CN106831658A - 一种烯烃的不对称环氧化方法 - Google Patents

一种烯烃的不对称环氧化方法 Download PDF

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CN106831658A
CN106831658A CN201510881556.0A CN201510881556A CN106831658A CN 106831658 A CN106831658 A CN 106831658A CN 201510881556 A CN201510881556 A CN 201510881556A CN 106831658 A CN106831658 A CN 106831658A
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chiral
accordance
cdcl3
nmr
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高爽
戴文
李国松
吕迎
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Dalian Institute of Chemical Physics of CAS
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D301/00—Preparation of oxiranes
    • C07D301/02—Synthesis of the oxirane ring
    • C07D301/03—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds
    • C07D301/14—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with organic peracids, or salts, anhydrides or esters thereof
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    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
    • C07D303/02—Compounds containing oxirane rings
    • C07D303/12—Compounds containing oxirane rings with hydrocarbon radicals, substituted by singly or doubly bound oxygen atoms
    • C07D303/32—Compounds containing oxirane rings with hydrocarbon radicals, substituted by singly or doubly bound oxygen atoms by aldehydo- or ketonic radicals

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Abstract

本发明提供一种不对称催化缺电子烯烃环氧化反应方法。采用四齿氮有机配体和金属钪化合物形成的手性络合物为催化剂，以过氧化氢为氧化剂，对非官能团化烯烃进行不对称催化环氧化反应，得到相应的手性环氧化合物。该反应具有清洁，反应条件温和，高转化率和对应选择性。具有工业前景。

Description

一种烯烃的不对称环氧化方法
技术领域
本发明涉及对烯烃进行不对称环氧化的方法，还涉及适用于此目的的有机配体本身。
背景技术
烯烃的不对称环氧化反应是一类重要的有机化学反应，他可以使潜手性的烯烃转化为含有手性碳的环氧化物，然后经过开环或官能团化反应生成一系列手性化合物，在医药，农药和香料等精细化学品合成领域具有非常重要的意义。自1980年Sharpless研究小组使用钛-酒石酸催化体系成功地进行烯丙醇不对称环氧化反应之后，30多年来，人们对烯烃的不对称催化环氧化体系的研究取得了许多成果。目前的缺电子烯烃不对称催化环氧化体系主要包括孙伟课题组的手性氨基吡啶-铁体系(Chem.Eur.J.,2012,18,7332-7335.)，Yamamotto课题组的手性邻菲罗啉类配体-铁体系(J.Am.Chem.Soc.2012,134,13538)。已经发展的缺电子烯烃的不对称环氧化体系，均存在手性配体合成步骤多，总收率相对较低，底物范围窄，对应选择性不高，且配体不可重复使用等缺点。
发明内容
本发明的目的在于提供一种高效，环境友好，反应条件温和的催化非官能团化烯烃不对称环氧化反应合成手性环氧化物的新方法。
为达到上述目的，本发明采用的技术方案：
一种用于不对称催化缺电子烯烃环氧化制备不对称环氧化合物的方法，在有机溶剂中，用过氧乙酸或间氯过氧苯甲酸氧化剂，以手性四齿氮有机配体和金属钪化合物形成的络合物为催化剂，将缺电子烯烃氧化为手性的环氧化物。其中，手性配体与钪化合物的摩尔比为1:1，手性配体与底物的摩尔比为1:30～1:2，优选1:20～1:5。过氧化氢与底物的摩尔比为1:1～10:1，优选为1:1～2:1。
本发明所述有机溶剂为乙腈。过氧乙酸的质量浓度为15wt％～70wt％,优选为30wt％。反应温度为-50℃～10℃，优选为-30℃～0℃。
反应时间1-5h。
本发明所述的锰化合物为三氟甲磺酸钪[Sc(OTf)3]。
本发明所述的手性四齿氮配体是具有如下结构的化合物，其中R1、R2、R3分别为氢、烷基(分子式为CnH2n+1，n＝1-5)、芳基，芳基烷基(分子式为C6H5CnH2n,n＝1-5)或烷氧基(分子式为OCnH2n+1,n＝1-5)，R1、R2、R3相同或不同；X为O、S或N。
本发明收率最高可达94％，对映选择性最高可达95％。该反应具有清洁，反应条件温和，高转化率和对应选择性。具有工业前景。
由于上述技术的运用，本发明与现有技术相比具有下列优点：
1.配体可回收；
2.底物范围广；
3.立体选择性高。
具体实施方式
下面通过一些实施例详细说明本发明的具体实施步骤，不应将这些实施例当作本发明范围限制。
实施例1
反应条件的考察
在25℃条件下，将1.0mL含有0.01mol/L钪化合物的乙腈溶液加入到1.0mL含有0.001mol/L配体L2的乙腈溶液中，搅拌8h。然后加入0.1mmol烯烃和0.5mL乙腈。将反应混合物冷却至-20℃，慢慢加入0.1mmol氧化剂，然后在-20℃下搅拌2h。反应结束后加入饱和碳酸氢钠水溶液(8mL)洗涤，乙酸乙酯(10mL×3)萃取，合并有机相，盐洗，干燥，色谱分析得到ee值，柱层析得到产物，计算得到收率。
由表可见，最佳配体为L2，最佳氧化剂种类为CH3CO3H，最佳氧化剂与底物的比例为2：1。
实施例2手性配体L2-Sc(OTf)3催化烯烃不对称环氧化反应
a反应条件：底物(0.1mmol),30％CH3CO3H(0.2mmol,溶于0.1mL乙腈),Fe(OTf)2(10mol％),L2(10mol％),CH3CN(1.5mL),-20℃,2h。b分离收率，ee值通过手性高效液相色谱检测。
产物的表征数据如下：
3'-phenyl-3,4-dihydro-1H-spiro[naphthalene-2,2'-oxiran]-1-one(2a).1H NMR(400MHz,CDCl3)δ8.12(d,J＝7.9Hz,1H),7.52(m,1H),7.37(m,6H),7.24(m,2H),4.37(s,1H),2.92–2.72(m,2H),2.54–2.37(m,1H),1.86(m,1H)；1H NMR(400MHz,CDCl3)δ193.6,143.4,134.2,132.7,128.7,128.4,128.3,127.7,127.0,126.7,64.3,64.1,27.4,25.4；HRMS(ESI-TOF)m/z calcd for C17H14O2[M+H]+251.1072,found251.1057；HPLC(DAICEL AD-H,hexane/isopropanol 95:5,flow rate:1.0mL/min,254nm):tr(major)＝16.5min,tr(minor)＝20.6min.
3'-(2-fluorophenyl)-3,4-dihydro-1H-spiro[naphthalene-2,2'-oxiran]-1-one(2b).1H NMR(400MHz,CDCl3)δ8.13(d,J＝7.8Hz,1H),7.53(m,1H),7.45–7.32(m,3H),7.26–7.16(m,2H),7.13–7.04(m,1H),4.46(s,1H),2.98–2.82(m,2H),2.48–2.37(m,1H),1.75(m,1H)；13C{1H}NMR(100MHz,CDCl3)δ193.0,144.5(d,J＝226.0Hz),134.3,132.7,129.9,128.7,128.6,127.8,127.0,124.1,124.0,122.1,121.9,115.3,115.1,63.9,59.7,27.4,25.8；HRMS(ESI-TOF)m/z calcdfor C17H13FO2[M+H]+269.0978,found 269.0967；HPLC(DAICEL AD-H,hexane/isopropanol 95:5,flow rate:1.0mL/min,254nm):tr(major)＝12.4min,tr(minor)＝15.1min.
3'-(2-chlorophenyl)-3,4-dihydro-1H-spiro[naphthalene-2,2'-oxiran]-1-one(2c).1H NMR(400MHz,CDCl3)δ8.14(d,J＝7.9Hz,1H),7.53(m,1H),7.46–7.42(m,1H),7.36(m,4H),7.24(d,J＝7.8Hz,1H),4.44(s,1H),3.07–2.95(m,1H),2.85(m,1H),2.40(m,1H),1.65(m,1H)；13C{1H}NMR(100MHz,CDCl3)δ193.0,134.3,133.1,132.7,129.5,129.2,128.7,128.5,127.8,127.0,126.7,64.0,62.8,27.7,25.9；HRMS(ESI-TOF)m/z calcd for C17H13ClO2[M+H]+285.0682,found 285.0693；HPLC(DAICEL AD-H,hexane/isopropanol 95:5,flow rate:1.0mL/min,254nm):tr(major)＝10.7min,tr(minor)＝13.5min.
3'-(2-bromophenyl)-3,4-dihydro-1H-spiro[naphthalene-2,2'-oxiran]-1-one(2d).1H NMR(400MHz,CDCl3)δ8.14(dd,J＝7.9,1.0Hz,1H),7.59–7.50(m,2H),7.44–7.36(m,3H),7.28–7.23(m,3H),4.38(s,1H),3.07(m,1H),2.86(m,1H),2.39(m,1H),1.73–1.57(m,1H)；13C{1H}NMR(100MHz,CDCl3)δ193.0,143.5,134.3,132.7,132.3,129.8,128.8,127.8,127.3,127.0,122.4,64.9,64.0,27.8,25.9；HRMS(ESI-TOF)m/z calcd for C17H13BrO2[M+H]+329.0177,found 329.0171；HPLC(DAICELAD-H,hexane/isopropanol 95:5,flow rate:1.0mL/min,254nm):tr(major)＝11.2min,tr(minor)＝13.8min.
3'-(2-(trifluoromethyl)phenyl)-3,4-dihydro-1H-spiro[naphthalene-2,2'-oxiran]-1-one(2e).1H NMR(400MHz,CDCl3)δ8.12(dd,J＝7.8,0.9Hz,1H),7.68(d,J＝7.8Hz,1H),7.62(m,2H),7.55–7.45(m,2H),7.36(m,1H),7.22(d,J＝7.7Hz,1H),4.66(d,J＝1.9Hz,1H),2.95–2.79(m,2H),2.36(m,1H),1.76(m,1H)；13C{1H}NMR(100MHz,CDCl3)δ192.7,143.3,134.3,132.7,132.5,131.8,128.4(q,J＝33.2Hz),128.0,127.8,127.0,126.0(q,J＝5.4Hz),124.2(d,J＝272.1),120.1,64.2,61.6(q,J＝30.0Hz),26.7,25.1；HRMS(ESI-TOF)m/z calcdfor C18H13F3O2[M+H]+319.0946,found 319.0962；HPLC(DAICEL AD-H,hexane/isopropanol 95:5,flow rate:1.0mL/min,254nm):tr(major)＝8.5min,tr(minor)＝10.4min.
3'-(2-nitrophenyl)-3,4-dihydro-1H-spiro[naphthalene-2,2'-oxiran]-1-one(2f).1H NMR(400MHz,CDCl3)δ8.20(m,2H),7.76(m,2H),7.62–7.47(m,2H),7.38(m,1H),7.21(d,J＝7.6Hz,1H),4.75(s,1H),2.92–2.76(m,2H),2.41(m,1H),1.63(m,1H)；13C{1H}NMR(100MHz,CDCl3)δ192.5,147.3,143.2,134.3,134.2,132.6,131.5,129.8,129.3,128.7,127.9,127.1,125.0,64.3,63.3,27.4,26.0；HRMS(ESI-TOF)m/z calcd for C17H13NO4[M+H]+296.0923,found 296.0912；HPLC(DAICELAD-H,hexane/isopropanol 95:5,flow rate:1.0mL/min,254nm):tr(major)＝35.8min,tr(minor)＝37.9min.
3'-(3-fluorophenyl)-3,4-dihydro-1H-spiro[naphthalene-2,2'-oxiran]-1-one(2g).1H NMR(400MHz,CDCl3)δ8.10(d,J＝7.8Hz,1H),7.53(m,J＝7.5,1.3Hz,1H),7.37(m,2H),7.24(d,J＝7.6Hz,1H),7.17(d,J＝7.7Hz,1H),7.11–7.02(m,2H),4.35(s,1H),2.95–2.75(m,2H),2.44(m,1H),1.85(m,1H)；13C{1H}NMR(100MHz,CDCl3)δ193.1,162.8(d,J＝245.6Hz),161.5,143.3,136.9(d,J＝7.6Hz),134.4,132.6,130.1(d,J＝8.2Hz),128.8,127.7,127.1,122.4,115.5,115.3,113.8,113.6,64.3,63.3,27.3,25.3；HRMS(ESI-TOF)m/z calcdfor C17H13FO2[M+H]+269.0978,found 269.0969；HPLC(DAICEL AD-H,hexane/isopropanol 95:5,flow rate:1.0mL/min,254nm):tr(major)＝15.6min,tr(minor)＝20.0min.
3'-(3-chlorophenyl)-3,4-dihydro-1H-spiro[naphthalene-2,2'-oxiran]-1-one(2h).1H NMR(400MHz,CDCl3)δ8.11(d,J＝7.8Hz,1H),7.53(m,1H),7.42–7.30(m,4H),7.26–7.21(m,2H),4.34(s,1H),2.96–2.77(m,2H),2.44(m,1H),1.84(m,1H)；13C{1H}NMR(100MHz,CDCl3)δ193.1,143.3,136.4,134.4,132.6,129.7,128.8,128.6,127.8,127.1,126.7,124.9,122.7,64.2,63.2,27.3,25.3；HRMS(ESI-TOF)m/z calcdfor C17H13ClO2[M+H]+285.0682,found 285.0673；HPLC(DAICEL AD-H,hexane/isopropanol 95:5,flow rate:1.0mL/min,254nm):tr(major)＝13.2min,tr(minor)＝16.3min.
3'-(3-bromophenyl)-3,4-dihydro-1H-spiro[naphthalene-2,2'-oxiran]-1-one(2i).1H NMR(400MHz,CDCl3)δ8.11(d,J＝7.8Hz,1H),7.56–7.48(m,3H),7.37(m,1H),7.33–7.22(m,3H),4.34(s,1H),3.03–2.73(m,2H),2.44(m,1H),1.84(m,1H),1.57(s,1H)；13C{1H}NMR(100MHz,CDCl3)δ193.0,143.3,136.6,134.4,132.6,131.6,130.0,129.6,128.8,127.74,127.1,125.3,122.7,64.3,63.1,27.3,25.3；HRMS(ESI-TOF)m/z calcd for C17H13BrO2[M+H]+329.0177,found 329.0167；HPLC(DAICEL AD-H,hexane/isopropanol 95:5,flow rate:1.0mL/min,254nm):tr(major)＝15.3min,tr(minor)＝19.9min.
3'-(3-(trifluoromethyl)phenyl)-3,4-dihydro-1H-spiro[naphthalene-2,2'-oxiran]-1-one(2j).1H NMR(400MHz,CDCl3)δ8.12(dd,J＝7.9,1.0Hz,1H),7.66–7.46(m,5H),7.38(m,1H),7.24(d,J＝7.7Hz,1H),4.43(s,1H),3.03–2.71(m,2H),2.44(m,1H),1.79(m,1H)；13C{1H}NMR(100MHz,CDCl3)δ192.9,143.2,135.4,134.4,132.6,130.0,129.0,128.8,127.8,127.2,125.3(d,J＝182.6Hz),123.5,64.2,63.2,27.2,25.3；HRMS(ESI-TOF)m/z calcd for C18H13F3O2[M+H]+319.0946,found 319.0937；HPLC(DAICEL AD-H,hexane/isopropanol 95:5,flow rate:1.0mL/min,254nm):tr(major)＝10.6min,tr(minor)＝12.9min.
3'-(4-fluorophenyl)-3,4-dihydro-1H-spiro[naphthalene-2,2'-oxiran]-1-one(2k).1H NMR(400MHz,CDCl3)δ8.09(dd,J＝7.9,1.0Hz,1H),7.52(m,1H),7.41–7.31(m,3H),7.23(d,J＝7.6Hz,1H),7.15–7.03(m,2H),4.34(s,1H),2.92–2.76(m,2H),2.43(m,1H),1.82(m,1H)；13C{1H}NMR(100MHz,CDCl3)δ193.30(s),162.7(d,J＝246Hz),143.3,134.3,132.7,129.9,128.8,128.4,128.3,127.6,127.1,115.6,115.3,64.3,63.5,27.3,25.3；HRMS(ESI-TOF)m/z calcd forC17H13FO2[M+H]+269.0978,found 269.0971；HPLC(DAICEL AD-H,hexane/isopropanol 95:5,flow rate:1.0mL/min,254nm):tr(major)＝17.0min,tr(minor)＝21.3min.
3'-(4-bromophenyl)-3,4-dihydro-1H-spiro[naphthalene-2,2'-oxiran]-1-one(2l).1H NMR(400MHz,CDCl3)δ8.11(dd,J＝7.8,1.0Hz,1H),7.58–7.49(m,3H),7.38(m,J＝7.6Hz,1H),7.29–7.22(m,3H),4.32(s,1H),2.92–2.74(m,2H),2.44(m,1H),1.81(m,1H)；13C{1H}NMR(100MHz,CDCl3)δ193.2,143.2,134.4,132.6,131.6,128.8,128.3,127.7,127.1,64.27(s),63.5,27.3,25.3；HRMS(ESI-TOF)m/z calcd forC17H13BrO2[M+H]+329.0177,found 329.0173；HPLC(DAICEL AD-H,hexane/isopropanol 95:5,flow rate:1.0mL/min,254nm):tr(major)＝18.0min,tr(minor)＝24.5min.
3'-(4-(trifluoromethyl)phenyl)-3,4-dihydro-1H-spiro[naphthalene-2,2'-oxiran]-1-one(2m).1H NMR(400MHz,CDCl3)δ8.19–8.09(m,1H),7.66(d,J＝8.2Hz,2H),7.54(m,3H),7.38(m,1H),7.25(m,1H),4.43(s,1H),2.95–2.76(m,2H),2.44(m,1H),1.80(m,1H)；13C{1H}NMR(100MHz,CDCl3)δ192.9,143.2,134.4,132.6,128.8,127.8,127.1,127.2,125.4,64.3,63.2,27.3,25.3；HRMS(ESI-TOF)m/z calcd forC18H13F3O2[M+H]+319.0946,found 319.0944；HPLC(DAICEL AD-H,hexane/isopropanol 95:5,flow rate:1.0mL/min,254nm):tr(major)＝11.7min,tr(minor)＝16.1min.
3'-(4-nitrophenyl)-3,4-dihydro-1H-spiro[naphthalene-2,2'-oxiran]-1-one(2n).1H NMR(400MHz,CDCl3)δ8.38–8.22(m,2H),8.12(d,J＝7.9Hz,1H),7.63–7.52(m,3H),7.39(m,1H),7.24(m,1H),4.47(s,1H),2.97–2.72(m,2H),2.45(m,1H),1.79(m,1H)；13C{1H}NMR(100MHz,CDCl3)δ192.4,148.0,143.1,141.5,134.6,132.5,128.8,127.9,127.6,127.3,123.7,64.4,62.8,27.2,25.3；HRMS(ESI-TOF)m/zcalcd for C17H13NO4[M+H]+296.0923,found 296.0912；HPLC(DAICEL OJ-H,hexane/isopropanol 50:50,flow rate:1.0mL/min,254nm):tr(minor)＝15.1min,tr(major)＝22.9min.
3'-(p-tolyl)-3,4-dihydro-1H-spiro[naphthalene-2,2'-oxiran]-1-one(2o).1H NMR(400MHz,CDCl3)δ8.12(m,1H),7.51(m,1H),7.35(d,J＝6.8Hz,1H),7.28–7.19(m,5H),4.33(s,1H),2.83(m,2H),2.49–2.41(m,1H),2.38(s,3H),1.86(m,1H)；13C{1H}NMR(100MHz,CDCl3)δ193.7,143.4,138.2,134.2,132.8,131.1,130.0,129.0,128.7,127.6,127.0,126.6,64.3,28.9,27.4,25.4,21.2.；HRMS(ESI-TOF)m/z calcdfor C18H16O2[M+H]+265.1229,found 265.1218；HPLC(DAICEL AD-H,hexane/isopropanol 95:5,flow rate:1.0mL/min,254nm):tr(major)＝17.4min,tr(minor)＝26.5min.
3'-(2,3-dichlorophenyl)-3,4-dihydro-1H-spiro[naphthalene-2,2'-oxiran]-1-one(2p).1H NMR(400MHz,CDCl3)δ8.14(dd,J＝7.9,1.0Hz,1H),7.59–7.46(m,2H),7.37(m,2H),7.30(d,J＝7.8Hz,1H),7.28–7.20(m,2H),4.44(s,1H),2.93(m,2H),2.46–2.31(m,1H),1.64(m,1H)；13C{1H}NMR(100MHz,CDCl3)δ192.7,143.4,135.1,134.4,133.1,132.6,131.2,130.3,128.8,127.8,127.4,127.1,126.7,64.0,62.8,27.7,25.9；HRMS(ESI-TOF)m/z calcd for C17H12Cl2O2[M+H]+319.0293,found 319.0291；HPLC(DAICEL AD-H,hexane/isopropanol 95:5,flow rate:1.0mL/min,254nm):tr(major)＝10.3min,tr(minor)＝14.2min.
3'-(2,4-dichlorophenyl)-3,4-dihydro-1H-spiro[naphthalene-2,2'-oxiran]-1-one(2q).1H NMR(400MHz,CDCl3)δ8.13(dd,J＝7.9,1.1Hz,1H),7.54(m,1H),7.46–7.30(m,4H),7.24(m,1H),4.40(s,1H),3.06–2.81(m,2H),2.47–2.33(m,1H),1.63(m,1H)；13C{1H}NMR(100MHz,CDCl3)δ192.7,143.3,134.9,134.4,132.6,131.4,129.4,129.1,128.8,127.8,127.2,127.1,64.0,62.2,27.6,25.9；HRMS(ESI-TOF)m/z calcd for C17H12Cl2O2[M+H]+319.0293,found 319.0287；HPLC(DAICELAD-H,hexane/isopropanol 95:5,flow rate:1.0mL/min,254nm):tr(major)＝10.1min,tr(minor)＝10.8min.
3'-(2-chloro-5-(trifluoromethyl)phenyl)-3,4-dihydro-1H-spiro[naphthalene-2,2'-oxiran]-1-one(2r).1H NMR(400MHz,CDCl3)δ8.14(d,J＝7.8Hz,1H),7.64–7.49(m,3H),7.39(m,1H),7.26(m,2H),4.49(s,1H),3.03–2.86(m,2H),2.40(m,1H),1.62(m,1H)；13C{1H}NMR(100MHz,CDCl3)δ192.3,143.3,136.8,134.5,134.0,132.5,129.8,128.8,127.9,127.1,126.4,125.6,64.0,62.1,27.6,25.9；HRMS(ESI-TOF)m/z calcd for C18H12ClF3O2[M+H]+353.0556,found 353.0573；HPLC(DAICELAD-H,hexane/isopropanol 95:5,flow rate:1.0mL/min,254nm):tr(major)＝8.0min,tr(minor)＝11.6min.
3'-(4-chloro-2-fluorophenyl)-3,4-dihydro-1H-spiro[naphthalene-2,2'-oxiran]-1-one(2s).1H NMR(400MHz,CDCl3)δ8.12(d,J＝7.8Hz,1H),7.54(m,1H),7.42–7.30(m,2H),7.26–7.18(m,2H),7.13(m,1H),4.41(s,1H),2.96–2.84(m,2H),2.42(m,1H),1.72(m,1H)；13C{1H}NMR(100MHz,CDCl3)δ192.6,143.3(d,J＝203.3Hz),135.15(d,J＝11.4Hz),134.4,129.4,128.7,127.8,127.1,124.6,120.8(d,J＝14.0Hz),116.3,116.0,63.9,59.1,27.4,25.8；HRMS(ESI-TOF)m/zcalcd for C17H12ClFO2[M+H]+303.0588,found 303.0592；HPLC(DAICEL AD-H,hexane/isopropanol 95:5,flow rate:1.0mL/min,254nm):tr(major)＝11.5min,tr(minor)＝13.4min.
3'-(2-bromo-4-chlorophenyl)-3,4-dihydro-1H-spiro[naphthalene-2,2'-oxiran]-1-one(2t).1H NMR(400MHz,CDCl3)δ8.14(d,J＝7.9Hz,1H),7.59(d,J＝1.6Hz,1H),7.53(m,1H),7.43–7.32(m,3H),7.24(m,1H),4.34(s,1H),3.16–2.78(m,2H),2.39(m,1H),1.62(m,1H)；13C{1H}NMR(100MHz,CDCl3)δ192.7,143.4,135.0,134.4,133.0,132.6,132.1,129.6,128.8,127.8,127.7,127.1,122.6,64.3,64.0,27.7,25.9；HRMS(ESI-TOF)m/z calcd for C17H12BrClO2[M+H]+362.9787,found362.9791；HPLC(DAICEL AD-H,hexane/isopropanol 95:5,flow rate:1.0mL/min,254nm):tr(major)＝12.2min,tr(minor)＝13.7min.
3'-(2-fluoro-4-methylphenyl)-3,4-dihydro-1H-spiro[naphthalene-2,2'-oxiran]-1-one(2u).1H NMR(400MHz,CDCl3)δ8.12(dd,J＝7.8,1.0Hz,1H),7.52(m,1H),7.37(m,1H),7.25(m,2H),7.00(d,J＝7.8Hz,1H),6.90(m,1H),4.41(s,1H),2.89(m,2H),2.47–2.40(m,1H),2.38(s,3H),1.75(m,1H)；13C{1H}NMR(100MHz,CDCl3)δ193.2,162.3,161.1(J＝246Hz),143.5,140.7,134.2,132.7,128.7,128.2,127.7,127.0,124.7,118.8,118.7,115.9,115.7,64.0,59.8,27.5,25.8,21.2；HRMS(ESI-TOF)m/z calcd for C18H15FO2[M+H]+283.1134,found 283.1137；HPLC(DAICEL AD-H,hexane/isopropanol 95:5,flow rate:1.0mL/min,254nm):tr(major)＝15.7min,tr(minor)＝23.0min.
3'-(2-chlorophenyl)-6-methoxy-3,4-dihydro-1H-spiro[naphthalene-2,2'-oxiran]-1-one(2v).1H NMR(400MHz,CDCl3)δ8.12(d,J＝8.8Hz,1H),7.46–7.42(m,1H),7.40–7.37(m,1H),7.34–7.30(m,2H),6.88(dd,J＝8.8,2.4Hz,1H),6.68(d,J＝2.3Hz,1H),4.43(s,1H),3.87(s,3H),2.99(m,1H),2.80(m,1H),2.37(m,1H),1.66–1.57(m,2H)；13C{1H}NMR(100MHz,CDCl3)δ191.6,164.3,146.0,133.0,132.9,130.4,129.4,129.1,128.5,126.7,126.4,113.4,112.7,63.9,62.6,55.5,28.0,26.0；HRMS(ESI-TOF)m/z calcd for C18H15ClO3[M+H]+315.0788,found 315.0796；HPLC(DAICEL AD-H,hexane/isopropanol 95:5,flow rate:1.0mL/min,254nm):tr(major)＝29.0min,tr(minor)＝39.8min.
(3-(2-chlorophenyl)oxiran-2-yl)(phenyl)methanone(2w).1H NMR(400MHz,CDCl3)δ8.13–8.02(m,2H),7.63(m,1H),7.51(m,2H),7.40(m,2H),7.36–7.29(m,2H),4.41(d,J＝1.8Hz,1H),4.16(d,J＝1.9Hz,1H)；13C{1H}NMR(100MHz,CDCl3)δ192.8,134.0,129.8,129.4,128.9,128.4,127.3,126.2,60.1,57.1；HRMS(ESI-TOF)m/z calcdfor C15H11ClO2[M+H]+259.0526,found 259.0518；HPLC(DAICEL AD-H,hexane/isopropanol 95:5,flow rate:1.0mL/min,254nm):tr(major)＝11.6min,tr(minor)＝12.8min。

Claims (8)

1.一种烯烃的不对称环氧化方法，其特征在于：
以乙腈为溶剂，过氧乙酸或间氯过氧苯甲酸中的一种或二种为氧源，以手性四齿氮有机配体和金属钪化合物形成的络合物为催化剂，将缺电子烯烃氧化为手性的环氧化物；其中，手性四齿氮有机配体与钪化合物的摩尔比为1:1，手性四齿氮有机配体与底物缺电子烯烃的摩尔比为1:30～1:2；过氧乙酸或间氯过氧苯甲酸中的一种或二种与缺电子烯烃的摩尔比为1:1～10:1。
2.按照权利要求1所述的方法，其特征在于：
手性四齿氮有机配体与底物非官能团化烯烃的摩尔比优选为1:20～1:5；过氧乙酸或间氯过氧苯甲酸与缺电子烯烃的摩尔比为优选为1:1～2:1。
3.按照权利要求1所述的方法，其特征在于：所述氧化剂采用的是过氧乙酸的乙酸溶液，其质量浓度为15wt％～70wt％；过氧化氢的质量浓度优选为30wt％。
4.按照权利要求1所述的方法，其特征在于：反应温度为-50℃～10℃；反应温度优选为-30℃～0℃。
5.按照权利要求1所述的方法，其特征在于：钪化合物为三氟甲磺酸钪[SC(OTf)3]。
6.按照权利要求1所述的方法，其特征在于：所述的手性四齿氮配体是具有如下结构的化合物，其中R1、R2、R3分别为氢、烷基(分子式为CnH2n+1，n＝1-5)、芳基，芳基烷基(分子式为C6H5CnH2n,n＝1-5)或烷氧基(分子式为OCnH2n+1,n＝1-5)，R1、R2、R3相同或不同；X为O、S或N；
7.按照权利要求1所述的方法，其特征在于：
所述的缺电子烯烃是具有如下结构的化合物，其中R5、R6分别为氢、烷基(分子式为CnH2n+1，n＝1-5)、芳基、芳基烷基(分子式为C6H5CnH2n,n＝1-5)、烷氧基(分子式为OCnH2n+1,n＝1-5或烷氨基(分子式为NCnH2n+1,n＝1-5)，R5、R6相同或不同
8.按照权利要求1所述的方法，其特征在于：
无需任何添加剂；手性四齿氮有机配体在反应后可回收。
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