CN114773382B - Chiral compound alpha-siloxylketone derivative containing indole/carbazole skeleton, preparation method and application - Google Patents

Chiral compound alpha-siloxylketone derivative containing indole/carbazole skeleton, preparation method and application Download PDF

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CN114773382B
CN114773382B CN202210638568.0A CN202210638568A CN114773382B CN 114773382 B CN114773382 B CN 114773382B CN 202210638568 A CN202210638568 A CN 202210638568A CN 114773382 B CN114773382 B CN 114773382B
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CN114773382A (en
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金智超
汤承浩
宋朝洋
鲍兆伟
蔡辉
池永贵
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Guizhou University
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic System
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
    • C07F7/1804—Compounds having Si-O-C linkages
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
    • A01N43/36—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom five-membered rings
    • A01N43/38—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom five-membered rings condensed with carbocyclic rings
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N55/00—Biocides, pest repellants or attractants, or plant growth regulators, containing organic compounds containing elements other than carbon, hydrogen, halogen, oxygen, nitrogen and sulfur
    • 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
    • C07D209/02—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom condensed with one carbocyclic ring
    • C07D209/04—Indoles; Hydrogenated indoles
    • C07D209/08—Indoles; Hydrogenated indoles with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, directly attached to carbon atoms of the hetero ring
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    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic System
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
    • C07F7/1804—Compounds having Si-O-C linkages
    • C07F7/1872—Preparation; Treatments not provided for in C07F7/20
    • C07F7/188—Preparation; Treatments not provided for in C07F7/20 by reactions involving the formation of Si-O linkages
    • 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 relates to a preparation method for synthesizing an alpha-siloxyl derivative containing an indole skeleton by catalyzing small molecules of N-heterocyclic carbene with high enantioselectivity and a good derivatization way. The structural general formula is as follows:wherein the carbon atoms marked are chiral carbon atoms, R is methyl, phenyl or substituted phenyl, R 1 And R is 2 Is methyl or phenyl, R 3 The substituent on the indole ring and the carbazole ring is halogen atom, methyl, ethyl, tertiary butyl or methoxy. The asymmetric cross Brook-Benzonin reaction of the acyl silane and the indole-7-formaldehyde disclosed by the invention is used for preparing the chiral alpha-siloxylketone derivative containing the indole skeleton, and the derivative has good universality, good yield, high yield up to 90%, high enantioselectivity up to 99:1 and good derivatization reaction.

Description

Chiral compound alpha-siloxylketone derivative containing indole/carbazole skeleton, preparation method and application
Technical Field
The invention relates to a preparation method for synthesizing chiral indole skeleton alpha-siloxyl ketone compounds by catalyzing nitrogen heterocyclic carbene organic small molecules and antibacterial activity research thereof.
Background
Indole and carbazole backbones are often present in natural and non-natural compounds, with good biological activity. Various molecules containing indole or carbazole nucleus have been widely studied in terms of antiviral, antibacterial, antifungal, anticancer, and agricultural chemicals. Therefore, the synthesis of indole and carbazole compounds has received a great deal of attention. The development of the preparation method of chiral indole and carbazole derivatives with high efficiency and high stereoselectivity has important application value. Common acyl silane and substituted indole-7-formaldehyde are used as raw materials, a series of chiral indole and carbazole compounds with high stereoselectivity are synthesized through catalysis of N-heterocyclic carbene (NHC), and a series of derivatizations are carried out by utilizing synthesized products. It was found to have good universality and good conversion. The indole and carbazole skeletons synthesized by using the organic micromolecules are a brand new and efficient synthesis method of chiral indole and carbazole compounds, have potential application prospects in the aspects of new pesticide creation and green chiral pesticide creation, and provide a brand new solution and synthesis strategy for the development of new structures on pesticides.
Disclosure of Invention
The invention aims to design and synthesize indole and carbazole skeleton chiral compounds with novel structure, good substrate universality and high enantioselectivity, and further research on derivatization and exploration of antibacterial activity of the compounds.
The technical scheme of the invention is as follows: a chiral compound contains indole/carbazole skeleton alpha-siloxylketone derivatives, and the derivatives are represented by the following general formula (1):
wherein the carbon atoms marked are chiral carbon atoms, R is methyl, phenyl or substituted phenyl, R 1 And R is 2 Is methyl or phenyl, R 3 The substituent on the indole ring and the carbazole ring is halogen atom, methyl, ethyl, tertiary butyl or methoxy.
The substituent of the substituted phenyl is halogen, methyl, ethyl, tertiary butyl or methoxy.
The halogen atom is fluorine, chlorine or bromine.
The preparation method of the chiral compound containing indole skeleton alpha-siloxyl ketone derivative comprises the following steps:
the reaction general formula and the process are as follows:
. The reaction temperature was 40 ℃.
The preparation method comprises the following steps of: the preparation method of the substituted acyl silane 1a comprises the following steps: weighing substituted aryl aldehyde S1, dissolving with dichloromethane, adding boron trifluoride diethyl etherate, reacting for about 3 hours, monitoring the reaction, adding saturated sodium bicarbonate solution to quench the reaction after the raw material S1 is completely consumed, extracting with dichloromethane, drying with anhydrous sodium sulfate, mixing organic phases, and desolventizing to obtain an intermediate S2; adding an intermediate S2 into a Schlenk bottle, adding a proper amount of dry tetrahydrofuran for dissolution, adding n-butyllithium for reaction at the temperature of minus 40 ℃ for 40 minutes, adding chlorosilane, continuing to react for one hour, recovering to room temperature, adding saturated ammonium chloride for quenching reaction, extracting with ethyl acetate, combining organic phases, drying with anhydrous sodium sulfate, and purifying the organic phases with a spin-dry petroleum ether ethyl acetate column to obtain an intermediate S3; taking a certain amount of intermediate S3, adding acetone for dissolution, adding copper chloride and copper oxide, carrying out reflux reaction for 8 hours, carrying out suction filtration, spinning an organic phase to dry petroleum ether, and purifying the organic phase by passing ethyl acetate through a column to obtain a product;
the preparation method of the substituted indole-7-formaldehyde 2a comprises the following steps: dissolving substituted o-nitrobenzaldehyde S4 in a certain amount of toluene solution, then adding n-butanol and p-toluenesulfonic acid, monitoring the reaction, after refluxing for about 16 hours, adding water to quench the reaction after the raw material o-nitrobenzaldehyde is completely reacted, extracting with ethyl acetate, and purifying an organic phase by using ethyl acetate as a solvent to obtain an intermediate S5; s5 is taken and added into a Schlenk bottle, ultra-dry tetrahydrofuran is added for dissolution, a proper amount of substituted vinyl magnesium bromide is added at the temperature of minus 45 ℃ for reaction for 1 hour, then the reaction is restored to room temperature, then 1MHCl with the same amount is added, saturated sodium bicarbonate is added for quenching reaction, ethyl acetate is used for extraction, and the organic phase is dried by spinning petroleum ether, namely ethyl acetate is subjected to column purification, thus obtaining the substituted indole-7-formaldehyde.
The chiral compound containing indole skeleton alpha-siloxyl ketone derivative is applied to preparation and inhibition of plant bacterial diseases.
The specific preparation content of the invention is as follows:
(1) Catalytic synthesized chiral compound indole and carbazole derivative
(2) Derivatization research on synthesized chiral indole compounds
The invention has the beneficial effects that:
chiral indole and carbazole compounds exist in various natural products and drug molecules, have various biological activities such as antibacterial activity, antiviral activity, anticancer activity and the like, and a plurality of chemists also synthesize various substituted indole and carbazole skeleton compounds, so that a certain foundation is laid for the research of indole and carbazole compounds.
In the method, an azacyclo-carbene organic micromolecular catalyst is adopted to catalyze an asymmetric crossover Brook-Benzonin reaction of acyl silane and indole-7-formaldehyde or carbazole-1-formaldehyde, chiral alpha-siloxyl derivatives containing indole or carbazole skeletons can be prepared through the reaction, and substrates involved in the reaction are easy to prepare, and the method has good yield and excellent universality; the catalytic reaction condition is mild, the yield and the enantiomer excess value are good, the yield can reach 90% at the highest, and the enantioselectivity can reach 99:1; in the further derivatization reaction, the diol compound containing chiral indole or carbazole skeleton can be efficiently constructed, and the derivative has good derivatization reaction and good universality.
In addition, the compound synthesized by the application has a good inhibition effect on kiwi fruit canker, the antibacterial activity of a plurality of compounds is larger than that of commercial medicines of the metconazole and the thiabendazole, especially the carbazole skeleton derivatives, and the compound has a very good bacterial disease biological activity inhibition effect, wherein the compounds 6b, 6c and 6h are the most excellent in performance.
Detailed description of the preferred embodiments
The examples of the invention are presented below, together with 39 preparation examples and 5 derivatization studies, as well as the study of the bacteriostatic activity of the compounds.
Preparation example 1
(1) Synthetic route for preparation of (S) -2- (1H-indol-7-yl) -2- ((methyldiphenylsilyl) -oxy) -1-phenylethyl-1-one:
the substituent R is Ph, R 1 Is CH 3 ，R 2 Is Ph, R 3 For H, the preparation method and conditions are as follows:
0.10mmol of benzoyl silane 1, 0.15mmol of indole-7-carbaldehyde 2 and 0.02mmol of N-heterocyclic carbene catalyst B are weighed respectively. Into a 4mL reaction tube equipped with a magnetic stirrer, 2mL of 1, 2-dichloroethane DCE and 0.08mmol of lithium bis (trimethylsilyl) amide (LiHMDS) as solvents were added, and the reaction wall was gently swirled to mix well. The bottle cap is covered, and the mixture is placed in an oil bath at 40 ℃ to be fully stirred for reaction for 14h. After the TLC monitoring reaction is finished, spin-drying, fully dissolving a small amount of dichloromethane, loading the mixture on a wet method, separating the mixture through column chromatography, obtaining a target compound 3a from eluent polar petroleum ether, namely ethyl acetate=6:1, calculating corresponding yield after weighing, and characterizing the compound through a melting point instrument, a polarimeter, a nuclear magnetic resonance instrument NMR, a high resolution mass spectrometer HRMS and a high performance liquid chromatograph HPLC.
The synthetic compounds were experimentally characterized as follows:
(S) -2- (1H-indol-7-yl) -2- ((methyldiphenylsilyl) -oxy) -1-phenylethyl-1-one (3 a):
6.27(s,1H),0.48(s,3H)；
13 C NMR(101MHz,CDCl 3 )δ197.5,135.1,135.0,134.7,134.5,134.4,133.7,133.3,130.1,130.0, 129.1,128.9,128.4,128.0,127.9,124.9,121.3,121.2,120.2,119.5,101.9,78.0,-2.7；
HRMS(ESI,m/z):Masscalcd.for C 29 H 25 NO 2 SiNa + [M+Na] + 470.1547,found470.1533；
HPLC analysis:99:1er(CHIRALCEL OD-Hcoloum；25℃,n-hexane/i-PrOH＝98/2,flow rate＝0.3 mL/min,λ＝254nm),Rt(major)＝22.8min,Rt(minor)＝20.6min.
preparation example 2
The substituent R is 4-F-Ph, R 1 Is CH 3 ，R 2 Is Ph, R 3 For H, the preparation implementation method and conditions are the same as 3a:
(S) -1- (4-fluorophenyl) -2- (1H-indol-7-yl) -2- ((methyldiphenylsilyl) -oxy) ethyl-1-one (3 b):
7.07–7.02(m,1H),6.97(t,J＝8.8Hz,2H),6.49(dd,J＝3.1,2.2Hz,1H),6.20(s,1H),0.50(s, 3H)；
13 C NMR(101MHz,CDCl 3 )δ196.0,165.7(d,J＝256.5Hz),134.9(d,J＝5.5Hz),134.4(d,J ＝16.6Hz),134.0,133.6,131.9(d,J＝9.3Hz),131.0,130.9,130.2,130.1,130.0,128.9,128.0(d,J＝2.7Hz),125.0,121.4,120.8,120.0,119.6,115.5(d,J＝21.9Hz),102.0,78.1,-2.8；
19 F NMR(376MHz,CDCl 3 )δ-104.3；
HRMS(ESI,m/z):Masscalcd.for C 29 H 24 FNO 2 SiNa + [M+Na] + 488.1453,found 488.1429；
HPLC analysis:97:3er(CHIRALCELIAcolumn,25℃,n-hexane/i-PrOH＝98/2,flowrate＝ 0.3mL/min,λ＝254nm),Rt(major)＝33.7min,Rt(minor)＝29.5min.
preparation example 3
The substituent R is 4-CH 3 -Ph，R 1 Is CH 3 ，R 2 Is Ph, R 3 For H, the preparation implementation method and conditions are the same as 3a:
(S) -2- (1H-indol-7-yl) -2- ((methyldiphenylsilyl) -oxy) -1- (4-methylphenyl) ethyl-1-one (3 c):
7.50(m,5H),7.38–7.32(m,6H),7.19(s,1H),7.14(s,1H),7.10(d,J＝8.0Hz,2H),7.02(d,J ＝7.8Hz,1H),6.47(dd,J＝3.2,2.2Hz,1H),6.26(s,1H),2.30(s,3H),0.47(s,3H)；
13 C NMR(101MHz,CDCl 3 )δ197.0,144.2,135.2,135.1,134.5,134.4,133.73,132.1,130.1, 130.0,129.2,129.1,128.9,128.0,127.9,124.9,121.2,121.1,120.4,119.5,101.8,77.9,21.7,-2.7；
HRMS(ESI,m/z):Mass calcd.for C 30 H 27 NO 2 SiNa + [M+Na] + 484.1703,found484.1706；
HPLC analysis:99:1er(CHIRALCELIC column；25℃,n-hexane/i-PrOH＝98/2,flow rate＝ 0.3mL/min,λ＝254nm),Rt(major)＝22.5min,Rt(minor)＝18.9min.
preparation example 4
Substituent R is 4-OCH 3 -Ph，R 1 Is CH 3 ，R 2 Is Ph, R 3 For H, the preparation implementation method and conditions are the same as 3a:
(S) -2- (1H-indol-7-yl) -1- (4-phenylmethoxy) -2- ((methyldiphenylsilyl) -oxy) ethyl-1-one (3 d):
4H),7.50(d,J＝1.4Hz,1H),7.41–7.28(m,7H),7.19(dd,J＝5.4,2.2Hz,2H),7.01(d,J＝ 7.6Hz,1H),6.76(d,J＝9.0Hz,2H),6.47(dd,J＝3.2,2.2Hz,1H),6.23(s,1H),3.75(s,3H),0.47(s,3H)；
13 C NMR(101MHz,CDCl 3 )δ195.9,163.6,135.3,135.2,134.5,134.5,133.7,131.6,130.1, 130.1,128.9,128.0,127.9,127.5,124.9,121.2,120.9,120.7,119.5,113.6,101.8,77.9,55.4,-2.7；
HRMS(ESI,m/z):Mass calcd.for C 30 H 27 NO 3 SiNa + [M+Na] + 500.1652,found500.1663；
HPLC analysis:95:5er(CHIRALCEL IC column；25℃,n-hexane/i-PrOH＝98/2,flow rate＝ 0.3mL/min,λ＝254nm),Rt(major)＝38.6min,Rt(minor)＝34.4min.
preparation example 5
The substituent R is 4-tBu-Ph, R 1 Is CH 3 ，R 2 Is Ph, R 3 For H, the preparation implementation method and conditions are the same as 3a:
(S) -1- (4- (tert-butyl) phenyl) -2- (1H-indol-7-yl) -2- ((methyldiphenylsilyl) -oxy) ethyl-1-one (3 e):
7.54(m,2H),7.53–7.49(m,3H),7.39(d,J＝7.4Hz,2H),7.34–7.29(m,6H),7.17(s,2H), 7.04(d,J＝7.6Hz,1H),6.49–6.46(m,1H),6.28(s,1H),1.25(s,9H),0.46(s,3H)；
13 C NMR(101MHz,CDCl 3 )δ196.9,157.1,135.3,135.2,134.5,134.4,133.7,131.9,130.1, 130.0,129.1,128.9,128.0,127.9,125.4,125.0,121.3,121.2,120.4,119.5,101.8,77.8,35.1,31.0,-2.7；
HRMS(ESI,m/z):Mass calcd.for C 33 H 33 NO 2 SiNa + [M+Na] + 526.2173,found526.2180；
HPLC analysis:96:4er(CHIRALCEL AD-H column；25℃,n-hexane/i-PrOH＝98/2,flow rate＝0.3mL/min,λ＝254nm),Rt(major)＝30.7min,Rt(minor)＝35.9min.
preparation example 6
The substituent R is 3-F-Ph, R 1 Is CH 3 ，R 2 Is Ph, R 3 For H, the preparation implementation method and conditions are the same as 3a:
(S) -1- (3-fluorophenyl) -2- (1H-indol-7-yl) -2- ((methyldiphenylsilyl) -oxy) ethyl-1-one (3 f):
＝7.8Hz,1H),7.55–7.49(m,5H),7.43–7.27(m,7H),7.22–7.20(m,1H),7.18(d,J＝7.2Hz, 1H),7.16–7.10(m,1H),7.07–7.02(m,1H),6.50(dd,J＝3.0,2.2Hz,1H),6.20(s,1H),0.50(s,3H)；
13 C NMR(101MHz,CDCl 3 )δ196.3,162.4(d,J＝247.8Hz),136.6(d,J＝6.5Hz),134.9,134.8, 134.5,134.4,134.0,133.6,130.2(d,J＝2.2Hz),130.0(d,J＝7.7Hz),129.0,128.1,128.0,125.0,124.9,124.8,121.5,121.1,120.3(d,J＝21.4Hz),119.6,115.8(d,J＝22.7Hz),102.0, 78.1,-2.7；
19 F NMR(376MHz,CDCl 3 )δ-111.7；
HRMS(ESI,m/z):Mass calcd.for C 29 H 24 FNO 2 SiNa + [M+Na] + 488.1453,found488.1447；
HPLC analysis:98:2er(CHIRALCEL AD-H column；25℃,n-hexane/i-PrOH＝98/2,flow rate＝0.3mL/min,λ＝254nm),Rt(major)＝26.6min,Rt(minor)＝28.9min.
preparation example 7
The substituent R is 3-Cl-Ph, R 1 Is CH 3 ，R 2 Is Ph, R 3 For H, the preparation implementation method and conditions are the same as 3a:
(S) -1- (3-chlorophenyl) -2- (1H-indol-7-yl) -2- ((methyldiphenylsilyl) -oxy) ethyl-1-one (3 g):
1H),7.58–7.49(m,5H),7.42–7.38(m,3H),7.35–7.31(m,4H),7.24–7.16(m,3H),7.05(t, J＝7.6Hz,1H),6.50(d,J＝2.2Hz,1H),6.18(s,1H),0.51(s,3H)；
13 C NMR(126MHz,CDCl 3 )δ196.5,136.2,134.9,134.8,134.7,134.5,134.0,133.6,133.2, 130.3,130.3,129.7,129.2,129.0,128.1,128.1,127.2,125.1,121.6,121.1,119.7,119.6,102.1,78.2,-2.7；
HRMS(ESI,m/z):Mass calcd.for C 29 H 24 ClNO 2 SiNa + [M+Na] + 504.1157,found504.1135；
HPLC analysis:92:8er(CHIRALCEL AD-H column；25℃,n-hexane/i-PrOH＝98/2,flow rate＝0.2mL/min,λ＝254nm),Rt(major)＝36.1min,Rt(minor)＝41.9min.
preparation example 8
The substituent R is 3-CH 3 -Ph，R 1 Is CH 3 ，R 2 Is Ph, R 3 For H, the preparation implementation method and conditions are the same as 3a:
(S) -2- (1H-indol-7-yl) -2- ((methyldiphenylsilyl) -oxy) -1- (3-methylphenyl) ethyl-1-one (3H):
7.11(m,4H),7.02(d,J＝7.8Hz,1H),6.48(dd,J＝3.2,2.2Hz,1H),6.27(s,1H),2.28(s,3H), 0.49(s,3H)；
13 C NMRδ197.7,138.2,135.2,135.1,134.8,134.5,134.4,134.1,133.7,130.1,130.0,129.6, 128.9,128.2,128.0,127.9,126.2,124.9,121.3,120.2,119.5,101.8,77.9,21.3,-2.7；
HRMS(ESI,m/z):Mass calcd.forC 30 H 27 NO 2 SiNa + [M+Na] + 484.1703,found484.1702；
HPLC analysis:97:3er(CHIRALCELIC column；25℃,n-hexane/i-PrOH＝98/2,flow rate＝ 0.3mL/min,λ＝254nm),Rt(major)＝19.6min,Rt(minor)＝17.3min.
preparation example 9
Substituent R is 3-OCH 3 -Ph，R 1 Is CH 3 ，R 2 Is Ph, R 3 For H, the preparation implementation method and conditions are the same as 3a:
(S) -2- (1H-indol-7-yl) -1- (3-methoxyphenyl) -2- ((methyldiphenylsilyl) -oxy) ethyl-1-one (3 i):
7.15(d,J＝7.2Hz,1H),7.03–6.96(m,2H),6.51–6.45(m,1H),6.26(s,1H),3.72(s,3H), 0.49(s,3H)；
13 C NMR(101MHz,CDCl 3 )δ197.2,159.5,135.9,135.1,134.5,134.4,133.7,130.2,130.1, 129.3,128.9,128.0,127.9,125.0,121.6,121.3,121.2,120.1,120.0,119.5,113.2,101.9,78.0,55.3,-2.7；
HRMS(ESI,m/z):Mass calcd.for C 30 H 27 NO 2 SiNa + [M+Na] + 500.1652,found500.1649；
HPLC analysis:97:3er(CHIRALCELIC column；25℃,n-hexane/i-PrOH＝98/2,flow rate＝ 0.3mL/min,λ＝254nm),Rt(major)＝26.3min,Rt(minor)＝22.2min.
preparation example 10
The substituent R is 3,5-dimethyl-Ph, R 1 Is CH 3 ，R 2 Is Ph, R 3 For H, the preparation implementation method and conditions are the same as 3a:
(S) -1- (3, 5-dimethylphenyl) -2- (1H-indol-7-yl) -2- ((methyldiphenylsilyl) -oxy) ethyl-1-one (3 j):
(m,4H),7.35–7.30(m,4H),7.22–7.19(m,1H),7.11(d,J＝7.2Hz,1H),7.06(s,1H),7.03– 6.98(m,1H),6.48(dd,J＝3.1,2.2Hz,1H),6.26(s,1H),2.24(s,6H),0.49(s,3H)；
13 C NMR(101MHz,CDCl 3 )δ197.9,138.0,135.3,135.2,135.0,134.9,134.5,134.4,133.8, 130.1,130.0,128.9,128.0,127.9,126.8,124.9,121.3,121.2,120.3,119.5,101.8,77.9,21.2,-2.7；
HRMS(ESI,m/z):Mass calcd.for C 31 H 29 NO 2 SiNa + [M+Na] + 498.1860,found498.1862；
HPLC analysis:99:1er(CHIRALCEL IC column；25℃,n-hexane/i-PrOH＝98/2,flow rate＝ 0.2mL/min,λ＝254nm),Rt(major)＝34.4min,Rt(minor)＝29.1min.
preparation example 11
The substituent R is PhCH 2 CH 2 ，R 1 Is CH 3 ，R 2 Is Ph, R 3 For H, the preparation implementation method and conditions are the same as 3a:
(S) -1- (1H-indol-7-yl) -1- ((methyldiphenylsilyl) -oxy) -4-phenylbutyl-2-one (3 k):
(m,3H),7.06–6.97(m,3H),6.57(dd,J＝3.2,2.2Hz,1H),5.17(t,J＝6.2Hz,1H),2.83(d,J＝ 7.0Hz,1H),2.76–2.67(m,1H),2.24–2.16(m,2H),0.63(s,3H)；
13 C NMR(101MHz,CDCl 3 )δ204.1,143.5,138.1,137.9,137.5,136.9,136.8,132.3,132.2, 131.8,130.8,130.7,130.2,130.1,129.7,128.3,128.0,126.6,120.9,119.7,104.7,77.3,40.2,34.0,-0.0；
HRMS(ESI,m/z):Mass calcd.for C 31 H 29 NO 2 SiNa + [M+Na] + 498.1860,found498.1861；
HPLC analysis:69:31er(CHIRALCEL IA column；25℃,n-hexane/i-PrOH＝98/2,flow rate ＝0.3mL/min,λ＝254nm),Rt(major)＝47.0min,Rt(minor)＝57.6min.
preparation example 12
The substituent R is Ph, R 1 Is Ph, R 2 Is CH 3 ，R 3 For H, the preparation implementation method and conditions are the same as 3a:
(S) -2- ((dimethyl (phenyl) silyl) -oxy) -2- (1H-indol-7-yl) -1-phenylethyl-1-one (3 l):
7.18(d,J＝7.2Hz,1H),7.05–7.00(m,1H),6.48(dd,J＝3.1,2.2Hz,1H),6.21(s,1H),0.33 (s,3H),0.25(s,3H)；
13 C NMR(101MHz,CDCl 3 )δ197.3,136.4,134.4,133.4,133.3,133.0,129.6,128.9,128.6, 128.1,127.6,124.6,121.0,120.8,120.0,119.2,101.6,77.5,-1.6,-1.9；
HRMS(ESI,m/z):Masscalcd.for C 24 H 23 NO 2 SiNa[M+Na] + 408.1396,found408.1379；
HPLC analysis:98:2er(CHIRALCEL IC column；25℃,n-hexane/i-PrOH＝98/2,flow rate＝ 0.3mL/min,λ＝254nm),Rt(major)＝19.0min,Rt(minor)＝15.6min.
preparation example 13
The substituent R is Ph, R 1 Is CH 3 ，R 2 Is CH 3 ，R 3 For H, the preparation implementation method and conditions are the same as 3a:
(S) -2- (1H-indol-7-yl) -1-phenyl-2- ((trimethylsilyl) -oxy) ethyl-1-one (3 m):
Hz,1H),7.25–7.23(m,1H),6.49(dd,J＝3.1,2.2Hz,1H),6.26(s,1H),0.06(s,9H)；
13 C NMR(101MHz,CDCl 3 )δ197.8,134.7,133.6,133.3,129.3,128.9,128.5,124.9,121.2, 121.0,120.6,119.6,101.9,77.8,-0.1；
HRMS(ESI,m/z):Mass calcd.for C 19 H 21 NO 2 SiNa[M+Na] + 346.1239,found346.1250；
HPLC analysis:94:6er(CHIRALCEL IC column；25℃,n-hexane/i-PrOH＝98/2,flow rate＝ 0.3mL/min,λ＝254nm),Rt(major)＝16.7min,Rt(minor)＝14.5min.
preparation example 14
The substituent R is Ph, R 1 Is CH 3 ，R 2 Is Ph, R 3 Is 2-CH 3 The preparation method and conditions are the same as 3a:
(S) -2- (2-methyl-1H-indol-7-yl) -2- ((methyldiphenylsilyl) -0-oxo) -1-phenylethyl-1-one (4 a):
Hz,3H),7.31–7.27(m,3H),7.09(d,J＝7.2Hz,1H),6.96(t,J＝7.6Hz,1H),6.25(s,1H), 6.14(dd,J＝2.2,1.1Hz,1H),2.40(s,3H),0.49(s,3H)；
13 C NMR(101MHz,CDCl 3 )δ197.6,136.0,135.2,135.2,134.8,134.5,134.4,133.9,133.2, 130.1,130.0,129.1,128.3,128.0,127.9,120.2,120.1,119.4,119.2,99.8,78.1,13.8,-2.7；
HRMS(ESI,m/z):Mass calcd.for C 30 H 27 NO 2 SiNa + [M+Na] + 484.1703,found484.1702；
HPLC analysis:94:6er(CHIRALCEL OD-H column；25℃,n-hexane/i-PrOH＝98/2,flow rate＝0.3mL/min,λ＝254nm),Rt(major)＝46.7min,Rt(minor)＝42.1min.
preparation example 15
The substituent R is Ph, R 1 Is CH 3 ，R 2 Is Ph, R 3 Is 3-CH 3 The preparation method and conditions are the same as 3a:
(S) -2- (3-methyl-1H-indol-7-yl) -2- ((methyldiphenylsilyl) -oxy) -1-phenylethyl-1-one (4 b):
25 [α] D ＝-73.5(c＝1.0in CHCl 3 )；
1 H NMR(400MHz,CDCl 3 )δ8.95(s,1H),7.84(m,2H),7.55–7.51(m,3H),7.51–7.47(m, 2H),7.45–7.39(m,2H),7.38–7.35(m,1H),7.34–7.27(m,6H),7.18(d,J＝7.2Hz,1H),7.05–7.00(m,1H),6.96(s,1H),6.25(s,1H),2.29(s,3H),0.49(s,3H)；
13 C NMR(101MHz,CDCl 3 )δ197.5,135.2,135.1,134.7,134.5,134.4,134.0,133.2,130.1, 130.0,129.2,129.1,128.3,128.0,127.9,122.5,121.1,119.9,119.4,118.8,110.9,78.1,9.6,-2.7；
HRMS(ESI,m/z):Mass calcd.for C 30 H 27 NO 2 SiNa + [M+Na] + 484.1703,found484.1700；
HPLC analysis:92:8er(CHIRALCEL IA column；25℃,n-hexane/i-PrOH＝98/2,flow rate＝ 0.3mL/min,λ＝254nm),Rt(major)＝25.0min,Rt(minor)＝26.4min.
preparation example 16
The substituent R is Ph, R 1 Is CH 3 ，R 2 Is Ph, R 3 For 2,3-dimethyl, the preparation method and conditions are the same as 3a:
(S) -2- (2, 3-dimethyl-1H-indol-7-yl) -2- ((methyldiphenylsilyl) -oxy) -1-phenylethyl-1-one (4 c):
＝7.6Hz,1H),6.23(s,1H),2.32(s,3H),2.17(s,3H),0.50(s,3H)；
13 C NMR(101MHz,CDCl 3 )δ197.6,135.3,135.2,134.8,134.5,134.4,133.1,132.9,131.6, 130.3,130.1,130.0,129.2,128.3,128.0,127.9,120.1,119.0,118.7,118.4,106.5,78.1,11.6,8.4,-2.7；
HRMS(ESI,m/z):Mass calcd.for C 31 H 29 NO 2 SiNa + [M+Na] + 498.1860,found498.1866；
HPLC analysis:95:5er(CHIRALCEL IC column；25℃,n-hexane/i-PrOH＝98/2,flow rate＝ 0.3mL/min,λ＝254nm),Rt(major)＝15.3min,Rt(minor)＝16.6min.
preparation example 17
The substituent R is Ph, R 1 Is CH 3 ，R 2 Is Ph, R 3 For 3-Cl, the preparation method and conditions are the same as 3a:
(S) -2- (3-chloro-1H-indol-7-yl) -2- ((methyldiphenylsilyl) -oxy) -1-phenylethyl-1-one (4 d):
25 [α] D ＝-43.5(c＝0.3in CHCl 3 )；
1 H NMR(400MHz,CDCl 3 )δ9.22(s,1H),7.83–7.80(m,2H),7.56–7.45(m,6H),7.40(d,J＝ 7.6Hz,2H),7.35–7.29(m,6H),7.20(d,J＝7.1Hz,1H),7.16(d,J＝2.6Hz,1H),7.11–7.06 (m,1H),6.27(s,1H),0.50(s,3H)；
13 C NMR(101MHz,CDCl 3 )δ197.4,134.9,134.8,134.5,134.4,134.4,134.0,133.5,132.8, 130.2,130.1,129.0,128.5,128.0,127.9,126.3,122.2,121.7,120.6,120.1,118.9,105.9,77.6,-2.7；
HRMS(ESI,m/z):Mass calcd.for C 29 H 24 ClNO 2 SiNa + [M+Na] + 504.1157,found504.1142；
HPLC analysis:>99:1er(CHIRALCEL OD-H column；25℃,n-hexane/i-PrOH＝98/2,flow rate＝0.3mL/min,λ＝254nm),Rt(major)＝21.9min,Rt(minor)＝19.7min.
preparation example 18
The substituent R is Ph, R 1 Is CH 3 ，R 2 Is Ph, R 3 For 3-Br, the preparation method and conditions are the same as 3a:
(S) -2- (3-bromo-1H-indol-7-yl) -2- ((methyldiphenylsilyl) -oxy) -1-phenylethyl-1-one (4 e):
(m,1H),6.27(s,1H),0.51(s,3H).
13 C NMR(101MHz,CDCl 3 )δ197.4,134.5,134.4,134.3,134.0,133.5,133.2,130.2,130.1, 129.9,129.0,128.5,128.0,127.9,127.7,124.2,122.2,120.6,120.3,119.8,90.9,77.6,-2.7.
HRMS(ESI,m/z):Mass calcd.for C 29 H 24 BrNO 2 SiNa + [M+Na] + 549.4948,found549.4945；
HPLC analysis:>99:1er(CHIRALCEL OD-H column；25℃,n-hexane/i-PrOH＝98/2,flow rate＝0.3mL/min,λ＝254nm),Rt(major)＝21.9min,Rt(minor)＝19.7min.
preparation example 19
The substituent R is Ph, R 1 Is CH 3 ，R 2 Is Ph, R 3 4-F, preparation and conditions were the same as 3a:
(S) -2- (4-fluoro-1H-indol-7-yl) -2- ((methyldiphenylsilyl) -oxy) -1-phenylethyl-1-one (4 f):
(dd,J＝10.8,4.4Hz,4H),7.43–7.34(m,4H),7.32–7.28(m,5H),7.16(t,J＝2.6Hz,1H), 7.03(d,J＝3.2Hz,1H),6.68–6.64(m,1H),6.55–6.54(m,1H),6.25(s,1H),0.49(s,3H)；
13 C NMR(101MHz,CDCl 3 )δ197.4,156.8(d,J＝248.5Hz),136.4(d,J＝12.0Hz),135.0(d,J ＝4.9Hz),134.7,134.5,134.4,133.3,130.2(d,J＝3.0Hz),129.0,128.4,128.0,128.0,124.9,122.0,121.9,117.9(d,J＝22.6Hz),116.6,116.6,104.3(d,J＝19.8Hz),98.2,77.3,-2.7；
19 F NMR(377MHz,CDCl 3 )δ-121.4；
HRMS(ESI,m/z):Mass calcd.for C 29 H 24 FNO 2 SiNa + [M+Na] + 488.1453,found488.1430；
HPLC analysis:99:1er(CHIRALCEL IB column；25℃,n-hexane/i-PrOH＝98/2,flow rate＝0.3mL/min,λ＝254nm),Rt(major)＝19.0min,Rt(minor)＝17.4min.
preparation example 20
The substituent R is Ph, R 1 Is CH 3 ，R 2 Is Ph, R 3 4-Cl, preparation and conditions were the same as 3a:
(S) -2- (4-chloro-1H-indol-7-yl) -2- ((methyldiphenylsilyl) -oxy) -1-phenylethyl-1-one (4 g):
6.58(d,J＝0.8Hz,1H),6.23(s,1H),0.51(s,3H)；
13 C NMR(101MHz,CDCl 3 )δ197.3,134.9,134.8,134.5,134.5,134.4,134.3,133.4,130.2, 130.1,129.0,128.5,128.0,128.0,127.6,126.7,125.5,121.7,119.3,119.2,100.7,-2.7；
HRMS(ESI,m/z):Mass calcd.for C 29 H 24 ClNO 2 SiNa + [M+Na] + 504.1157,found504.1161；
HPLC analysis:99:1er(CHIRALCEL OD-H column；25℃,n-hexane/i-PrOH＝98/2,flow rate＝0.3mL/min,λ＝254nm),Rt(major)＝23.0min,Rt(minor)＝20.0min.
preparation example 21
The substituent R is Ph, R 1 Is CH 3 ，R 2 Is Ph, R 3 4-Br, preparation and conditions were the same as 3a:
(S) -2- (4-bromo-1H-indol-7-yl) -2- ((methyldiphenylsilyl) -oxy) -1-phenylethyl-1-one (4H):
8.0,1.4Hz,3H),7.49(d,J＝1.4Hz,1H),7.46–7.40(m,2H),7.37(dd,J＝5.2,3.8Hz,1H), 7.33(dd,J＝5.2,2.2Hz,3H),7.32–7.29(m,3H),7.25(d,J＝2.8Hz,1H),7.18(d,J＝7.6Hz,1H),7.00(d,J＝7.8Hz,1H),6.52(dd,J＝3.2,2.4Hz,1H),6.22(s,1H),0.51(s,3H)；
13 C NMR(101MHz,CDCl 3 )δ197.2,134.8,134.7,134.5,134.4,134.3,133.8,133.5,130.2, 130.1,129.6,129.0,128.5,128.0,127.9,125.6,122.4,122.0,119.7,115.4,102.4,77.4,-2.7；
HRMS(ESI,m/z):Mass calcd.for C 29 H 24 BrNO 2 SiNa + [M+Na] + 549.4948,found549.4949；
HPLC analysis:99:1er(CHIRALCEL OD-H column；25℃,n-hexane/i-PrOH＝98/2,flow rate＝0.3mL/min,λ＝254nm),Rt(major)＝23.5min,Rt(minor)＝20.6min.
preparation example 22
The substituent R is Ph, R 1 Is CH 3 ，R 2 Is Ph, R 3 Is 4-CH 3 The preparation method and conditions are the same as 3a:
(S) -2- (4-methyl-1H-indol-7-yl) -2- ((methyldiphenylsilyl) -oxy) -1-phenylethyl-1-one (4 i):
7.07(d,J＝7.4Hz,1H),6.82(d,J＝7.2Hz,1H),6.49(dd,J＝3.1,2.2Hz,1H), 6.26(s,1H),2.51(s,3H),0.48(s,3H)；
13 C NMR(101MHz,CDCl 3 )δ197.5,178.4,135.2,135.1,134.7,134.5,134.4,133.3,133.2, 131.1,130.1,130.0,129.1,128.7,128.4,128.0,127.9,124.3,121.5,119.7,117.8,100.4,77.8,18.8,-2.7；
HRMS(ESI,m/z):Mass calcd.for C 30 H 27 NO 2 SiNa + [M+Na] + 484.1703,found484.1700；
HPLC analysis:98:2er(CHIRALCEL IA column；25℃,n-hexane/i-PrOH＝98/2,flow rate＝ 0.3mL/min,λ＝254nm),Rt(major)＝27.8min,Rt(minor)＝29.2min.
preparation example 23
The substituent R is Ph, R 1 Is CH 3 ，R 2 Is Ph, R 3 Is 4-OCH 3 The preparation method and conditions are the same as 3a:
(S) -2- (4-methoxy-1H-indol-7-yl) -2- ((methyldiphenylsilyl) -oxy) -1-phenylethyl-1-one (4 j):
1 H NMR(400MHz,CDCl 3 )δ9.27(s,1H),7.84–7.80(m,2H),7.55–7.50(m,4H),7.46–7.37 (m,3H),7.35(dd,J＝4.2,2.8Hz,1H),7.33–7.28(m,5H),7.12–7.10(m,1H),7.03(d,J＝8.0Hz,1H),6.57(dd,J＝3.2,2.2Hz,1H),6.40(d,J＝8.0Hz,1H),6.24(s,1H),3.91(s,3H), 0.46(s,3H)；
13 C NMR(101MHz,CDCl 3 )δ197.3,153.9,135.3,135.0,134.9,134.5,134.4,134.0,133.1, 130.1,130.0,128.9,128.4,128.0,127.9,123.4,122.6,119.3,113.6,99.3,99.1,55.3,-2.7；
HRMS(ESI,m/z):Mass calcd.for C 30 H 27 NO 3 SiNa + [M+Na] + 500.1652,found500.1652；
HPLC analysis:99:1er(CHIRALCEL IC column；25℃,n-hexane/i-PrOH＝98/2,flow rate＝ 0.3mL/min,λ＝254nm),Rt(major)＝31.8min,Rt(minor)＝25.9min.
preparation example 24
The substituent R is Ph, R 1 Is CH 3 ，R 2 Is Ph, R 3 For 5-Cl, the preparation method and conditions are the same as 3a:
(S) -2- (5-chloro-1H-indol-7-yl) -2- ((methyldiphenylsilyl) -oxy) -1-phenylethyl-1-one (4 k):
white solid; 70% yield, 33.7mg, melting point 117-118 ℃;
(s,3H)；
13 C NMR(101MHz,CDCl 3 )δ197.3,134.7,134.6,134.4,134.3,134.0,133.6,132.1,130.3, 130.2,129.9,129.1,128.5,128.1,128.0,126.3,124.9,121.4,120.9,120.6,101.7,77.4,-2.7；
HRMS(ESI,m/z):Mass calcd.for C 29 H 24 ClNO 2 SiNa + [M+Na] + 504.1157,found504.1142；
HPLC analysis:90:10er(CHIRALCEL OD-H column,25℃,n-hexane/i-PrOH＝98/2,flow rate＝0.3mL/min,λ＝254nm),Rt(major)＝23.3min,Rt(minor)＝22.3min.
preparation example 25
The substituent R is Ph, R 1 Is CH 3 ，R 2 Is Ph, R 3 5-Br, preparation and conditions were the same as 3a:
(S) -2- (5-bromo-1H-indol-7-yl) -2- ((methyldiphenylsilyl) -oxy) -1-phenylethyl-1-one (4 l):
1 H NMR 1 HNMR(400MHz,CDCl 3 )δ9.33(s,1H),7.88–7.81(m,2H),7.69(d,J＝1.6Hz,1H), 7.52(m,5H),7.45–7.32(m,8H),7.27–7.21(m,2H),6.45(dd,J＝3.0,2.2Hz,1H),6.20(s,1H),0.55(s,3H)；
13 C NMR(101MHz,CDCl 3 )δ197.3,134.7,134.6,134.4,134.4,134.4,133.6,132.4,130.6, 130.3,130.2,129.1,128.5,128.1,128.0,126.1,123.7,123.4,121.8,112.4,101.6,77.2,-2.7；
HRMS(ESI,m/z):Mass calcd.for C 29 H 24 BrNO 2 SiNa + [M+Na] + 549.4948,found549.4939；
HPLC analysis:97:3er(CHIRALCEL IB column；25℃,n-hexane/i-PrOH＝98/2,flow rate＝ 0.3mL/min,λ＝254nm),Rt(major)＝20.9min,Rt(minor)＝19.5min.
preparation example 26
The substituent R is Ph, R 1 Is CH 3 ，R 2 Is Ph, R 3 For 6-F, the preparation implementation method and conditions are the same as 3a:
(S) -2- (6-fluoro-1H-indol-7-yl) -2- ((methyldiphenylsilyl) -oxy) -1-phenylethyl-1-one (4 m):
7.24(s,2H),7.22–7.19(m,3H),7.10(dd,J＝3.1,2.5Hz,1H),6.83(dd,J＝11.2,8.6Hz,1H), 6.74(s,1H),6.68(dd,J＝10.7,8.6Hz,1H),6.48(dd,J＝3.3,2.2Hz,1H),6.33(dd,J＝3.2, 2.2Hz,1H),0.45(s,3H)；
13 C NMR(101MHz,CDCl 3 )δ196.3,155.5(d,J＝244.3Hz),135.0,134.9,134.3(d,J＝6.1 Hz),134.0,133.6,130.1,130.0,128.6,128.4(d,J＝2.6Hz),128.0,127.9,125.4(d,J＝16.8Hz),125.4,125.2,122.3(d,J＝11.2Hz),108.0(d,J＝25.6Hz),107.1,107.0,101.7,68.8,-3.0；
19 F NMR(376MHz,CDCl 3 )δ-127.2；
HRMS(ESI,m/z):Mass calcd.for C 29 H 24 FNO 2 SiNa + [M+Na] + 488.1453,found488.1433；
HPLC analysis:93:7er(CHIRALCEL IA column,25℃,n-hexane/i-PrOH＝98/2,flow rate＝ 0.3mL/min,λ＝254nm),Rt(major)＝19.1min,Rt(minor)＝21.6min.
preparation example 27
(2) Synthetic route for preparation of (S) -2- (9H-carbazol-1-yl) -2- ((methyldiphenylsilyl) -oxy) -1-phenylethyl-1-one:
the substituent R is Ph, R 1 Is CH 3 ，R 2 Is Ph, R 3 For H, the preparation method and conditions are as follows:
0.10mmol of benzoyl silane 1, 0.15mmol of carbazole-1-formaldehyde 5 and 0.02mmol of N-heterocyclic carbene catalyst B are weighed respectively. Into a 4mL reaction tube equipped with a magnetic stirrer, 2mL of 1, 2-dichloroethane DCE and 0.06mmol of lithium bis (trimethylsilyl) amide (LiHMDS) as solvents were added, and the reaction wall was gently swirled to mix well. The bottle cap is covered, and the mixture is placed in an oil bath at 40 ℃ to be fully stirred for reaction for 14h. After the TLC monitoring reaction is finished, spin-drying, fully dissolving a small amount of dichloromethane, loading the mixture on a wet method, separating the mixture through column chromatography, obtaining a target compound 6a from eluent polar petroleum ether, namely ethyl acetate=6:1, weighing the target compound, and calculating the corresponding yield, wherein the compound is characterized by a melting point instrument, a polarimeter, a Nuclear Magnetic Resonance (NMR), a High Resolution Mass Spectrometer (HRMS) and a High Performance Liquid Chromatograph (HPLC).
The synthetic compounds were experimentally characterized as follows:
(S) -2- (9H-carbazol-1-yl) -2- ((methyldiphenylsilyl) -oxy) -1-phenylethyl-1-one (6 a):
7.20(t,J＝6.8Hz,1H),7.14(t,J＝7.6Hz,1H),6.33(s,1H),0.53(s,3H)；
13 C NMR(101MHz,CDCl 3 )δ197.2,139.7,137.7,135.0,135.0,134.7,134.5,134.4,133.3, 130.2,130.2,129.1,128.4,128.0,128.0,126.0,124.9,124.3,122.6,120.6,120.2,119.4,119.2,119.1,111.2,78.0,-2.7；
HRMS(ESI,m/z):Mass calcd.for C 33 H 27 NO 2 SiNa + [M+Na] + 520.1703,found520.1698；
HPLC analysis:95:5er(CHIRALCEL IG column,25℃,n-hexane/i-PrOH＝98/2,flow rate＝ 0.3mL/min,λ＝254nm),Rt(major)＝50.6min,Rt(minor)＝48.3min.
preparation example 28
The substituent R is 4-F-Ph, R 1 Is CH 3 ，R 2 Is Ph, R 3 For H, the preparation method and conditions are the same as 6a:
(S) -2- (9H-carbazol-1-yl) -1- (4-fluorophenyl) -2- ((methyldiphenylsilyl) -oxy) ethyl-1-one (6 b):
1H),7.44–7.36(m,2H),7.32(q,J＝7.0Hz,4H),7.23–7.14(m,3H),6.97(t,J＝8.6Hz,2H), 6.26(s,1H),0.54(s,2H)；
13 C NMR(101MHz,CDCl 3 )δ195.8,165.7(d,J＝262.6Hz),139.8,137.5,134.8(d,J＝14.4 Hz),134.5(d,J＝3.0Hz),134.0,131.9(d,J＝10.1Hz),130.9,130.8,130.3,130.2,128.1,128.0,129.9,126.1,124.5,124.3,122.7,120.7,120.2,119.4,119.3(d,J＝5.1Hz),115.6(d,J ＝21.2Hz)111.2,78.2,-2.7；
19 F NMR(376MHz,CDCl 3 )δ-104.1；
HRMS(ESI,m/z):Mass calcd.for C 33 H 26 FNO 2 SiNa + [M+Na] + 538.1615,found538.1605；
HPLC analysis:>99:1er(CHIRALCEL OD-H column,25℃,n-hexane/i-PrOH＝95/5,flow rate＝0.3mL/min,λ＝254nm),Rt(major)＝38.9min,Rt(minor)＝30.0min.
preparation example 29
The substituent R is 4-F-Cl, R 1 Is CH 3 ，R 2 Is Ph, R 3 For H, the preparation method and conditions are the same as 6a:
(S) -2- (9H-carbazol-1-yl) -1- (4-chlorophenyl) -2- ((methyldiphenylsilyl) -oxy) ethyl-1-one (6 c):
0.54(s,2H)；
13 C NMR(101MHz,CDCl 3 )δ196.1,139.8,139.7,137.5,134.8,134.7,134.5,134.4,134.0, 132.8,130.5,130.3,130.3,128.7,128.1,128.0,126.1,124.5,124.3,122.6,120.8,120.2,119.4,119.2,119.1,111.2,78.2,-2.7；
HRMS(ESI,m/z):Mass calcd.for C 33 H 26 ClNO 2 SiNa + [M+Na] + 554.1319,found554.1304；
HPLC analysis:>99:1er(CHIRALCEL OD-H column,25℃,n-hexane/i-PrOH＝95/5,flow rate＝0.3mL/min,λ＝254nm),Rt(major)＝36.8min,Rt(minor)＝29.0min.
preparation example 30
Substituent R is 4-OCH 3 -Ph，R 1 Is CH 3 ，R 2 Is Ph, R 3 For H, the preparation method and conditions are the same as 6a:
(S) -2- (9H-carbazol-1-yl) -1- (4-methoxyphenyl) -2- ((methyldiphenylsilyl) -oxy) ethyl-1-one (6 d):
25 [α] D ＝-207.1(c＝0.3in CHCl 3 )；
1 H NMR(400MHz,CDCl 3 )δ7.91(d,J＝9.0Hz,1H),7.60–7.49(m,1H),7.45–7.28(m,6H), 7.21–7.11(m,3H),6.78(d,J＝9.0Hz,2H),6.28(s,1H),3.77(s,2H),0.52(s,2H)； 13 C NMR(101MHz,CDCl 3 )δ195.6,163.7,139.7,137.7,135.1,135.0,134.5,134.4,131.6, 130.1,130.0,128.1,128.0,127.4,125.9,124.6,124.2,122.7,120.5,120.2,120.0,119.2,119.0,113.7,111.2,77.9,55.4,-2.7；
HRMS(ESI,m/z):Mass calcd.for C 34 H 29 NO 3 SiNa + [M+Na] + 550.1814,found550.1811；
HPLC analysis:99:1er(CHIRALCEL OD-H column,25℃,n-hexane/i-PrOH＝95/5,flow rate＝0.3mL/min,λ＝254nm),Rt(major)＝55.2min,Rt(minor)＝39.5min.
preparation example 31
The substituent R is 4-tBu-Ph, R 1 Is CH 3 ，R 2 Is Ph, R 3 For H, the preparation method and conditions are the same as 6a:
(S) -1- (4- (tert-butyl) phenyl) -2- (9H-carbazol-1-yl) -2- ((methyldiphenylsilyl) -oxy) ethyl-1-one (6 e):
6.8Hz,5H),7.20–7.12(m,4H),6.33(s,1H),1.25(s,3H),0.50(s,1H)；
13 C NMR(101MHz,CDCl 3 )δ195.8,156.4,138.9,136.9,134.3,133.7,133.6,131.1,129.3, 129.2,128.3,127.2,127.1,125.1,124.6,124.1,123.4,121.8,119.7,119.3,118.9,118.4,118.2,110.3,77.0,34.3,30.2,-3.5；
HRMS(ESI,m/z):Mass calcd.for C 37 H 35 NO 2 SiNa + [M+Na] + 576.2335,found576.2329；
HPLC analysis:97:3er(CHIRALCEL OD-H column,25℃,n-hexane/i-PrOH＝95/5,flow rate＝0.3mL/min,λ＝254nm),Rt(major)＝28.4min,Rt(minor)＝24.3min.
preparation example 32
The substituent R is 3-F-Ph, R 1 Is CH 3 ，R 2 Is Ph, R 3 For H, the preparation method and conditions are the same as 6a:
(S) -2- (9H-carbazol-1-yl) -1- (3-fluorophenyl) -2- ((methyldiphenylsilyl) -oxy) ethyl-1-one (6 f):
1 H NMR(400MHz,CDCl 3 )δ7.57(d,J＝7.8Hz,-1H),7.46(dd,J＝11.5,7.3Hz,1H),7.35(dt,J ＝22.2,7.3Hz,1H),7.29–7.20(m,4H),7.16–7.06(m,4H),6.18(s,1H),0.47(s,1H)；
13 C NMR(101MHz,CDCl 3 )δ194.8,162.5(d,J＝249.5Hz),139.7,137.6,136.6(d,J＝6.1 Hz),134.8,134.7,134.5(d,J＝2.6Hz),130.3,130.3,130.1(d,J＝8.1Hz),128.1,128.0, 126.1,124.9,124.8,124.7,124.4,122.6,120.8,120.5,120.3,120.2,119.3(d,J＝15.1Hz),118.9,115.9(d,J＝23.2Hz),111.2,78.2,-2.7；
19 F NMR(376MHz,CDCl 3 )δ-111.6；
HRMS(ESI,m/z):Mass calcd.for C 33 H 26 FNO 2 SiNa + [M+Na] + 538.1615,found538.1605；
HPLC analysis:>99:1er(CHIRALCEL OD-H column,25℃,n-hexane/i-PrOH＝95/5,flow rate＝0.3mL/min,λ＝254nm),Rt(major)＝33.0min,Rt(minor)＝26.1min.
preparation example 33
The substituent R is 3-CH 3 -Ph，R 1 Is CH 3 ，R 2 Is Ph, R 3 For H, the preparation method and conditions are the same as 6a:
(S) -2- (9H-carbazol-1-yl) -1- (3-chlorophenyl) -2- ((methyldiphenylsilyl) -oxy) ethyl-1-one (6 g):
7.19(t,J＝7.4Hz,2H),7.12(t,J＝7.6Hz,2H),6.32(s,1H),2.28(s,1H),0.52(s,1H)；
13 C NMR(101MHz,CDCl 3 )δ197.4,139.7,138.3,137.7,135.1,135.0,134.7,134.5,134.4, 134.1,130.2,130.1,129.6,128.2,128.0,126.2,126.0,125.0,124.3,122.6,120.5,120.1,119.5,119.2,119.0,111.2,78.0,21.3,-2.7；
HRMS(ESI,m/z):Mass calcd.for C 34 H 29 NO 2 SiNa + [M+Na] + 534.1865,found534.1861；
HPLC analysis:>99:1er(CHIRALCEL OD-H column,25℃,n-hexane/i-PrOH＝95/5,flow rate＝0.3mL/min,λ＝254nm),Rt(major)＝33.8min,Rt(minor)＝25.9min.
preparation example 34
The substituent R is 3,5-dimethyl-Ph, R 1 Is CH 3 ，R 2 Is Ph, R 3 For H, the preparation method and conditions are the same as 6a:
(S) -2- (9H-carbazol-1-yl) -1- (3, 5-dimethylphenyl) -2- ((methyldiphenylsilyl) -oxy) ethyl-1-one (6H):
25 [α] D ＝-236.8(c＝0.3in CHCl 3 )；
1 H NMR(400MHz,CDCl 3 )δ7.57–7.53(m,1H),7.47–7.37(m,2H),7.35–7.28(m,5H),7.21 –7.17(m,1H),7.12(t,J＝7.6Hz,1H),7.06(s,2H),6.31(s,1H),2.24(s,4H),0.53(s,2H)；
13 C NMR(101MHz,CDCl 3 )δ197.7,139.7,138.0,137.8,135.2,135.1,135.0,134.9,134.5, 134.4,130.1,130.0,128.0,127.9,126.8,126.0,125.0,124.3,122.6,120.6,120.1,119.6,119.2,119.0,111.2,77.9,21.2,-2.6；
HRMS(ESI,m/z):Mass calcd.for C 35 H 31 NO 2 SiNa + [M+Na] + 548.2022,found548.2019；
HPLC analysis:>99:1er(CHIRALCEL OD-H column,25℃,n-hexane/i-PrOH＝95/5,flow rate＝0.3mL/min,λ＝254nm),Rt(major)＝37.5min,Rt(minor)＝27.6min.
preparation example 35
The substituent R is PhCH 2 CH 2 ，R 1 Is CH 3 ，R 2 Is Ph, R 3 For H, the preparation method and conditions are the same as 6a:
(S) -1- (9H-carbazol-1-yl) -1- ((methyldiphenylsilyl) -oxy) -4-phenylbutyl-2-one (6 i):
7.11–7.01(m,1H),6.89(d,J＝6.5Hz,2H),2.80–2.58(m,1H)；
13 C NMR(101MHz,CDCl 3 )δ207.4,140.5,139.8,137.3,134.8,134.8,134.4,134.4,130.3, 130.3,128.3,128.1,128.1,128.0,126.0,126.0,124.2,124.2,122.8,120.6,120.2,119.4,119.3,119.2,111.2,80.7,39.0,29.4,-2.8；
HRMS(ESI,m/z):Mass calcd.for C 35 H 31 NO 2 SiNa + [M+Na] + 548.2022,found548.2017；
HPLC analysis:94:6er(CHIRALCEL IG column,25℃,n-hexane/i-PrOH＝95/5,flow rate＝ 0.3mL/min,λ＝254nm),Rt(major)＝34.2min,Rt(minor)＝30.8min.
preparation example 36
The substituent R is Ph, R 1 Is CH 3 ，R 2 Is Ph, R 3 Is 6-CH 3 The preparation method and conditions are the same as 6a:
(S) -2- (6-methyl-9H-carbazol-1-yl) -2- ((methyldiphenylsilyl) -oxy) -1-phenylethyl-1-one (6 j):
1 H NMR(400MHz,CDCl 3 )δ9.06(s,1H),7.94(d,J＝7.5Hz,1H),7.88–7.83(m,2H),7.81(s, 1H),7.57–7.50(m,4H),7.46–7.38(m,3H),7.36–7.28(m,8H),7.23(dd,J＝8.2,1.7Hz,1H),7.11(t,J＝7.6Hz,1H),6.31(s,1H),2.50(s,3H),0.50(s,3H)；
13 C NMR(101MHz,CDCl 3 )δ197.1,137.9,137.9,134.9,134.6,134.4,134.4,133.2,130.1, 130.1,129.0,128.5,128.3,127.9,127.9,127.3,124.6,124.0,122.7,120.5,120.0,119.3,118.8,110.7,78.0,21.4,-2.8；
HRMS(ESI,m/z):Mass calcd.for C 34 H 29 NO 2 SiNa + [M+Na] + 534.1860,found534.1863；
HPLC analysis:>99:1er(CHIRALCEL OD-H column,25℃,n-hexane/i-PrOH＝98/2,flow rate＝0.3mL/min,λ＝254nm),Rt(major)＝33.5min,Rt(minor)＝31.8min.
preparation example 37
The substituent R is Ph, R 1 Is CH 3 ，R 2 Is Ph, R 3 Is 6-CH 2 CH 3 The preparation method and conditions are the same as 6a:
(S) -2- (6-ethyl-9H-carbazol-1-yl) -2- ((methyldiphenylsilyl) -oxy) -1-phenylethyl-1-one (6 k):
7.43–7.30(m,9H),7.17(t,J＝7.6Hz,1H),6.39(s,1H),2.86(q,J＝7.6Hz,2H),1.37(t,J＝ 7.6Hz,3H),0.58(s,3H)；
13 C NMR(101MHz,CDCl 3 )δ197.2,138.3,138.1,135.4,135.1,134.8,134.6,134.5,133.3, 130.3,130.2,129.1,128.5,128.1,128.1,126.5,124.8,124.3,122.8,120.6,119.4,118.9,118.9,111.0,78.1,29.1,16.7,-2.6；
HRMS(ESI,m/z):Mass calcd.for C 35 H 31 NO 2 SiNa + [M+Na] + 548.2016,found548.2022；
HPLC analysis:>99:1er(CHIRALCEL OD-H column,25℃,n-hexane/i-PrOH＝95/5,flow rate＝0.3mL/min,λ＝254nm),Rt(major)＝25.7min,Rt(minor)＝24.4min.
preparation example 38
The substituent R is Ph, R 1 Is CH 3 ，R 2 Is Ph, R 3 For 6-tBu, the preparation method and conditions are the same as 6a:
(S) -2- (6-tert-butyl-9H-carbazol-1-yl) -2- ((methyldiphenylsilyl) -oxy) -1-phenylethyl-1-one (6 l):
25 [α] D ＝-45.7(c＝0.3inCHCl 3 )；
1 H NMR(400MHz,CDCl 3 )δ9.06(s,1H),8.03–7.96(m,2H),7.83(d,J＝7.1Hz,2H),7.58–7.51(m,4H),7.49(dd,J＝8.6,1.9Hz,1H),7.44–7.36(m,4H),7.35–7.27(m,7H),7.11(t,J ＝7.6Hz,1H),6.31(s,1H),1.42(s,9H),0.51(s,3H)；
13 C NMR(101MHz,CDCl 3 )δ197.2,142.3,138.1,137.9,135.1,134.7,134.5,134.4,133.2, 130.2,130.1,129.0,128.4,128.0,128.0,124.7,124.5,124.1,122.3,120.5,119.4,118.9,116.1,110.6,34.7,32.0,-2.7；
HRMS(ESI,m/z):Mass calcd.for C 37 H 35 NO 2 SiNa + [M+Na] + 576.2329,found576.2321；
HPLC analysis:>99:1er(CHIRALCEL OD-H column,25℃,n-hexane/i-PrOH＝98/2,flow rate＝0.3mL/min,λ＝254nm),Rt(major)＝27.1min,Rt(minor)＝25.4min.
preparation example 39
The substituent R is Ph, R 1 Is Ph, R 2 Is CH 3 ，R 3 For H, the preparation method and conditions are the same as 6a:
(S) -2- (9H-carbazol-1-yl) -2- ((dimethyl (phenyl) silyl) -oxy) -1-phenylethyl-1-one (6 m):
0.27(s,2H)；
13 C NMR(101MHz,CDCl 3 )δ198.6,153.5,141.1,139.0,137.9,136.0,135.0,134.7,131.3, 130.4,129.8,129.3,127.3,126.2,125.6,124.0,121.9,121.5,120.9,120.6,120.4,112.5,79.1,-0.2；
HRMS(ESI,m/z):Mass calcd.for C 28 H 25 NO 2 SiNa + [M+Na] + 458.1552,found458.1545；
HPLC analysis:>99:1er(CHIRALCEL OD-H column,25℃,n-hexane/i-PrOH＝95/5,flow rate＝0.3mL/min,λ＝254nm),Rt(major)＝30.8min,Rt(minor)＝25.3min.
(3) Derivatization research is carried out on the synthesized chiral indole compounds:
preparation example 40
Process for the preparation of compound 3a to compound 7
223.6mg3a was added to a 25mL clean bottle equipped with a magnetic stirrer, dissolved in 5mL dry tetrahydrofuran solvent, and cooled to 0 ℃. And adding 1mL of borane dimethyl sulfide, restoring to room temperature, stirring for 2 hours, adding a proper amount of methanol for quenching reaction after TLC monitoring, and spin-drying to obtain the target compound 7164mg with 73% yield by using eluent of polar petroleum ether and ethyl acetate=5:1. The target compound was obtained, and the corresponding yield was calculated after weighing, and the compound was characterized by a melting point meter, a polarimeter, nuclear magnetic resonance NMR, a high resolution mass spectrometer HRMS and a high performance liquid chromatograph HPLC.
(1 r,2 s) -2- (1H-indol-7-yl) -2- ((methyldiphenylsilyl) -oxy) -1-phenylethyl-1-ol (7):
6.99(t,J＝7.4Hz,1H),6.81(d,J＝7.2Hz,1H),6.52–6.48(m,1H),4.94–4.88(m,2H),2.01 (s,1H),0.17(s,3H)；
13 C NMR(101MHz,CDCl 3 )δ140.7,135.3,135.0,134.4,134.3,133.9,129.9,128.8,128.1, 128.0,127.8,127.7,127.5,124.3,122.8,121.2,120.8,119.1,102.1,81.0,77.5,-3.7；
HRMS(ESI,m/z):Mass calcd.for C 29 H 27 NO 2 SiNa + [M+Na] + 472.1703,found472.1704；
HPLC analysis:>99:1er(CHIRALCEL IF column,25℃,n-hexane/i-PrOH＝90/10,flow rate ＝0.5mL/min,λ＝254nm),Rt(major)＝20.0min,Rt(minor)＝18.4min.
preparation examples 41, 42
Process for the preparation of compounds 3a to compounds 8 and 9
223.6mg3a was added to a 25mL clean bottle equipped with a magnetic stirrer, dissolved in 10mL dry tetrahydrofuran solvent, and cooled to 0 ℃. Then 580 mu L of pyridine and 175 mu L of hydrofluoric acid (48-55% aqueous solution) are added, the mixture is stirred for 0.5 hour at room temperature, after TLC monitoring is finished, a proper amount of sodium chloride is added for quenching reaction, spin drying is carried out, and the eluent of polar petroleum ether and ethyl acetate=5:1 is used for obtaining 8110.5mg of the target compound, and the yield of 88%.
A25 mL clean bottle equipped with a magnetic stirrer was charged with 125.5mg of 8 in 5mL dry tetrahydrofuran solvent and cooled to 0deg.C. After 1mL of borane dimethyl sulfide was added, the mixture was returned to room temperature and stirred for 2 hours. After the TLC monitoring, an appropriate amount of methanol was added to quench the reaction, spin-dry, eluent polar petroleum ether: ethyl acetate=3:1 to give 9121.5mg of the target compound in 96% yield.
(S) -2-hydroxy-2- (1H-indol-7-yl) -1-phenylethyl-1-one (8):
2H),7.05(t,J＝7.6Hz,1H),6.50(d,J＝2.8Hz,1H),6.30(s,1H),4.21(s,1H)；
13 C NMR(101MHz,CDCl 3 )δ199.8,134.2,133.8,133.7,129.3,129.2,128.7,124.9,122.6, 121.7,120.8,119.8,102.5,75.9；
HRMS(ESI,m/z):Mass calcd.for C 16 H 13 NO 2 Na + [M+Na] + 274.0839,found274.0840；
HPLC analysis:>99:1er(CHIRALCEL IB column,25℃,n-hexane/i-PrOH＝85/15,flow rate ＝0.5mL/min,λ＝254nm),Rt(major)＝25.0min,Rt(minor)＝35.2min.
(1 s,2 r) -1- (1H-indol-7-yl) -2-phenylethyl-1, 2-diol (9):
J＝56.4Hz,2H),4.84(dd,J＝75.2,7.0Hz,2H)；
13 C NMR(101MHz,DMSO)δ144.4,134.7,128.3,128.0,127.7,127.5,127.1,125.4,120.2, 119.1,118.7,101.2,76.8,75.7；
HRMS(ESI,m/z):Mass calcd.for C 16 H 15 NO 2 Na + [M+Na] + 276.0995,found276.0999；
HPLC analysis:>99:1er(CHIRALCEL IG column,25℃,n-hexane/i-PrOH＝80/20,flow rate ＝0.3mL/min,λ＝254nm),Rt(major)＝28.3min,Rt(minor)＝26.5min.
preparation example 43
Process for the preparation of compound 3a to compound 10
A25 mL clean bottle equipped with a magnetic stirrer was charged with 223.6mg of 3a, then 6.1 mg of 4-dimethylaminopyridine and 1.2g of di-tert-butyl dicarbonate, and then 10mL of methylene chloride as a solvent. After the reaction was completed by TLC monitoring, it was dried by spin-drying and separated by column chromatography, and the eluent, polar petroleum ether, ethyl acetate=20:1, gave 10270.9mg of the target compound in 99% yield. Tert-butyl (S) -7- (1- ((methyldiphenylsilyl) -oxy) -2-oxo-2-phenylethyl) -1H-indol-1-one (10):
7.34(m,2H),7.33–7.24(m,9H),6.56(d,J＝3.8Hz,1H),1.47(s,9H),0.48(s,3H)；
13 C NMR(101MHz,CDCl 3 )δ198.2,149.9,136.4,136.0,135.7,134.7,134.5,133.0,132.2, 132.1,129.7,129.6,129.1,128.0,127.9,127.6,127.6,126.2,126.1,123.4,121.1,107.6,83.5,27.9,-2.3；
HRMS(ESI,m/z):Mass calcd.for C 34 H 33 NO 4 SiH + [M+H] + 548.2257,found548.2253；
HPLC analysis:99:1er(CHIRALCEL OD-H column,25℃,n-hexane/i-PrOH＝98/2,flow rate＝0.3mL/min,λ＝254nm),Rt(major)＝21.4min,Rt(minor)＝18.0min.
preparation example 44
Process for the preparation of compound 3a to compound 11
A25 mL clean bottle equipped with a magnetic stirrer was charged with 223.6mg of 3a, followed by 156.5mg of tetrabutylammonium fluoride and 5mL of tetrahydrofuran as solvents. After the reaction was completed by TLC monitoring, 5mL of water was added to quench the reaction, followed by spin-drying, separation by column chromatography, and eluent polar petroleum ether: ethyl acetate=20:1 to give 11270.9mg of the target compound in 99% yield.
1- (1H-indol-7-yl) -2-phenylethyl-1, 2-dione (11):
13 C NMR(101MHz,CDCl 3 )δ196.3,194.0,134.8,133.3,130.0,129.7,129.3,129.0,127.8, 126.3,119.3,116.5,103.1；
HRMS(ESI,m/z):Mass calcd.for C 16 H 11 NO 2 H + [M+H] + 250.0864,found250.0866.
(4) Antibacterial activity research on synthesized compound and derivative product
All target compounds were tested for their activity against kiwi fruit canker (Psa) using nephelometry with thiabendazole and metconazole as control agents. The compound was dissolved in 150. Mu. L N, N-dimethylformamide, and 0.1% (V/V) Tween-20 was diluted to a solution of both 100 and 50. Mu.g/mL. 1mL of the above solution was added to a liquid medium of a nontoxic nutrient broth (NB: beef extract 1.5g, peptone 2.5g, yeast powder 0.5g, glucose 5.0g, distilled water 500mL, pH=7.0 to 7.2), and a 4-mL tube was taken. Then, 40. Mu.L of NB solution containing Psa was added to 5mL of NB solution containing the test compound. The inoculated test tube was continuously shaken at 180rpm for 48 hours at (28.+ -. 1) C, and the optical density at 595nm (OD 595) was measured to correct turbidity.
The inhibition rate was calculated as follows:
I(％)＝(C tur -T tur )/C tur ×100％
C tur corrected turbidity values for bacterial growth on untreated NB;
T tur corrected turbidity values for bacterial growth on NB after drug treatment;
and I, relative inhibition rate.
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Biological activity researches show that the synthesized target compound has better inhibition effect on kiwi fruit canker pathogens, the antibacterial activity of a plurality of compounds is larger than that of commercial medicaments of metconazole and thiabendazole, especially carbazole skeleton derivatives, and the target compound has very good bacterial pathogen biological inhibition activity, wherein the compounds 6b, 6c and 6h are most excellent in performance.

Claims (3)

1. A chiral compound containing indole/carbazole skeleton alpha-siloxylketone derivative is characterized in that: the derivative is represented by the following general formula (1):
wherein the carbon atoms marked are chiral carbon atoms, R is methyl, phenyl or substituted phenyl, and the substituent of the substituted phenyl is halogen, methyl, ethyl, tertiary butyl or methoxy; r is R 1 And R is 2 Is methyl or phenyl, R 3 The substituent on the indole ring and the carbazole ring is halogen, methyl, ethyl, tertiary butyl or methoxy.
2. The chiral compound of claim 1, which comprises an indole/carbazole skeleton α -siloxylketone derivative, and is characterized in that: the halogen is fluorine, chlorine or bromine.
3. The use of a class of chiral compounds containing indole/carbazole skeleton α -siloxylone derivatives according to any one of claims 1-2 for the preparation of a medicament for the treatment and inhibition of plant bacterial diseases.
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Non-Patent Citations (1)

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Carbene-CatalyzedActivation of C Si Bonds for Chemo- and EnantioselectiveCrossBrook–Benzoin Reaction;Chenghao Tang et al.;《Angewandte Chemie》;全文 *

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