本發(fā)明涉及對(duì)烯烴進(jìn)行不對(duì)稱(chēng)環(huán)氧化的方法，還涉及適用于此目的的有機(jī)配體本身。

背景技術(shù)：

烯烴的不對(duì)稱(chēng)環(huán)氧化反應(yīng)是一類(lèi)重要的有機(jī)化學(xué)反應(yīng)，他可以使?jié)撌中缘南N轉(zhuǎn)化為含有手性碳的環(huán)氧化物，然后經(jīng)過(guò)開(kāi)環(huán)或官能團(tuán)化反應(yīng)生成一系列手性化合物，在醫(yī)藥，農(nóng)藥和香料等精細(xì)化學(xué)品合成領(lǐng)域具有非常重要的意義。自1980年Sharpless研究小組使用鈦-酒石酸催化體系成功地進(jìn)行烯丙醇不對(duì)稱(chēng)環(huán)氧化反應(yīng)之后，30多年來(lái)，人們對(duì)烯烴的不對(duì)稱(chēng)催化環(huán)氧化體系的研究取得了許多成果。目前的缺電子烯烴不對(duì)稱(chēng)催化環(huán)氧化體系主要包括孫偉課題組的手性氨基吡啶-鐵體系(Chem.Eur.J.,2012,18,7332-7335.)，Yamamotto課題組的手性鄰菲羅啉類(lèi)配體-鐵體系(J.Am.Chem.Soc.2012,134,13538)。已經(jīng)發(fā)展的缺電子烯烴的不對(duì)稱(chēng)環(huán)氧化體系，均存在手性配體合成步驟多，總收率相對(duì)較低，底物范圍窄，對(duì)應(yīng)選擇性不高，且配體不可重復(fù)使用等缺點(diǎn)。

技術(shù)實(shí)現(xiàn)要素：

本發(fā)明的目的在于提供一種高效，環(huán)境友好，反應(yīng)條件溫和的催化非官能團(tuán)化烯烴不對(duì)稱(chēng)環(huán)氧化反應(yīng)合成手性環(huán)氧化物的新方法。

為達(dá)到上述目的，本發(fā)明采用的技術(shù)方案：

一種用于不對(duì)稱(chēng)催化缺電子烯烴環(huán)氧化制備不對(duì)稱(chēng)環(huán)氧化合物的方法，在有機(jī)溶劑中，用過(guò)氧乙酸或間氯過(guò)氧苯甲酸氧化劑，以手性四齒氮有機(jī)配體和金屬鈧化合物形成的絡(luò)合物為催化劑，將缺電子烯烴氧化為手性的環(huán)氧化物。其中，手性配體與鈧化合物的摩爾比為1:1，手性配體與底物的摩爾比為1:30～1:2，優(yōu)選1:20～1:5。過(guò)氧化氫與底物的摩爾比為1:1～10:1，優(yōu)選為1:1～2:1。

本發(fā)明所述有機(jī)溶劑為乙腈。過(guò)氧乙酸的質(zhì)量濃度為15wt％～70wt％,優(yōu)選為30wt％。反應(yīng)溫度為-50℃～10℃，優(yōu)選為-30℃～0℃。

反應(yīng)時(shí)間1-5h。

本發(fā)明所述的錳化合物為三氟甲磺酸鈧[Sc(OTf)3]。

本發(fā)明所述的手性四齒氮配體是具有如下結(jié)構(gòu)的化合物，其中R1、R2、R3分別為氫、烷基(分子式為CnH2n+1，n＝1-5)、芳基，芳基烷基(分子式為C6H5CnH2n,n＝1-5)或烷氧基(分子式為OCnH2n+1,n＝1-5)，R1、R2、R3相同或不同；X為O、S或N。

本發(fā)明收率最高可達(dá)94％，對(duì)映選擇性最高可達(dá)95％。該反應(yīng)具有清潔，反應(yīng)條件溫和，高轉(zhuǎn)化率和對(duì)應(yīng)選擇性。具有工業(yè)前景。

由于上述技術(shù)的運(yùn)用，本發(fā)明與現(xiàn)有技術(shù)相比具有下列優(yōu)點(diǎn)：

1.配體可回收；

2.底物范圍廣；

3.立體選擇性高。

具體實(shí)施方式

下面通過(guò)一些實(shí)施例詳細(xì)說(shuō)明本發(fā)明的具體實(shí)施步驟，不應(yīng)將這些實(shí)施例當(dāng)作本發(fā)明范圍限制。

實(shí)施例1

反應(yīng)條件的考察

在25℃條件下，將1.0mL含有0.01mol/L鈧化合物的乙腈溶液加入到1.0mL含有0.001mol/L配體L2的乙腈溶液中，攪拌8h。然后加入0.1mmol 烯烴和0.5mL乙腈。將反應(yīng)混合物冷卻至-20℃，慢慢加入0.1mmol氧化劑，然后在-20℃下攪拌2h。反應(yīng)結(jié)束后加入飽和碳酸氫鈉水溶液(8mL)洗滌，乙酸乙酯(10mL×3)萃取，合并有機(jī)相，鹽洗，干燥，色譜分析得到ee值，柱層析得到產(chǎn)物，計(jì)算得到收率。

由表可見(jiàn)，最佳配體為L(zhǎng)2，最佳氧化劑種類(lèi)為CH3CO3H，最佳氧化劑與底物的比例為2：1。

實(shí)施例2手性配體L2-Sc(OTf)3催化烯烴不對(duì)稱(chēng)環(huán)氧化反應(yīng)

a反應(yīng)條件：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分離收率，ee值通過(guò)手性高效液相色譜檢測(cè)。

產(chǎn)物的表征數(shù)據(jù)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'-oxira n]-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 calcd for 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'-oxira n]-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(DAICEL AD-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 calcd for 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(DAICEL AD-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'-oxira n]-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 calcd for 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'-oxira n]-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 calcd for 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'-oxira n]-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 for C17H13FO2[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 for C17H13BrO2[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 for C18H13F3O2[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/z calcd 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-on e(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 calcd for 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'-o xiran]-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'-o xiran]-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(DAICEL AD-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[na phthalene-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(DAICEL AD-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/z calcd 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 calcd for 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。