N- ((S) 6-methoxy-9-p-toluenesulfonyl-2, 3,4, 9-tetrahydro-1H-carbazol-4-yl) -2-methylpropan-2-sulfinamide (I-p 1);
(R) -N- ((R) 6-methoxy-9-p-toluenesulfonyl-2, 3,4, 9-tetrahydro-1H-carbazol-4-yl) -2-methylpropan-2-sulfinamide (I-p 2);
(R) -N- ((S) 6-fluoro-9-p-toluenesulfonyl-2, 3,4, 9-tetrahydro-1H-carbazol-4-yl) -2-methylpropan-2-sulfinamide (I-q 1);
(R) -N- ((R) 6-fluoro-9-p-toluenesulfonyl-2, 3,4, 9-tetrahydro-1H-carbazol-4-yl) -2-methylpropan-2-sulfinamide (I-q 2);
(R) -N- ((S) 6-chloro-9-p-toluenesulfonyl-2, 3,4, 9-tetrahydro-1H-carbazol-4-yl) -2-methylpropan-2-sulfinamide (I-R1);
(R) -N- ((R) 6-chloro-9-p-toluenesulfonyl-2, 3,4, 9-tetrahydro-1H-carbazol-4-yl) -2-methylpropan-2-sulfinamide (I-R2);
(R) -N- ((S) 6-bromo-9-p-toluenesulfonyl-2, 3,4, 9-tetrahydro-1H-carbazol-4-yl) -2-methylpropan-2-sulfinamide (I-S1);
(R) -N- ((R) 6-bromo-9-p-toluenesulfonyl-2, 3,4, 9-tetrahydro-1H-carbazol-4-yl) -2-methylpropan-2-sulfinamide (I-s 2);
(R) -N- ((S) 7-chloro-9-p-toluenesulfonyl-2, 3,4, 9-tetrahydro-1H-carbazol-4-yl) -2-methylpropan-2-sulfinamide (I-t 1);
(R) -N- ((R) 7-chloro-9-p-toluenesulfonyl-2, 3,4, 9-tetrahydro-1H-carbazol-4-yl) -2-methylpropan-2-sulfinamide (I-t 2).
The invention provides a preparation method of the chiral 4-aminotetrahydro carbazole derivative, which comprises the following steps: in the presence of a catalyst and an additive, in an organic solvent, carrying out a serial cyclization reaction on 6-phenyl-5-hexyne imine shown in a formula (II) to obtain a compound shown in the formula (I);
according to the present invention, the compound represented by formula (II) may be specifically selected according to the desired formula (I), R 1 ，R 2 ，R 3 ，R 4 R is as described above, and the present invention is not described herein.
Preferably, the catalyst is AgNTf 2 、AgSbF 6 、AgOTf、AgTFA、AgOAc、AgBF 4 One or more of PhCOOAg.
Wherein the amount of catalyst may vary within wide limits, for example the molar ratio of 6-phenyl-5-hexyne imine of formula (II) to the amount of catalyst is from 1:0.1 to 0.5, preferably from 1:0.1 to 0.3.
Preferably, the additive is LiCl, liBr, liOAc, liOTf, liClO 4 、Li 2 CO 3 One or more of the following.
Wherein the amount of the additive may vary within a wide range, for example the molar ratio of 6-phenyl-5-hexyne imine of formula (II) to the amount of additive is 1:1-5, preferably 1:1-3.
Preferably, the organic solvent is one or more of acetonitrile, dichloromethane, dichloroethane, toluene, tetrahydrofuran and dioxane.
Preferably, the organic solvent is used in such an amount that the concentration of 6-phenyl-5-hexyne imine represented by formula (II) is 0.05-0.5mmol/mL.
Preferably, the conditions of the tandem reaction include: the temperature is 60-90 ℃ and the time is 4-12h.
The following examples are intended to further illustrate the invention but are not meant to limit it.
Example 1:
synthesis of (R) -2-methyl-N- ((S) 9-p-toluenesulfonyl-2, 3,4, 9-tetrahydro-1H-carbazol-4-yl) propane-2-sulfinamide (I-a 1) and (R) -2-methyl-N- ((R) 9-p-toluenesulfonyl-2, 3,4, 9-tetrahydro-1H-carbazol-4-yl) propane-2-sulfinamide (I-a 2)
Raw material (R, E) -N- (2- (6- (tert-butylsulfinylimino) hex-1-yne-1-) phenyl) -4-methylbenzenesulfonamide V-1 (1 mmol) was added to a Schlenk tube of 10 mL, then lithium carbonate (0.24 mg,3 mmol), silver hexafluoroantimonate (6.8 mg,0.2 mmol) was added, air was removed, argon was injected, dry toluene (1 mL) was added, heated to 60 ℃ C., the reaction was checked for about 6 hours, cooled, a small amount of water quench reaction was added, extracted twice with DCM, washed once with saturated saline, the organic phases were combined, dried over anhydrous sodium sulfate, desolventized, and separated by column chromatography to give (I-a 1) and (I-a 2) dr values of about 1:1, with a total yield of 85%.
(R) -2-methyl-N- ((S) 9-p-toluenesulfonyl-2, 3,4, 9-tetrahydro-1H-carbazol-4-yl) propane-2-sulfinamide (I-a 1)
A pale yellow liquid, which is a mixture of a light yellow liquid, 1 H NMR(400MHz，CDCl 3 )δ8.16(d，J＝8.0Hz，1H)， 7.69(d，J＝8.0Hz，2H)，7.49(d，J＝8.0Hz，1H)，7.30-7.26(m，1H)，7.23-7.21(m，3H)，4.64 -4.62(m，1H)，3.47-3.45(m，1H)，3.18-3.14(m，1H)，2.88-2.80(m，1H)，2.35(s，3H)， 2.20-1.91(m，4H)，1.21(s，9H)； 13 C NMR(100MHz，CDCl 3 )δ144.9，137.7，136.3，136.2，130.0， 128.8，126.5，124.2，123.3，119.2，118.2，114.3，56.4，50.5，31.5，24.4，22.8，21.6，18.6.
compounds I-a2 to I-t2 are completed by repeating the steps of I-1a and I-a 2.
The characterization results of the obtained compounds are shown below:
(R) -2-methyl-N- ((R) 9-p-toluenesulfonyl-2, 3,4, 9-tetrahydro-1H-carbazol-4-yl) propane-2-sulfinamide (I-a 2)
A pale yellow liquid, which is a mixture of a light yellow liquid, 1 H NMR(400MHz，CDCl 3 )δ8.15(d，J＝8.0Hz，1H)， 7.74-7.65(m，3H)，7.32-7.25(m，2H)，7.22(d，J＝8.0Hz，2H)，4.71(s，1H)，3.34(s，1H)，3.24 (d，J＝17.6Hz，1H)，2.86-2.73(m，1H)，2.35(s，3H)，2.00-1.75(m，4H)，1.18(s，9H). 13 C NMR (100MHz，CDCl 3 )δ144.9，138.2，136.2，136.0，130.0，128.0，126.5，124.5，123.9，118.7，117.3，114.3，55.4，46.4，29.9，24.4，22.6，21.6，17.7.HRMS(ESI)calcd for C 23 H 28 N 2 O 3 S 2 Na[M+Na] + 467.1434,found 467.1438 (high resolution of V-2a-1 and V-2a-2 mixtures, as is the case for the following compounds).
(S) -2-methyl-N- ((R) 9-p-toluenesulfonyl-2, 3,4, 9-tetrahydro-1H-carbazol-4-yl) propane-2-sulfinamide (I-a 3)
The overall yield of I-a3 and I-a4 was 77%.
A pale yellow liquid, which is a mixture of a light yellow liquid, 1 H NMR(400MHz，CDCl 3 )δ8.17(d，J＝7.6Hz，1H)， 7.76-7.70(m，3H)，7.34-7.28(m，2H)，7.25(d，J＝8.4Hz，2H)，4.73(d，J＝2.0Hz，1H)，3.32(s， 1H)，3.30-3.22(m，1H)，2.88-2.75(m，1H)，2.38(s，3H)，2.00-1.76(m，4H)，1.20(s，9H). 13 C NMR(100MHz，CDCl 3 )δ144.9，138.2，136.2，136.1，130.0，128.0，126.5，124.5，123.9，118.7， 117.3，114.3，55.4，46.3，29.9，24.4，22.6，21.6，17.7.
(S) -2-methyl-N- ((S) 9-p-toluenesulfonyl-2, 3,4, 9-tetrahydro-1H-carbazol-4-yl) propane-2-sulfinamide (I-a 4)
A pale yellow liquid, which is a mixture of a light yellow liquid, 1 H NMR(400MHz，CDCl 3 )δ8.19(d，J＝8.4Hz，1H)，7.72(d，J＝8.4Hz，2H)，7.52(d，J＝7.6Hz，1H)，7.32-7.30(m，1H)，7.27-7.21(m，3H)，4.73- 4.57(m，1H)，3.39(d，J＝10.4Hz，1H)，3.22-3.16(m，1H)，2.95-2.78(m，1H)，2.38(s，3H)，2.26 -1.93(m，4H)，1.23(s，9H). 13 C NMR(100MHz，CDCl 3 )δ144.9，137.7，136.3，136.2，130.0， 128.8，126.5，124.2，123.3，119.2，118.3，114.3，56.3，50.4，31.5，24.4，22.7，21.6，18.6.HRMS(ESI) calcd for C 23 H 28 N 2 O 3 S 2 Na[M+Na] + 467.1434，found 467.1437.
(R) -2-methyl-N- ((S) 9- (benzenesulfonyl) -2,3,4, 9-tetrahydro-1H-carbazol-4-yl) propane-2-sulfinamide (I-b 1)
I-b1 and I-b2 yield 81% overall.
A pale yellow liquid, which is a mixture of a light yellow liquid, 1 H NMR(400MHz，CDCl 3 )δ8.16(d，J＝7.6Hz，1H)， 7.82(d，J＝7.6Hz，2H)，7.72(d，J＝7.2Hz，1H)，7.56(t，J＝7.6Hz，1H)，7.45(t，J＝7.6Hz，2H)， 7.33-7.27(m，2H)，4.72(s，1H)，3.31(s，1H)，3.28-3.20(m，1H)，2.87-2.73(m，1H)，2.03- 1.90(m，3H)，1.83-1.77(m，1H)，1.18(s，9H). 13 C NMR(100MHz，CDCl 3 )δ139.0，138.2，136.2， 133.8，129.4，128.0，126.5，124.6，124.0，118.8，117.5，114.3，55.4，46.3，29.9，24.4，22.6，17.7.
(R) -2-methyl-N- ((R) 9- (benzenesulfonyl) -2,3,4, 9-tetrahydro-1H-carbazol-4-yl) propane-2-sulfinamide (I-b 2)
A pale yellow liquid, which is a mixture of a light yellow liquid, 1 H NMR(400MHz，CDCl 3 )δ8.20(d，J＝8.4Hz，1H)， 7.86-7.80(m，2H)，7.61-7.55(m，1H)，7.52(d，J＝7.6Hz，1H)，7.47(t，J＝8.0Hz，2H)，7.34- 7.29(m，1H)，7.28-7.22(m，1H)，4.71-4.60(m，1H)，3.39(d，J＝10.4Hz，1H)，3.19(dt，J＝18.4， 4.8Hz，1H)，2.94-2.81(m，1H)，2.28-2.19(m，1H)，2.12-2.03(m，1H)，1.98-1.90(m，2H)， 1.23(s，9H). 13 C NMR(100MHz，CDCl 3 )δ139.1，137.6，136.3，133.8，129.4，128.8，126.5，124.3， 123.4，119.2，118.5，114.3，56.4，50.4，31.5，24.4，22.8，18.6.HRMS(ESI)calcd for C 22 H 26 N 2 O 3 S 2 Na[M+Na] + 453.1277，found 453.1281.
(R) -N- ((S) 9- ((4-tert-Butylbenzenesulfonyl) -2,3,4, 9-tetrahydro-1H-carbazol-4-yl) -2-methylpropan-2-sulfinamide (I-c 1)
The total yield of I-c1 and I-c2 was 73%.
A pale yellow liquid, which is a mixture of a light yellow liquid, 1 H NMR(400MHz，CDCl 3 )δ8.16(d，J＝7.6Hz，1H)， 7.77-7.71(m，3H)，7.45(d，J＝8.8Hz，2H)，7.33-7.26(m，2H)，4.73(d，J＝2.4Hz，1H)，3.35- 3.21(m，2H)，2.90-2.75(m，1H)，2.04-1.78(m，4H)，1.28(s，9H)，1.18(s，9H). 13 C NMR(100 MHz，CDCl 3 )δ157.8，138.2，136.2，136.1，127.9，126.4，126.4，124.5，123.8，118.7，117.1，114.3， 55.4，46.3，35.3，31.0，29.9，24.4，22.6，17.7.
(R) -N- ((R) 9- ((4-tert-butylbenzenesulfonyl) -2,3,4, 9-tetrahydro-1H-carbazol-4-yl) -2-methylpropan-2-sulfinamide (I-c 2) as a pale yellow liquid, 1 H NMR(400MHz，CDCl 3 )δ8.19(d，J＝8.4Hz，1H)， 7.78-7.71(m，2H)，7.51(d，J＝7.6Hz，1H)，7.47-7.43(m，2H)，7.31-7.28(m，1H)，7.25-7.21 (m，1H)，4.69-4.60(m，1H)，3.36(d，J＝10.4Hz，1H)，3.20(d，J＝18.4Hz，1H)，2.92-2.82(m， 1H)，2.21-1.95(m，4H)，1.28(s，9H)，1.21(s，9H). 13 CNMR(100MHz，CDCl 3 )δ157.8，137.7， 136.3，128.7，126.4，126.4，124.2，123.2，119.2，118.1，114.3，56.3，50.4，35.3，31.5，31.0，24.4，22.8， 18.6.HRMS(ESI)calcd for C 26 H 34 N 2 O 3 S 2 Na[M+Na] + 509.1903，found 509.1907.
(R) -N- ((S) 9- (4-methoxybenzenesulfonyl) -2,3,4, 9-tetrahydro-1H-carbazol-4-yl) -2-methylpropan-2-sulfinamide (I-d 1)
The total yield of I-d1 and I-d2 was 73%.
A pale yellow liquid, which is a mixture of a light yellow liquid, 1 H NMR(400MHz，CDCl 3 )δ8.13(d，J＝7.6Hz，1H)， 7.74(d，J＝8.8Hz，2H)，7.69(d，J＝7.2Hz，1H)，7.30-7.26(m，1H)，7.24(s，1H)，6.86(d，J＝8.8 Hz，2H)，4.69(s，1H)，3.78(s，3H)，3.28(s，1H)，3.25-3.17(m，1H)，2.83-2.71(m，1H)，2.03- 1.73(m，4H)，1.15(s，9H). 13 CNMR(100MHz，CDCl 3 )δ163.7，138.2，136.2，130.6，128.8，128.0， 124.4，123.8，118.7，117.2，114.5，114.3，55.7，55.4，46.3，29.9，24.5，22.6，17.8.
(R) -N- ((R) 9- (4-methoxybenzenesulfonyl) -2,3,4, 9-tetrahydro-1H-carbazol-4-yl) -2-methylpropan-2-sulfinamide (I-d 2)
A pale yellow liquid, which is a mixture of a light yellow liquid, 1 H NMR(400MHz，CDCl 3 )δ8.15(d，J＝8.4Hz，1H)， 7.73(d，J＝8.8Hz，2H)，7.47(d，J＝7.6Hz，1H)，7.24(s，1H)，7.20-7.17(m，1H)，6.86(d，J＝8.8 Hz，2H)，4.66-4.55(m，1H)，3.78(s，3H)，3.34(d，J＝10.4Hz，1H)，3.17-3.11(m，1H)，2.88- 2.77(m，1H)，2.23-1.87(m，4H)，1.19(s，9H). 13 C NMR(100MHz，CDCl 3 )δ163.7，137.6，136.2， 130.7，128.7，128.1，124.2，123.2，119.2，118.2，114.5，114.3，56.3，55.7，50.5，31.5，24.4，22.8，18.6. HRMS(ESI)calcd for C 23 H 28 N 2 O 4 S 2 Na[M+Na] + 483.1383，found 483.1387.
(R) -N- ((S) 9- (4-fluorobenzenesulfonyl) -2,3,4, 9-tetrahydro-1H-carbazol-4-yl) -2-methylpropan-2-sulfinamide (I-e 1)
The total yield of I-e1 and I-e2 was 82%.
A pale yellow liquid, which is a mixture of a light yellow liquid, 1 H NMR(400MHz，CDCl 3 )δ8.13(d，J＝7.2，1H)，7.87 -7.80(m，2H)，7.73-7.71(m，1H)，7.34-7.27(m，2H)，7.12(t，J＝8.4Hz，2H)，4.76-4.69(m， 1H)，3.31-3.18(m，2H)，2.86-2.73(m，1H)，2.05-1.90(m，3H)，1.82-1.73(m，1H)，1.18(s， 9H). 13 C NMR(100MHz，CDCl 3 )δ165.6(d，J＝278.0)，138.1，136.1，129.3(d，J＝10)，128.1， 124.7，124.2，118.9，117.8，116.9，116.6，114.2，55.4，46.3，29.9，24.5，22.6，17.8.
(R) -N- ((R) 9- (4-fluorobenzenesulfonyl) -2,3,4, 9-tetrahydro-1H-carbazol-4-yl) -2-methylpropan-2-sulfinamide (I-e 2)
A pale yellow liquid, which is a mixture of a light yellow liquid, 1 H NMR(400MHz，CDCl 3 )δ8.17(d，J＝8.4Hz，1H)， 7.88-7.82(m，2H)，7.53(d，J＝7.6Hz，1H)，7.32(t，J＝7.2Hz，1H)，7.28-7.24(m，1H)，7.14(t， J＝8.4Hz，2H)，4.70-4.60(m，1H)，3.38(d，J＝10.4Hz，1H)，3.18(dt，J＝18.4，4.8Hz，1H)，2.91 -2.80(m，1H)，2.27-2.21(m，1H)，2.12-2.03(m，1H)，2.00-1.91(m，2H)，1.23(s，9H). 13 C NMR(100MHz，CDCl 3 )δ165.6(d，J＝274.6)，137.5，136.2，129.3(d，J＝10)，128.9，124.5，123.6，119.4，118.8，116.8，116.6，114.3，56.3，50.4，31.5，24.4，22.7，18.6.HRMS(ESI)calcd for C 22 H 25 FN 2 O 3 S 2 Na[M+Na] + 471.1184，found 471.1188.
(R) -N- ((S) 9- (4-Chlorenesulfonyl) -2,3,4, 9-tetrahydro-1H-carbazol-4-yl) -2-methylpropan-2-sulfinamide (I-f 1)
The total yield of I-f1 and I-f2 was 80%.
A pale yellow liquid, which is a mixture of a light yellow liquid, 1 H NMR(400MHz，CDCl 3 )δ8.14-8.12(m，1H)，7.76 -7.71(m，3H)，7.41(d，J＝8.8Hz，2H)，7.33-7.28(m，2H)，4.72-4.68(m，1H)，3.29(d，J＝1.6 Hz，1H)，3.25-3.18(m，1H)，2.83-2.73(m，1H)，2.03-1.91(m，3H)，1.81-1.73(m，1H)，1.18(s， 9H). 13 C NMR(100MHz，CDCl 3 )δ140.5，138.1，137.3，136.2，129.7，128.1，127.9，124.8，124.3， 118.9，118.0，114.2，55.4，46.3，29.9，24.5，22.6，17.8.
(R) -N- ((R) 9- (4-Chlorenesulfonyl) -2,3,4, 9-tetrahydro-1H-carbazol-4-yl) -2-methylpropan-2-sulfinamide (I-f 2)
A pale yellow liquid, which is a mixture of a light yellow liquid, 1 H NMR(400MHz，CDCl 3 )δ8.14(d，J＝8.4Hz，1H)， 7.74(d，J＝8.8Hz，2H)，7.51(d，J＝7.6Hz，1H)，7.41(d，J＝8.8Hz，2H)，7.30(t，J＝7.2Hz，1H)， 7.25-7.22(m，1H)，4.68-4.58(m，1H)，3.36(d，J＝8.4Hz，1H)，3.15(dt，J＝18.4，4.8Hz，1H)，2.90-2.78(m，1H)，2.26-2.18(m，1H)，2.11-2.02(m，1H)，1.97-1.89(m，2H)，1.21(s，9H). 13 C NMR(100MHz，CDCl 3 )δ140.5，137.5，137.4，136.2，129.7，128.9，127.9，124.5，123.7，119.4， 119.0，114.3，56.4，50.4，31.4，24.5，22.8，18.6.HRMS(ESI)calcd for C 22 H 25 ClN 2 O 3 S 2 Na[M+Na] + 487.0887，found 487.0892.
(R) -N- ((S) 9- (4-bromobenzenesulfonyl) -2,3,4, 9-tetrahydro-1H-carbazol-4-yl) -2-methylpropan-2-sulfinamide (I-g 1)
I-g1 and I-g2 yield 70% overall.
A pale yellow liquid, which is a mixture of a light yellow liquid, 1 H NMR(400MHz，CDCl 3 )δ8.14(d，J＝8.0，1H)，7.76 -7.74(m，1H)，7.68(d，J＝8.8Hz，2H)，7.59(d，J＝8.8Hz，2H)，7.36-7.29(m，2H)，4.73-4.71 (m，1H)，3.32(s，1H)，3.27-3.19(m，1H)，2.86-2.75(m，1H)，2.06-1.81(m，4H)，1.20(s，9H). 13 C NMR(100MHz，CDCl 3 )δ138.1，137.9，136.2，132.7，129.0，128.1，127.9，124.8，124.3，118.9， 118.0，114.2，55.4，46.4，29.9，24.5，22.6，17.8.
(R) -N- ((R) 9- (4-bromophenylsulfonyl) -2,3,4, 9-tetrahydro-1H-carbazol-4-yl) -2-methylpropan-2-sulfinamide (I-g 2)
A pale yellow liquid, which is a mixture of a light yellow liquid, 1 H NMR(400MHz，CDCl 3 )δ8.09(d，J＝8.0，1H)，7.77 -7.74(m，1H)，7.69(d，J＝8.8Hz，2H)，7.60(d，J＝8.8Hz，2H)，7.35-7.27(m，2H)，4.73-4.70 (m，1H)，3.34(s，1H)，3.26-3.18(m，1H)，2.85-2.76(m，1H)，2.09-1.85(m，4H)，1.23(s，9H). 13 C NMR(100MHz，CDCl 3 )δ138.4，137.6，136.1，132.5，129.1，128.1，127.8，124.7，124.3，118.8， 118.2，114.3，55.5，46.4，29.8，24.7，22.6，17.7.HRMS(ESI)calcd for C 22 H 25 BrN 2 O 3 S 2 Na[M+Na] + 531.0382，found 531.0388.
(R) -N- ((S) 9- (4-cyanobenzenesulfonyl) -2,3,4, 9-tetrahydro-1H-carbazol-4-yl) -2-methylpropan-2-sulfinamide (I-H1)
The total yield of I-h1 and I-h2 was 71%.
A pale yellow liquid, which is a mixture of a light yellow liquid, 1 H NMR(400MHz，CDCl 3 )δ8.10(d，J＝7.2Hz，1H)， 7.90(d，J＝8.4Hz，2H)，7.73(d，J＝8.4Hz，3H)，7.34-7.28(m，2H)，4.71-4.68(m，1H)，3.31(d， J＝1.6Hz，1H)，3.23-3.17(m，1H)，2.84-2.70(m，1H)，2.05-1.76(m，4H)，1.18(s，9H). 13 C NMR(100MHz，CDCl 3 )δ142.6，138.0，136.0，133.2，128.3，127.1，125.1，124.6，119.2，118.6， 117.5，116.9，114.2，55.5，46.4，30.0，24.5，22.6，17.7.
(R) -N- ((R) 9- (4-cyanobenzenesulfonyl) -2,3,4, 9-tetrahydro-1H-carbazol-4-yl) -2-methylpropan-2-sulfinamide (I-H2)
A pale yellow liquid, which is a mixture of a light yellow liquid, 1 H NMR(400MHz，CDCl 3 )δ8.11(d，J＝8.4Hz，1H)， 7.90(d，J＝8.0Hz，2H)，7.73(d，J＝8.4Hz，2H)，7.52(d，J＝7.6Hz，1H)，7.31(t，J＝7.6Hz，1H)， 7.27-7.23(m，1H)，4.69-4.58(m，1H)，3.38(d，J＝8.4Hz，1H)，3.20-3.09(m，1H)，2.88-2.76 (m，1H)，2.23-1.95(m，4H)，1.21(s，9H). 13 C NMR(100MHz，CDCl 3 )δ142.7，137.4，136.1，133.2，129.0，127.1，124.8，124.0，119.6，118.7，117.6，116.9，114.2，56.4，50.3，31.4，24.5，22.7， 18.6.HRMS(ESI)calcd for C 24 H 27 N 3 O 3 S 2 Na[M+Na] + 478.1235，found 478.1235.
(R) -2-methyl-N- ((S) 9-methanesulfonyl-2, 3,4, 9-tetrahydro-1H-carbazol-4-yl) propane-2-sulfinamide (I-I1)
I-I1 and I-I2 yield 76% overall.
A pale yellow liquid, which is a mixture of a light yellow liquid, 1 H NMR(400MHz，CDCl 3 )δ8.01-7.96(m，1H)，7.81 -7.77(m，1H)，7.33-7.30(m，2H)，4.79(s，1H)，3.38(s，1H)，3.18-3.11(m，1H)，3.07(s，3H)， 2.85-2.75(m，1H)，2.09-1.84(m，4H)，1.21(s，9H). 13 C NMR(100MHz，CDCl 3 )δ138.2，136.0， 128.0，124.7，124.1，119.0，117.2，113.7，55.5，46.4，40.9，20.0，24.3，22.6，17.7.
(R) -2-methyl-N- ((R) 9-methanesulfonyl-2, 3,4, 9-tetrahydro-1H-carbazol-4-yl) propane-2-sulfinamide (I-I2)
A pale yellow liquid, which is a mixture of a light yellow liquid, 1 H NMR(400MHz，CDCl 3 )δ7.96(d，J＝7.6Hz，1H)， 7.58-7.53(m，1H)，7.30-7.27(m，1H)，7.25-7.23(m，1H)，4.71-4.65(m，1H)，3.42(d，J＝8.4 Hz，1H)，3.12-3.05(m，1H)，3.04(s，3H)，2.86-2.77(m，1H)，2.27-1.89(m，4H)，1.22(s，9H). 13 C NMR(100MHz，CDCl 3 )δ137.7，136.0，128.8，124.5，123.5，119.4，118.2，113.8，56.4，50.5， 41.0，31.5，24.3，22.8，18.6.HRMS(ESI)calcd for C 17 H 24 N 2 O 3 S 2 Na[M+Na] + 391.1121，found 391.1125.
(R) -N- ((S) 9-cyclopropylsulfonyl-2, 3,4, 9-tetrahydro-1H-carbazol-4-yl) -2-methylpropan-2-sulfinamide (I-j 1)
The total yield of I-j1 and I-j2 was 69%.
A pale yellow liquid, which is a mixture of a light yellow liquid, 1 H NMR(400MHz，CDCl 3 )δ8.03-7.97(m，1H)，7.81 -7.76(m，1H)，7.32-7.28(m，2H)，4.80(s，1H)，3.37(s，1H)，3.21-3.11(m，1H)，2.85-2.71(m， 1H)，2.63-2.56(m，1H)，2.07-1.83(m，4H)，1.40-1.34(m，2H)，1.21(s，9H)，1.03-0.97(m， 2H). 13 C NMR(100MHz，CDCl 3 )δ138.2，136.3，127.9，124.4，123.8，118.8，116.8，113.9，55.4， 46.3，31.7，29.9，24.4，22.6，17.8，5.8.
(R) -N- ((R) 9-cyclopropylsulfonyl-2, 3,4, 9-tetrahydro-1H-carbazol-4-yl) -2-methylpropan-2-sulfinamide (I-j 2)
A pale yellow liquid, which is a mixture of a light yellow liquid, 1 H NMR(400MHz，CDCl 3 )δ8.00(d，J＝7.2Hz，1H)，7.62-7.53(m，1H)，7.29-7.23(m，2H)，4.78-4.66(m，1H)，3.44(d，J＝10.4Hz，1H)，3.14- 3.07(m，1H)，2.89-2.79(m，1H)，2.64-2.55(m，1H)，2.31-2.23(m，1H)，2.17-2.08(m，1H)， 2.01-1.93(m，2H)，1.40-1.34(m，2H)，1.25(s，9H)，1.04-0.98(m，2H). 13 C NMR(100MHz， CDCl 3 )δ137.7，136.3，128.7，124.2，123.2，119.3，117.8，114.0，56.4，50.6，31.7，31.6，24.4，22.8， 18.7，5.8.HRMS(ESI)calcd for C 19 H 26 N 2 O 3 S 2 Na[M+Na] + 417.1277，found 417.1282.
(R) -2-methyl-N- ((S) 9- (thiophene-2-sulfonyl) -2,3,4, 9-tetrahydro-1H-carbazol-4-yl) propane-2-sulfinamide (I-k 1)
I-k1 and I-k2 yield 76% overall.
A pale yellow liquid, which is a mixture of a light yellow liquid, 1 H NMR(400MHz，CDCl 3 )δ8.13(d，J＝8.0，1H)， 7.73(d，J＝7.6.1H)，7.64(dd，J＝4.0，1.2Hz，1H)，7.54(dd，J＝5.6，1.2Hz，1H)，7.34-7.28(m， 2H)，7.00(t，J＝4.8，4.0Hz，1H)，4.72(s，1H)，3.31(s，1H)，3.30-3.23(m，1H)，2.93-2.82(m，1H)，2.05-1.92(m，3H)，1.83-1.77(m，1H)，1.19(s，9H). 13 C NMR(100MHz，CDCl 3 )δ138.8， 138.3，135.9，133.2，132.6，128.3，127.5，124.6，124.3，118.9，118.1，114.5，55.4，46.3，29.9，24.6， 22.6，17.7.
(R) -2-methyl-N- ((R) 9- (thiophene-2-sulfonyl) -2,3,4, 9-tetrahydro-1H-carbazol-4-yl) propane-2-sulfinamide (I-k 2)
A pale yellow liquid, which is a mixture of a light yellow liquid, 1 H NMR(400MHz，CDCl 3 )δ8.14(d，J＝8.4Hz，1H)， 7.64(d，J＝7.6Hz，1H)，7.55-7.49(m，2H)，7.31(t，J＝7.2Hz，1H)，7.23(d，J＝7.2Hz，1H)，7.00 (t，J＝4.4Hz，1H)，4.71-4.58(m，1H)，3.39(d，J＝8.4Hz，1H)，3.20(dt，J＝18.4，4.8Hz，1H)， 2.96-2.86(m，1H)，2.22(dt，J＝8.4，4.8Hz，1H)，2.12-2.03(m，1H)，2.00-1.91(m，2H)，1.22(s， 9H). 13 C NMR(100MHz，CDCl 3 )δ138.9，137.7，135.9，133.2，132.5，129.1，127.5，124.4，123.7， 119.3，119.1，114.5，56.4，50.4，31.5，24.5，22.8，18.6.HRMS(ESI)calcd for C 20 H 24 N 2 O 3 S 2 Na [M+Na] + 459.0841，found 459.0846.
(R) -2-methyl-N- ((S) 6-methyl-9-p-toluenesulfonyl-2, 3,4, 9-tetrahydro-1H-carbazol-4-yl) propane-2-sulfinamide (I-l 1)
I-l1 and I-l2 yield 74% overall.
A colorless liquid, which is a liquid, 1 H NMR(400MHz，CDCl 3 )δ8.02(d，J＝8.4Hz，1H)， 7.68(d，J＝8.4Hz，2H)，7.46(s，1H)，7.21(d，J＝8.0Hz，2H)，7.10(d，J＝8.0，Hz，1H)，4.68(s， 1H)，3.29-3.18(m，2H)，2.84-2.70(m，1H)，2.42(s，3H)，2.35(s，3H)，2.03-1.69(m，4H)1.18 (s，9H). 13 C NMR(100MHz，CDCl 3 )δ144.8，138.3，136.1，134.4，133.6，129.9，128.3，126.5125.8， 118.5，117.1，114.0，55.4，46.2，29.7，24.5，22.6，21.6，21.4，17.6.
(R) -2-methyl-N- ((R) 6-methyl-9-p-toluenesulfonyl-2, 3,4, 9-tetrahydro-1H-carbazol-4-yl) propane-2-sulfinamide (I-l 2)
A colorless liquid, which is a liquid, 1 H NMR(400MHz，CDCl 3 )δ8.02(d，J＝8.0Hz，1H)， 7.67(d，J＝8.4Hz，2H)，7.28(s，1H)，7.22(d，J＝8.0Hz，2H)，7.10(d，J＝8.4，1H)，4.64-4.55(m， 1H)，3.34(d，J＝10.4Hz，1H)，3.18-3.09(m，1H)，2.89-2.78(m，1H)，2.22-1.22(m，4H)，1.22 (s，9H)， 13 C NMR(100MHz，CDCl 3 )δ144.8，137.6，136.2，134.5，132.8，129.9，129.0，126.5， 125.5，119.4，118.2，114.0，56.4，50.7，31.6，24.4，22.7，21.6，21.3，18.8.HRMS(ESI)calcd for C 24 H 30 N 2 O 3 S 2 Na[M+Na] + 481.1590，found 481.1594.
(R) -2-methyl-N- ((S) 6-phenyl-9-p-toluenesulfonyl-2, 3,4, 9-tetrahydro-1H-carbazol-4-yl) propane-2-sulfinamide (I-m 1) I-m1 and I-m2 in a total yield of 72%.
A pale yellow liquid, which is a mixture of a light yellow liquid, 1 H NMR(400MHz，CDCl 3 )δ8.20(d，J＝8.8Hz， 1H)，7.93(d，J＝1.6Hz，1H)，7.73(d，J＝8.4Hz，2H)，7.66(d，J＝7.2Hz，2H)，7.56(dd，J＝8.8， 1.6Hz，1H)，7.43(t，J＝7.6Hz，2H)，7.31(t，J＝7.6Hz，1H)，7.24(d，J＝8.4Hz，2H)，4.76(s，1H)， 3.35-3.21(m，2H)，2.87-2.74(m，1H)，2.36(s，3H)，2.04-1.76(m，4H)，1.19(s，9H). 13 C NMR (100MHz，CDCl 3 )δ145.0，140.8，138.8，137.0，136.1，135.6，130.0，128.9，128.6，127.2，127.0， 126.6，123.8，117.6，116.8，114.5，55.4，46.4，29.9，24.5，22.6，21.6，17.7.
(R) -2-methyl-N- ((R) 6-phenyl-9-p-toluenesulfonyl-2, 3,4, 9-tetrahydro-1H-carbazol-4-yl) propane-2-sulfinamide (I-m 2) as a pale yellow liquid, 1 H NMR(400MHz，CDCl 3 )δ8.21(d，J＝8.8Hz，1H)， 7.76-7.70(m，3H)，7.58-7.55(m，2H)，7.52(dd，J＝8.8，1.6Hz，1H)，7.42(t，J＝7.6Hz，2H)， 7.35-7.30(m，1H)，7.24(s，2H)，4.71-4.62(m，1H)，3.40(d，J＝10.4Hz，1H)，3.21-3.12(m，1H)，2.93-2.82(m，1H)，2.37(s，3H)，2.23-1.93(m，4H)， 13 C NMR(100MHz，CDCl 3 )δ145.0， 141.2，138.3，136.6，136.1，135.7，130.0，129.3，128.8，127.6，127.4，126.6，123.7，118.4，117.7， 114.5，56.3，50.8，31.6，24.4，22.8，21.6，18.8.HRMS(ESI)calcd for C 29 H 32 N 2 O 3 S 2 [M+Na] + 543.1747，found 543.1750.
(R) -N- ((S) 6-tert-butyl-9-p-toluenesulfonyl-2, 3,4, 9-tetrahydro-1H-carbazol-4-yl) -2-methylpropan-2-sulfinamide (I-N1)
I-n1 and I-n2 yield 75% overall.
A pale yellow liquid, which is a mixture of a light yellow liquid, 1 H NMR(400MHz，CDCl 3 )δ8.05(d，J＝8.8Hz，1H)，7.73-7.71(m，3H)，7.37-7.34(m，1H)，7.23(d，J＝8.0Hz，2H)，4.72(s，1H)，3.33(s，1H)，3.25 -3.16(m，1H)，2.82-2.73(m，1H)，2.36(s，3H)，2.03-1.76(m，4H)，1.36(s，9H)，1.18(s，9H). 13 C NMR(100MHz，CDCl 3 )δ147.1，144.8，138.1，136.2，134.2，130.0，127.8，126.6，122.2，117.3， 115.1，113.7，55.3，46.4，34.8，31.8，30.1，24.4，22.6，21.6，17.9.
(R) -N- ((R) 6-tert-butyl-9-p-toluenesulfonyl-2, 3,4, 9-tetrahydro-1H-carbazol-4-yl) -2-methylpropan-2-sulfinamide (I-N2), pale yellow liquid, 1 H NMR(400MHz，CDCl 3 )δ8.07(d，J＝8.8 Hz，1H)，7.72(d，J＝8.4Hz，2H)，7.46(s，1H)，7.35(d，J＝8.8Hz，1H)，7.24(d，J＝8.0Hz，2H)， 4.68-4.59(m，1H)，3.35(d，J＝10.4Hz，1H)，3.19-3.12(m，1H)，2.88-2.75(m，1H)，2.37(s， 3H)，2.30-1.81.(m，4H)，1.33(s，9H)，1.23(s，9H). 13 C NMR(100MHz，CDCl 3 )δ146.4，144.8， 137.6，136.3，134.2，130.0，128.4，126.6，122.2，118.2，115.3，113.8，56.3，50.6，34.7，31.7，31.4， 24.6，22.8，21.6，18.5.HRMS(ESI)calcd for C 27 H 36 N 2 O 3 S 2 Na[M+Na] + 523.2060，found 523.2065.
(R) -N- ((S) 6-isopropyl-9-p-toluenesulfonyl-2, 3,4, 9-tetrahydro-1H-carbazol-4-yl) -2-methylpropan-2-sulfinamide (1-o 1)
The total yield of I-o1 and I-o2 was 68%.
A pale yellow liquid, which is a mixture of a light yellow liquid, 1 H NMR(400MHz，CDCl 3 )δ8.03(d，J＝8.4Hz，1H)， 7.69(d，J＝8.4Hz，2H)，7.52(s，1H)，7.21(d，J＝8.4Hz，2H)，7.17-7.14(m，1H)，4.69(s，1H)， 3.29(s，1H)，3.23-3.15(m，1H)，3.03-2.92(m，1H)，2.82-2.71(m，1H)，2.34(s，3H)，2.03- 1.69(m，4H)，1.25(dd，J＝7.2，1.2Hz，6H)，1.16(s，9H). 13 C NMR(100MHz，CDCl 3 )δ144.8， 138.2，136.3，134.6，129.9，128.1，126.6，123.3，117.2，116.0，114.1，55.3，46.3，34.0，29.9，24.4， 23.7，22.6，21.6，17.8.
(R) -N- ((R) 6-isopropyl-9-p-toluenesulfonyl-2, 3,4, 9-tetrahydro-1H-carbazol-4-yl) -2-methylpropan-2-sulfinamide (I-o 2)
A pale yellow liquid, which is a mixture of a light yellow liquid, 1 H NMR(400MHz，CDCl 3 )δ8.07(d，J＝8.4Hz，1H)， 7.65(d，J＝8.4Hz，2H)，7.52(s，1H)，7.20-7.17(m，2H)，7.18-7.13(m，1H)，4.66(s，1H)，3.27(s， 1H)，3.23-3.17(m，1H)，3.05-2.92(m，1H)，2.82-2.71(m，1H)，2.34(s，3H)，2.03-1.69(m， 4H)，1.26(dd，J＝7.2，1.2Hz，6H)，1.16(s，9H). 13 C NMR(100MHz，CDCl 3 )δ144.9，138.4，136.4， 134.6，130.1，128.3，126.7，123.5，117.2，116.1，114.1，55.4，46.5，34.0，30.1，24.5，23.6，22.6，21.4， 17.8.HRMS(ESI)calcd for C 26 H 35 N 2 O 3 S 2 [M+H] + 487.2089，found 487.2088.
(R) -N- ((S) 6-methoxy-9-p-toluenesulfonyl-2, 3,4, 9-tetrahydro-1H-carbazol-4-yl) -2-methylpropan-2-sulfinamide (I-p 1)
The total yield of I-p1 and I-p2 was 79%.
A pale yellow liquid, which is a mixture of a light yellow liquid, 1 H NMR(400MHz，CDCl 3 )δ8.02(d，J＝9.2Hz，1H)， 7.66(d，J＝8.4Hz，2H)，7.27-7.25(m，1H)，7.21(d，J＝8.0Hz，2H)，6.89-6.70(m，1H)，4.66(s， 1H)，3.84(s，3H)，3.29(s，1H)，3.24-3.17(m，1H)，2.84-2.71(m，1H)，2.35(s，3H)，1.97-1.89 (m，3H)，1.81-1.75(m，1H)，1.18(s，9H). 13 C NMR(100MHz，CDCl 3 )δ156.8，144.8，138.7， 136.0，130.5，129.9，129.0，126.4，117.5，115.3，113.6，100.8，55.8，55.4，46.7，30.4，24.5，22.6，21.6， 18.0.
(R) -N- ((R) 6-methoxy-9-p-toluenesulfonyl-2, 3,4, 9-tetrahydro-1H-carbazol-4-yl) -2-methylpropan-2-sulfinamide (I-p 2)
A pale yellow liquid, which is a mixture of a light yellow liquid, 1 HNMR(400MHz，CDCl 3 )δ8.05(d，J＝9.2Hz，1H)， 7.66(d，J＝8.4Hz，2H)，7.22(d，J＝8.4Hz，2H)，6.95(d，J＝2.4Hz，1H)，6.90-6.70(m，1H)， 4.64-4.54(m，1H)，3.79(s，3H)，3.36(d，J＝8.4Hz，1H)，3.14(dt，J＝18.4，4.8Hz，1H)，2.88- 2.76(m，1H)，2.36(s，3H)，2.24-2.17(m，1H)，2.08-1.99(m，1H)，1.95-1.86(m，2H)，1.22(s， 9H). 13 C NMR(100MHz，CDCl 3 )δ156.3，144.8，138.4，136.0，130.7，129.9，129.8，126.4，118.3， 115.3，112.9，101.8，56.3，55.6，50.5，31.5，24.5，22.8，21.6，18.6.HRMS(ESI)calcd for C 24 H 30 N 2 O 4 S 2 Na[M+Na] + 497.1539，found 497.1542.
(R) -N- ((S) 6-fluoro-9-p-toluenesulfonyl-2, 3,4, 9-tetrahydro-1H-carbazol-4-yl) -2-methylpropan-2-sulfinamide (I-q 1)
I-q1 and I-q2 yield 78% overall.
A pale yellow liquid, which is a mixture of a light yellow liquid, 1 H NMR(400MHz，CDCl 3 )δ8.09(dd，J＝9.2，4.4 Hz，1H)，7.67(d，J＝8.4Hz，2H)，7.41(dd，J＝8.4，2.4Hz，1H)，7.24(d，J＝8.0Hz，2H)，7.03- 6.97(m，1H)，4.64(s，1H)，3.25-3.21(m，2H)，2.85-2.73(m，1H)，2.37(s，3H)，2.04-1.89(m， 3H)，1.82-1.74(m，1H)，1.18(s，9H). 13 C NMR(100MHz，CDCl 3 )δ159.9，(d，J＝250.2)，145.1， 140.0，135.8，132.4，130.0，126.5，122.2，117.3，115.4(d，J＝9.0)，112.2(d，J＝25.3)，104.7(d，J＝ 24.2)，55.4，46.5，30.1，24.5，22.6，21.6，17.7.
(R) -N- ((R) 6-fluoro-9-p-toluenesulfonyl-2, 3,4, 9-tetrahydro-1H-carbazol-4-yl) -2-methylpropan-2-sulfinamide (I-q 2)
A pale yellow liquid, which is a mixture of a light yellow liquid, 1 H NMR(400MHz，CDCl 3 )δ8.11(dd，J＝9.2，4.4Hz， 1H)，7.67(d，J＝8.4Hz，2H)，7.24(d，J＝8.0Hz，2H)，7.14(dd，J＝8.8，2.4Hz，1H)，7.02-6.98 (m，1H)，4.61-4.52(m，1H)，3.33(d，J＝8.4Hz，1H)，3.17-3.10(m，1H)，2.90-2.78(m，1H)， 2.38(s，3H)，2.23-2.15(m，1H)，2.12-2.03(m，1H)，1.96-1.88(m，2H)，1.22(s，9H). 13 C NMR (100MHz，CDCl 3 )δ159.7(d，J＝254.2)，145.1，139.4，135.9，132.8，130.0，126.5，123.4，118.2， 115.4(d，J＝9.0)111.9(d，J＝26.3)，105.1，(d，J＝24.6)，56.4，50.6，31.5，24.4，22.7，21.6，18.7.HRMS(ESI)calcd for C 23 H 27 FN 2 O 3 S 2 Na[M+Na] + 485.1339，found 485.1343.
(R) -N- ((S) 6-chloro-9-p-toluenesulfonyl-2, 3,4, 9-tetrahydro-1H-carbazol-4-yl) -2-methylpropan-2-sulfinamide (I-R1)
I-r1 and I-r2 yield 70% overall.
A pale yellow liquid, which is a mixture of a light yellow liquid, 1 H NMR(400MHz，CDCl 3 )δ8.07(d，J＝8.8Hz，1H)， 7.69(d，J＝2.4Hz，1H)，7.67(d，J＝8.4Hz，2H)，7.26-7.22(m，3H)，4.65-4.62(m，1H)，3.28- 3.18(m，2H)，2.82-2.73(m，1H)，2.37(s，3H)，2.04-1.76(m，4H)，1.18(s，9H). 13 C NMR(100 MHz，CDCl 3 )δ145.2，139.8，135.7，134.6，130.1，129.7，129.4，126.5，124.6，118.5，116.8，115.3， 55.5，46.5，30.0，24.4，22.6，21.7，17.7.
(R) -N- ((R) 6-chloro-9-p-toluenesulfonyl-2, 3,4, 9-tetrahydro-1H-carbazol-4-yl) -2-methylpropan-2-sulfinamide (I-R2)
A pale yellow liquid, which is a mixture of a light yellow liquid, 1 H NMR(400MHz，CDCl 3 )δ8.08(d，J＝8.8Hz，1H)， 7.67(d，J＝8.4Hz，2H)，7.46(d，J＝2.4Hz，1H)，7.27(s，1H)，7.25-7.22(m，2H)，4.59-4.54(m， 1H)，3.34(d，J＝8.4Hz，1H)，3.16-3.09(m，1H)，2.89-2.81(m，1H)，2.38(s，3H)，2.19-1.90(m， 4H)，1.23(s，9H). 13 C NMR(100MHz，CDCl 3 )δ145.2，139.1，135.9，134.6，130.1，129.1，126.5， 124.3，119.2，117.8，115.3，100.0，56.5，50.8，31.7，24.4，22.8，21.6，18.9.HRMS(ESI)calcd for C 23 H 27 ClN 2 O 3 S 2 Na[M+Na] + 501.1044，found 501.1048.
(R) -N- ((S) 6-bromo-9-p-toluenesulfonyl-2, 3,4, 9-tetrahydro-1H-carbazol-4-yl) -2-methylpropan-2-sulfinamide (I-S1)
The total yield of I-s1 and I-s2 was 68%.
A pale yellow liquid, which is a mixture of a light yellow liquid, 1 H NMR(400MHz，CDCl 3 )δ8.03(d，J＝8.8Hz，1H)， 7.84(d，J＝2.0Hz，1H)，7.67(d，J＝8.4Hz，2H)，7.39(dd，J＝8.8，2.0Hz，1H)，7.24(d，J＝8.4Hz， 2H)，4.68-4.61(m，1H)，3.28-3.16(m，2H)，2.85-2.73(m，1H)，2.37(s，3H)，2.04-1.87(m， 3H)，1.80-1.72(m，1H)，1.18(s，9H). 13 C NMR(100MHz，CDCl 3 )δ145.2，139.6，135.8，135.0， 130.1，129.9，127.3，126.5，121.5，117.3，116.6，115.7，55.5，46.5，30.0，24.4，22.6，21.6，17.7.
(R) -N- ((R) 6-bromo-9-p-toluenesulfonyl-2, 3,4, 9-tetrahydro-1H-carbazol-4-yl) -2-methylpropan-2-sulfinamide (I-s 2)
A pale yellow liquid, which is a mixture of a light yellow liquid, 1 H NMR(400MHz，CDCl 3 )δ8.04(d，J＝8.8Hz，1H)， 7.67(d，J＝8.4Hz，2H)，7.63(d，J＝2.0Hz，1H)，7.37(dd，J＝8.8，2.0Hz，1H)，7.25(d，J＝8.4Hz， 2H)，4.60-4.54(m，1H)，3.32(d，J＝10.4Hz，1H)，3.12(dt，J＝18.4，5.2Hz，1H)，2.90-2.81(m， 1H)，2.38(s，3H)，2.16-2.10(m，2H)，1.93-1.87(m，2H)，1.24(s，9H). 13 C NMR(100MHz， CDCl 3 )δ145.2，138.9，135.9，135.0，130.5，130.1，126.9，126.5，122.8，117.8，116.7，115.7，56.5， 50.8，31.7，24.3，22.8，21.6，19.0.HRMS(ESI)calcd for C 23 H 27 BfN 2 O 3 S 2 Na[M+Na] + 545.0539， found 545.0542./>
(R) -N- ((S) 7-chloro-9-p-toluenesulfonyl-2, 3,4, 9-tetrahydro-1H-carbazol-4-yl) -2-methylpropan-2-sulfinamide (I-t 1)
The overall yield of I-t1 and I-t2 was 72%.
A pale yellow liquid, which is a mixture of a light yellow liquid, 1 H NMR(400MHz，CDCl 3 )δ8.19(d，J＝1.6Hz，1H)， 7.70(d，J＝8.4Hz，2H)，7.66(d，J＝8.4Hz，1H)，7.27(s，1H)，7.26-7.22(m，2H)，4.67(s，1H)，3.26-3.17(m，2H)，2.80-2.72(m，1H)，2.38(s，3H)，1.99-1.75(m，4H)，1.18(s，9H). 13 C NMR (101MHz，CDCl 3 )δ145.4，138.8，136.6，135.9，130.5，130.1，126.6，126.5，124.4，119.6，117.0， 114.5，55.5，46.5，30.1，24.3，22.6，21.6，17.7.
(R) -N- ((R) 7-chloro-9-p-toluenesulfonyl-2, 3,4, 9-tetrahydro-1H-carbazol-4-yl) -2-methylpropan-2-sulfinamide (I-t 2)
A pale yellow liquid, which is a mixture of a light yellow liquid, 1 H NMR(400MHz，CDCl 3 )δ8.21(d，J＝1.6Hz，1H)， 7.70(d，J＝8.4Hz，2H)，7.40(d，J＝8.4Hz，1H)，7.28(s，1H)，7.26(s，1H)，7.20(dd，J＝8.4，2.0 Hz，1H)，4.63-4.54(m，1H)，3.34(d，J＝10.4Hz，1H)，3.15-3.10(m，1H)，2.86-2.78(m，1H)， 2.39(s，3H)，2.18-1.91.(m，4H)，1.20(s，9H). 13 C NMR(100MHz，CDCl 3 )δ145.3，138.3，136.6， 135.9，130.2，130.1，127.2，126.6，123.9，119.9，117.9，114.5，56.4，50.2，31.4，24.3，22.7，21.7，18.6. HRMS(ESI)calcd for C 23 H 27 ClN 2 O 3 S 2 Na[M+Na] + 501.1044，found 501.1047./>

Claims (3)

1. a process for the preparation of a chiral 4-aminotetrazole derivative, the process comprising: in the presence of a catalyst and an additive, in an organic solvent, carrying out a serial cyclization reaction on 6-phenyl-5-hexyne imine shown in a formula (II) to obtain a compound shown in the formula (I);
wherein the compound represented by formula (I) is selected from one of the compounds represented by the following formulas:
(R) -2-methyl-N- ((S) 9- (benzenesulfonyl) -2,3,4, 9-tetrahydro-1H-carbazol-4-yl) propane-2-sulfinamide (I-b 1);
(R) -2-methyl-N- ((R) 9- (benzenesulfonyl) -2,3,4, 9-tetrahydro-1H-carbazol-4-yl) propane-2-sulfinamide (I-b 2);
(R) -N- ((S) 9- ((4-tert-butylbenzenesulfonyl) -2,3,4, 9-tetrahydro-1H-carbazol-4-yl) -2-methylpropan-2-sulfinamide (I-c 1);
(R) -N- ((R) 9- ((4-tert-butylbenzenesulfonyl) -2,3,4, 9-tetrahydro-1H-carbazol-4-yl) -2-methylpropan-2-sulfinamide (I-c 2);
(R) -N- ((S) 9- (4-methoxybenzenesulfonyl) -2,3,4, 9-tetrahydro-1H-carbazol-4-yl) -2-methylpropan-2-sulfinamide (I-d 1);
(R) -N- ((R) 9- (4-methoxybenzenesulfonyl) -2,3,4, 9-tetrahydro-1H-carbazol-4-yl) -2-methylpropan-2-sulfinamide (I-d 2);
(R) -N- ((S) 9- (4-fluorobenzenesulfonyl) -2,3,4, 9-tetrahydro-1H-carbazol-4-yl) -2-methylpropan-2-sulfinamide (I-e 1);
(R) -B- ((R) 9- (4-fluorobenzenesulfonyl) -2,3,4, 9-tetrahydro-1H-carbazol-4-yl) -2-methylpropan-2-sulfinamide (I-e 2);
(R) -N- ((S) 9- (4-chlorobenzenesulfonyl) -2,3,4, 9-tetrahydro-1H-carbazol-4-yl) -2-methylpropan-2-sulfinamide (I-f 1);
(R) -N- ((R) 9- (4-chlorobenzenesulfonyl) -2,3,4, 9-tetrahydro-1H-carbazol-4-yl) -2-methylpropan-2-sulfinamide (I-f 2);
(R) -N- ((S) 9- (4-bromobenzenesulfonyl) -2,3,4, 9-tetrahydro-1H-carbazol-4-yl) -2-methylpropan-2-sulfinamide (I-g 1);
(R) -N- ((R) 9- (4-bromobenzenesulfonyl) -2,3,4, 9-tetrahydro-1H-carbazol-4-yl) -2-methylpropan-2-sulfinamide (I-g 2);
(R) -N- ((S) 9- (4-cyanobenzenesulfonyl) -2,3,4, 9-tetrahydro-1H-carbazol-4-yl) -2-methylpropan-2-sulfinamide (I-H1);
(R) -N- ((R) 9- (4-cyanobenzenesulfonyl) -2,3,4, 9-tetrahydro-1H-carbazol-4-yl) -2-methylpropan-2-sulfinamide (I-H2);
(R) -2-methyl-N- ((S) 9-methanesulfonyl-2, 3,4, 9-tetrahydro-1H-carbazol-4-yl) propane-2-sulfinamide (I-I1);
(R) -2-methyl-N- ((R) 9-methanesulfonyl-2, 3,4, 9-tetrahydro-1H-carbazol-4-yl) propane-2-sulfinamide (I-I2);
(R) -N- ((S) 9-cyclopropylsulfonyl-2, 3,4, 9-tetrahydro-1H-carbazol-4-yl) -2-methylpropan-2-sulfinamide (I-j 1);
(R) -N- ((R) 9-cyclopropylsulfonyl-2, 3,4, 9-tetrahydro-1H-carbazol-4-yl) -2-methylpropan-2-sulfinamide (I-j 2);
(R) -2-methyl-N- ((S) 9- (thiophene-2-sulfonyl) -2,3,4, 9-tetrahydro-1H-carbazol-4-yl) propane-2-sulfinamide (I-k 1);
(R) -2-methyl-N- ((R) 9- (thiophene-2-sulfonyl) -2,3,4, 9-tetrahydro-1H-carbazol-4-yl) propane-2-sulfinamide (I-k 2);
(R) -2-methyl-N- ((S) 6-methyl-9-p-toluenesulfonyl-2, 3,4, 9-tetrahydro-1H-carbazol-4-yl) propane-2-sulfinamide (I-l 1);
(R) -2-methyl-N- ((R) 6-methyl-9-p-toluenesulfonyl-2, 3,4, 9-tetrahydro-1H-carbazol-4-yl) propane-2-sulfinamide (I-l 2);
(R) -2-methyl-N- ((S) 6-phenyl-9-p-toluenesulfonyl-2, 3,4, 9-tetrahydro-1H-carbazol-4-yl) propane-2-sulfinamide (I-m 1);
(R) -2-methyl-N- ((R) 6-phenyl-9-p-toluenesulfonyl-2, 3,4, 9-tetrahydro-1H-carbazol-4-yl) propane-2-sulfinamide (I-m 2);
(R) -N- ((S) 6-tert-butyl-9-p-toluenesulfonyl-2, 3,4, 9-tetrahydro-1H-carbazol-4-yl) -2-methylpropan-2-sulfinamide (I-N1);
the compound shown in the formula (II) is specifically selected according to the compound shown in the formula (I) which is required to be synthesized;
the catalyst is AgNTf 2 ，AgSbF 6 ，AgOTf，AgTFA，AgOAc，AgBF 4 One or more of PhCOOAg;
the additive is LiCl, liBr, liOAc, liOTf, liClO 4 ，Li 2 CO 3 One or more of the following;
the organic solvent is one or more of acetonitrile, dichloromethane, dichloroethane, toluene, tetrahydrofuran and dioxane.
2. The process according to claim 1, wherein the molar ratio of 6-phenyl-5-hexyne imine of formula (II) to the catalyst is from 1:0.1 to 0.3;
the molar ratio of the 6-phenyl-5-hexyne imine shown in the formula (II) to the additive is 1:1-3;
the organic solvent is used in an amount such that the concentration of 6-phenyl-5-hexyne imine represented by formula (II) is 0.05-0.5mmol/mL.
3. The method of claim 1, the conditions of the tandem reaction are: the temperature was 60℃and the time was 6 hours.
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Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
Silver–copper co-catalyzed cascade intramolecular cyclization/desulfinamide/dehydrogenation:one-pot synthesis of substituted carbazoles;Yuanqiong Huang等;《Chemical Communications》;20181231;第54卷(第52期);第7143-7146页 *
中国农业百科全书总编辑委员会 等.《中国农业百科全书 农药卷》.农业出版社,1993, *

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