CN115028645A - 双吲哚酮[螺]苯并二氢呋喃类化合物的合成方法 - Google Patents
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Abstract
本发明公开了双吲哚酮[螺]苯并二氢呋喃类化合物的合成方法，属于有机合成技术领域。以N‑苯氧基乙酰胺类化合物1和重氮吲哚酮类化合物2为原料，在铑(III)催化剂和添加剂存在下，有机溶剂中升温反应，得到双吲哚酮[螺]苯并二氢呋喃类化合物3。本发明通过N‑苯氧基乙酰胺和重氮吲哚酮之间的一锅多步串联反应，高效合成了双吲哚酮[螺]苯并二氢呋喃类化合物；该合成方法具有原料简单易得、操作简便、底物适用范围广等优点。
Description
技术领域
本发明属于有机合成技术领域，具体涉及双吲哚酮[螺]苯并二氢呋喃类化合物的合成方法。
背景技术
苯并二氢呋喃类化合物具有显著抗抑郁、抗真菌、抗结核、镇咳、镇痛、抗心律失常和抗增殖等生物活性。螺环为具有较高刚性和独特三维结构，在药物开发的先导化合物中引入螺环往往可以有效改变母体化合物的理化性能并提高其药物活性。例如：螺吲哚酮类化合物表现出强烈的抗病毒、抗菌、抗癌、抗结核和抗疟活性，是药物发现的重要来源。
鉴于苯并二氢呋喃和螺吲哚酮类化合物的重要性，包含这两种优势结构单元的双吲哚酮[螺]苯并二氢呋喃类化合物可能具有更为优异的生物活性和理化性能。因此，研究并开发该类化合物的高效合成方法，不仅具有重要的理论意义，而且具有潜在的应用价值。
发明内容
本发明主要提供了一种双吲哚酮[螺]苯并二氢呋喃类化合物的合成方法，该方法通过N-苯氧基乙酰胺和重氮吲哚酮之间的一锅多步串联反应，高效合成双吲哚酮[螺]苯并二氢呋喃类化合物。该合成方法具有原料简单易得、操作简便、底物适用范围广等优点。
本发明所合成的双吲哚酮[螺]苯并二氢呋喃类化合物，其结构通式为：
其中，R1为氢、C1-6链状烷基、C1-4取代烷基、C1-4烷氧基、苯基、取代苯基、C1-4烷氧羰基或卤素，R1为一元或二元取代，R2为C1-6链状烷基或卤素，R3为C1-4烷基、C1-4取代烷基、苯基或取代苯基，上述取代烷基的取代基为苯基、取代苯基或C1-4烷氧羰基，上述取代苯基苯环上的取代基为C1-4烷基。
本发明还提供了上述双吲哚酮[螺]苯并二氢呋喃类化合物的合成方法，采用的技术方案为：
双吲哚酮[螺]苯并二氢呋喃类化合物的合成方法，包括如下操作：以N-苯氧基乙酰胺类化合物1和重氮吲哚酮类化合物2为原料，在铑(III)催化剂和添加剂存在下，有机溶剂中升温反应，得到双吲哚酮[螺]苯并二氢呋喃类化合物3；反应方程式为：
其中，R1为氢、C1-6链状烷基、C1-4取代烷基、C1-4烷氧基、苯基、取代苯基、C1-4烷氧羰基或卤素，R1为一元或二元取代，R2为C1-6链状烷基或卤素，R3为C1-4烷基、C1-4取代烷基、苯基或取代苯基，上述取代烷基的取代基为苯基、取代苯基或C1-4烷氧羰基，上述取代苯基苯环上的取代基为C1-4烷基。
进一步地，在上述技术方案中，所述反应溶剂为起到溶解原料的作用，优选1,2-二氯乙烷、四氢呋喃或1,4-二氧六环。
进一步地，在上述技术方案中，所述铑(III)催化剂为二氯(五甲基环戊二烯基)合铑(III)二聚体([RhCp*Cl2]2)。
进一步地，在上述技术方案中，所述添加剂为醋酸钠、醋酸铯或1-金刚烷甲酸。
进一步地，在上述技术方案中，所述N-苯氧基乙酰胺类化合物1、重氮吲哚酮类化合物2、铑(III)催化剂、添加剂的投料摩尔比为1-1.2:1-3:0.05-0.08:0.05-1。
进一步地，在上述技术方案中，反应温度为30-60℃。
进一步地，在上述技术方案中，反应在空气氛围下进行。
发明有益效果：
本发明与现有技术相比具有以下优点：(1)通过N-苯氧基乙酰胺类化合物和重氮吲哚酮类化合物的一锅串联反应，高效合成了双吲哚酮[螺]苯并二氢呋喃类化合物，合成过程简单、高效；(2)原料价廉易得；(3)氧化还原中性条件，无需氧化剂，操作简便，底物的适用范围广。
说明书附图
图1为实施例1中化合物3a的X-射线单晶衍射图。
具体实施方式
以下通过实施例对本发明的上述内容做进一步详细说明，但不应该将此理解为本发明上述主题的范围仅限于以下的实施例，凡基于本发明上述内容实现的技术均属于本发明的范围。
实施例1
向15mL反应管中，依次加入化合物1a、有机溶剂、催化剂、添加剂和化合物2a，在空气条件下将反应管密封，将其置于加热模块中升温搅拌反应。待反应结束后，冷却至室温，加入水淬灭反应，用乙酸乙酯萃取，有机相干燥后，抽滤，旋干，过硅胶柱分离(石油醚/乙酸乙酯＝3/1)得白色固体产物3a。
通过改变反应的有机溶剂、催化剂、添加剂、反应温度以及物料比等反应条件，得到一系列的结果，见表1。
表1不同条件下3a的合成a
实施例2
向15mL耐压管中，依次加入1a(30.2mg,0.2mmol)、1,4-二氧六环(2mL)、[RhCp*Cl2]2(8.7mg,0.014mmol)、CsOAc(3.8mg,0.02mmol)和2a(86.6mg,0.5mmol)，将反应管密封并置于40℃反应模块中搅拌反应4h。反应结束后，将反应体系冷却至室温，加入水淬灭反应，用乙酸乙酯萃取，有机相干燥后，抽滤，旋干，过硅胶柱分离(石油醚/乙酸乙酯＝3/1)得白色固体产物3a(50.5mg,66％)。1H NMR(CDCl3,600MHz):δ7.30(dd,J1＝7.8Hz,J2＝1.2Hz,1H),7.28-7.22(m,2H),7.13(d,J＝8.4Hz,1H),7.00-6.99(m,1H),6.97-6.93(m,2H),6.88(dd,J1＝7.8Hz,J2＝1.2Hz,1H),6.82(d,J＝7.2Hz,1H),6.75-6.72(m,2H),6.68(d,J＝7.8Hz,1H),3.12(s,3H),3.09(s,3H).13C{1H}NMR(CDCl3,150MHz):δ172.9,172.2,160.6,144.6,142.9,131.1,129.7,129.5,129.2,127.5,125.8,125.7,123.7,123.0,122.6,122.3,121.9,111.2,108.3,108.2,91.3,64.2,26.8,26.4.HRMS(ESI)m/z:[M+Na]+Calcdfor C24H18N2NaO3 405.1210；Found 405.1209.
实施例3
依照实施例2的方法和步骤a,b，通过改变反应物1和反应物2，合成出双吲哚酮[螺]苯并二氢呋喃类化合物3a-3hh，具体结果如下：
a反应条件:1(0.2mmol),2(0.5mmol),[RhCp*Cl2]2(0.014mmol),CsOAc(0.02mmol),1,4-二氧六环(2mL),40℃,4h,空气氛围；b分离收率。
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代表性产物表征数据如下：
1,1”-Diphenyldispiro[indoline-3,2'-benzofuran-3',3”-indoline]-2,2”-dione(3b)
1H NMR(CDCl3,400MHz):δ7.44-7.38(m,4H),7.37-7.32(m,3H),7.28-7.25(m,2H),7.21-7.15(m,5H),7.10(dd,J1＝7.6Hz,J2＝1.2Hz,1H),7.05-6.97(m,3H),6.85(dd,J1＝7.6Hz,J2＝1.2Hz,1H),6.77(td,J1＝7.6Hz,J2＝1.2Hz,1H),6.69(t,J＝8.8Hz,2H).13C{1H}NMR(CDCl3,150MHz):δ172.3,171.5,161.2,144.3,143.0,134.2,133.8,131.0,129.9,129.6,129.5,128.2,128.13,128.09,127.1,126.52,126.49,126.0,125.8,124.3,122.8,122.7,122.6,122.2,111.3,109.5,109.3,91.9,65.3.HRMS(ESI)m/z:[M+Na]+Calcd forC34H22N2NaO3 529.1523；Found 529.1516.
1,1”,5'-Trimethyldispiro[indoline-3,2'-benzofuran-3',3”-indoline]-2,2”-dione(3c)
1H NMR(CDCl3,600MHz):δ7.27-7.21(m,2H),7.08(dd,J1＝8.4Hz,J2＝1.2Hz,1H),7.02-7.01(m,2H),6.95(t,J＝7.8Hz,1H),6.83(d,J＝6.6Hz,1H),6.74-6.72(m,2H),6.69(s,1H),6.67(d,J＝7.8Hz,1H),3.12(s,3H),3.08(s,3H),2.23(s,3H).13C{1H}NMR(CDCl3,150MHz):δ173.0,172.3,158.5,144.6,142.9,132.1,131.0,130.1,129.5,129.1,127.7,125.8,125.7,124.2,123.0,122.3,121.8,110.7,108.2,108.1,91.3,64.2,26.7,26.3,20.9.HRMS(ESI)m/z:[M+Na]+Calcd for C25H20N2NaO3 419.1366；Found419.1361.
5'-Isopropyl-1,1”-dimethyldispiro[indoline-3,2'-benzofuran-3',3”-indoline]-2,2”-dione(3d)
1H NMR(CDCl3,600MHz):δ7.27-7.21(m,2H),7.14(dd,J1＝9.0Hz,J2＝1.8Hz,1H),7.04(d,J＝8.4Hz,1H),6.99(dd,J1＝7.8Hz,J2＝1.2Hz,1H),6.94(td,J1＝7.8Hz,J2＝1.2Hz,1H),6.79(dd,J1＝7.8Hz,J2＝1.2Hz,1H),6.74-6.71(m,3H),6.67(d,J＝8.4Hz,1H),3.12(s,3H),3.08(s,3H),2.83-2.79(m,1H),1.18-1.16(m,6H).13C{1H}NMR(CDCl3,150MHz):δ173.1,172.3,158.7,144.6,143.2,142.9,131.0,129.4,128.9,127.7,127.5,125.9,125.7,123.2,122.3,121.8,121.7,110.7,108.2,108.1,91.4,64.4,33.7,26.7,26.3,24.3,24.1.HRMS(ESI)m/z:[M+Na]+Calcd for C27H24N2NaO3 447.1679；Found477.1672.
5'-(tert-Butyl)-1,1”-dimethyldispiro[indoline-3,2'-benzofuran-3',3”-indoline]-2,2”-dione(3e)
1H NMR(CDCl3,400MHz):δ7.31(dd,J1＝8.4Hz,J2＝2.0Hz,1H),7.28-7.20(m,2H),7.05(d,J＝8.4Hz,1H),6.98-6.92(m,2H),6.85(d,J＝2.0Hz,1H),6.78-6.70(m,3H),6.67(d,J＝7.6Hz,1H),3.13(s,3H),3.08(s,3H),1.24(s,9H).13C{1H}NMR(CDCl3,100MHz):δ173.1,172.3,158.4,145.7,144.6,142.9,131.0,129.4,128.5,127.7,126.7,125.9,125.6,123.2,122.3,121.8,120.5,110.4,108.2,108.1,91.5,64.5,34.6,31.7,26.8,26.3.HRMS(ESI)m/z:[M+Na]+Calcd for C28H26N2NaO3 461.1836；Found 461.1831.
1,1”-Dimethyl-5'-phenyldispiro[indoline-3,2'-benzofuran-3',3”-indoline]-2,2”-dione(3f)
1H NMR(CDCl3,600MHz):δ7.53(dd,J1＝8.4Hz,J2＝1.8Hz,1H),7.48(d,J＝7.8Hz,2H),7.34(t,J＝7.8Hz,2H),7.27-7.23(m,3H),7.20(d,J＝8.4Hz,1H),7.08(d,J＝1.8Hz,1H),7.03(d,J＝7.2Hz,1H),6.95(t,J＝7.8Hz,1H),6.87(d,J＝7.2Hz,1H),6.77-6.73(m,2H),6.69(d,J＝7.8Hz,1H),3.14(s,3H),3.10(s,3H).13C{1H}NMR(CDCl3,100MHz):δ172.8,172.1,160.2,144.6,142.9,140.7,136.2,131.2,130.0,129.6,128.7,128.6,127.4,127.0,126.8,125.9,125.8,122.9,122.6,122.4,121.9,111.3,108.3,108.26,91.6,64.2,26.8,26.4.HRMS(ESI)m/z:[M+Na]+Calcd for C30H22N2NaO3 481.1523；Found 481.1524.
5'-Fluoro-1,1”-dimethyldispiro[indoline-3,2'-benzofuran-3',3”-indoline]-2,2”-dione(3g)
1H NMR(CDCl3,400MHz):δ7.30-7.27(m,1H),7.24(dd,J1＝8.0Hz,J2＝1.6Hz,1H),7.07-6.95(m,4H),6.81(dd,J1＝7.6Hz,J2＝1.2Hz,1H),6.76-6.72(m,2H),6.69(d,J＝7.6Hz,1H),6.63(dd,J1＝7.6Hz,J2＝2.8Hz,1H),3.12(s,3H),3.10(s,3H).13C{1H}NMR(CDCl3,150MHz):δ172.3,172.0,158.5(d,1JC-F＝239.9Hz),156.5,144.6,142.8,131.3,130.6(d,3JC-F＝8.6Hz),129.8,127.0,125.74,125.73,122.50,122.49,122.0,115.9(d,2JC-F＝25.1Hz),111.5(d,3JC-F＝8.0Hz),111.4(d,2JC-F＝25.4Hz),108.4,108.3,91.8,64.1,26.8,26.4.19F NMR(376MHz,CDCl3)δ:-121.13(td,J1＝9.4Hz,J2＝4.5Hz).HRMS(ESI)m/z:[M+H]+Calcd for C24H18FN2O3 401.1296；Found 401.1285.
5'-Chloro-1,1”-dimethyldispiro[indoline-3,2'-benzofuran-3',3”-indoline]-2,2”-dione(3h)
1H NMR(CDCl3,600MHz):δ7.30-7.24(m,3H),7.05(d,J＝9.0Hz,1H),7.01(dd,J1＝7.8Hz,J2＝1.2Hz,1H),6.98(td,J1＝7.8Hz,J2＝0.6Hz,1H),6.87(d,J＝1.8Hz,1H),6.82(dd,J1＝7.8Hz,J2＝1.2Hz,1H),6.76-6.74(m,2H),6.70(d,J＝8.4Hz,1H),3.12(s,3H),3.09(s,3H).13C{1H}NMR(CDCl3,150MHz):δ172.2,171.8,159.2,144.6,142.8,131.4,131.1,129.9,129.6,127.4,126.9,125.8,124.0,122.5,122.4,122.0,112.1,108.5,108.3,91.7,63.9,26.8,26.4.HRMS(ESI)m/z:[M+Na]+Calcd for C24H17ClN2NaO3439.0820；Found 439.0811.
5'-Bromo-1,1”-dimethyldispiro[indoline-3,2'-benzofuran-3',3”-indoline]-2,2”-dione(3i)
1H NMR(CDCl3,400MHz):δ7.40(dd,J1＝8.8Hz,J2＝2.0Hz,1H),7.30-7.23(m,2H),7.02-6.96(m,4H),6.83(d,J＝6.8Hz,1H),6.77-6.73(m,2H),6.70(d,J＝8.0Hz,1H),3.12(s,3H),3.10(s,3H).13C{1H}NMR(CDCl3,150MHz):δ172.2,171.8,159.7,144.6,142.8,132.5,131.5,131.3,129.9,126.9,126.8,125.8,122.5,122.3,122.0,114.6,112.7,108.5,108.3,91.7,63.9,26.8,26.4.HRMS(ESI)m/z:[M+Na]+Calcd for C24H17BrN2NaO3483.0315；Found 483.0309.
5'-Iodo-1,1”-dimethyldispiro[indoline-3,2'-benzofuran-3',3”-indoline]-2,2”-dione(3j)
1H NMR(CDCl3,400MHz):δ7.58(dd,J1＝8.8Hz,J2＝2.0Hz,1H),7.30-7.23(m,2H),7.16(d,J＝1.6Hz,1H),7.02-6.96(m,2H),6.92(d,J＝8.4Hz,1H),6.82(dd,J1＝7.6Hz,J2＝1.2Hz,1H),6.77-6.73(m,2H),6.69(d,J＝7.6Hz,1H),3.12(s,3H),3.09(s,3H).13C{1H}NMR(CDCl3,150MHz):δ172.2,171.8,160.6,144.6,142.8,138.5,132.4,132.0,131.4,129.9,126.9,125.8,122.5,122.3,122.0,113.4,108.5,108.3,91.6,84.4,63.7,26.8,26.4.HRMS(ESI)m/z:[M+Na]+Calcd for C24H17IN2NaO3 531.0176；Found 531.0165.
Ethyl 1,1”-dimethyl-2,2”-dioxodispiro[indoline-3,2'-benzofuran-3',3”-indoline]-5'-carboxylate(3k)
1H NMR(CDCl3,600MHz):δ8.08(dd,J1＝8.4Hz,J2＝1.8Hz,1H),7.59(d,J＝1.8Hz,1H),7.29-7.25(m,2H),7.16(d,J＝8.4Hz,1H),7.01-6.95(m,2H),6.83(dd,J1＝7.8Hz,J2＝0.6Hz,1H),6.76-6.74(m,2H),6.71(d,J＝7.8Hz,1H),4.33-4.25(m,2H),3.14(s,3H),3.10(s,3H),1.32(t,J＝7.2Hz,3H).13C{1H}NMR(CDCl3,150MHz):δ172.3,171.7,165.9,164.4,144.7,142.9,132.5,131.4,129.9,129.8,127.1,125.9,125.7,125.4,125.3,122.5,122.2,122.0,110.9,108.5,108.4,92.0,63.6,60.9,26.9,26.4,14.4.HRMS(ESI)m/z:[M+Na]+Calcd for C27H22N2NaO5 477.1421；Found 477.1405.
Methyl 3-(1,1”-dimethyl-2,2”-dioxodispiro[indoline-3,2'-benzofuran-3',3”-indolin]-5'-yl)-propanoate(3l)
1H NMR(CDCl3,400MHz):δ7.28-7.21(m,2H),7.12(dd,J1＝8.0Hz,J2＝1.6Hz,1H),7.04(d,J＝8.4Hz,1H),7.00-6.94(m,2H),6.81(d,J＝7.2Hz,1H),6.75-6.67(m,4H),3.60(s,3H),3.12(s,3H),3.09(s,3H),2.84(t,J＝8.0Hz,2H),2.58-2.53(m,2H).13C{1H}NMR(CDCl3,150MHz):δ173.4,172.9,172.2,159.1,144.6,142.8,134.8,131.1,129.5,129.45,127.6,125.8,125.7,123.5,122.9,122.3,121.9,111.0,108.3,108.2,91.4,64.2,51.6,35.9,30.5,26.7,26.3.HRMS(ESI)m/z:[M+Na]+Calcd for C28H24N2NaO5 491.1577；Found491.1567.
1,1”,6'-Trimethyldispiro[indoline-3,2'-benzofuran-3',3”-indoline]-2,2”-dione(3m)
1H NMR(CDCl3,400MHz):δ7.25-7.21(m,2H),6.99(dd,J1＝7.6Hz,J2＝1.2Hz,1H),6.95-6.91(m,2H),6.83(dd,J1＝7.6Hz,J2＝0.8Hz,1H),6.76-6.70(m,4H),6.67(d,J＝7.6Hz,1H),3.11(s,3H),3.08(s,3H),2.37(s,3H).13C{1H}NMR(CDCl3,100MHz):δ173.1,172.2,160.8,144.6,142.9,140.1,131.0,129.4,127.7,126.2,125.8,125.7,123.3,123.2,123.1,122.3,121.9,111.9,108.20,108.16,91.4,64.0,26.7,26.4,21.8.HRMS(ESI)m/z:[M+Na]+Calcd for C25H20N2NaO3419.1366；Found 419.1367.
6'-Isopropyl-1,1”-dimethyldispiro[indoline-3,2'-benzofuran-3',3”-indoline]-2,2”-dione(3n)
1H NMR(CDCl3,400MHz):δ7.25-7.21(m,2H),7.01-6.97(m,2H),6.93(t,J＝7.6Hz,1H),6.85-6.81(m,2H),6.78-6.70(m,3H),6.67(d,J＝8.0Hz,1H),3.11(s,3H),3.08(s,3H),2.96-2.89(m,1H),1.27-1.25(m,6H).13C{1H}NMR(CDCl3,100MHz):δ173.2,172.3,160.9,151.3,144.6,143.0,131.0,129.4,127.6,126.3,125.9,125.7,123.3,123.2,122.2,121.8,120.8,109.3,108.15,108.13,91.4,64.1,34.4,26.7,26.3,24.1,23.9.HRMS(ESI)m/z:[M+Na]+Calcd for C27H24N2NaO3447.1679；Found 447.1661.
1,1”,5',6'-Tetramethyldispiro[indoline-3,2'-benzofuran-3',3”-indoline]-2,2”-dione(3o)
1H NMR(CDCl3,600MHz):δ7.26-7.21(m,2H),7.01(dd,J1＝7.2Hz,J2＝0.6Hz,1H),6.96-6.93(m,2H),6.84(dd,J1＝7.2Hz,J2＝0.6Hz,1H),6.74-6.71(m,2H),6.67(d,J＝8.4Hz,1H),6.64(s,1H),3.11(s,3H),3.08(s,3H),2.26(s,3H),2.12(s,3H).13C{1H}NMR(CDCl3,150MHz):δ173.3,172.4,158.9,144.6,142.9,138.2,131.0,130.5,129.3,127.9,126.2,125.8,125.7,124.5,123.2,122.3,121.8,112.3,108.2,108.1,91.3,64.2,26.7,26.3,20.4,19.4.HRMS(ESI)m/z:[M+Na]+Calcd for C26H22N2NaO3433.1523；Found433.1512.
1,1”,6'-Trimethyldispiro[indoline-3,2'-benzofuran-3',3”-indoline]-2,2”-dione(3p)
1H NMR(CDCl3,400MHz):δ7.24-7.21(m,2H),7.10(d,J＝7.6Hz,1H),6.95-6.89(m,2H),6.86-6.81(m,2H),6.76-6.66(m,4H),3.11(s,3H),3.07(s,3H),2.34(s,3H).13C{1H}NMR(CDCl3,100MHz):δ173.0,172.2,159.1,144.5,143.1,131.1,131.0,129.4,128.4,127.4,125.9,125.6,123.5,122.4,122.2,121.9,121.4,121.0,108.2,91.1,64.5,26.7,26.4,15.4.HRMS(ESI)m/z:[M+Na]+Calcd for C25H20N2NaO3 419.1366；Found 419.1360.
1,1”-Dimethyl-7'-phenyldispiro[indoline-3,2'-benzofuran-3',3”-indoline]-2,2”-dione(3q)
1H NMR(CDCl3,600MHz):δ7.78-7.76(m,2H),7.45(dd,J1＝7.8Hz,J2＝1.2Hz,1H),7.39(t,J＝7.8Hz,2H),7.30-7.20(m,3H),7.04-7.02(m,2H),6.95(td,J1＝7.8Hz,J2＝0.6Hz,1H),6.85-6.82(m,2H),6.73-6.69(m,2H),6.67(d,J＝7.2Hz,1H),3.13(s,3H),3.09(s,3H).13C{1H}NMR(CDCl3,150MHz):δ172.9,172.3,157.9,144.7,142.8,136.6,131.0,130.0,129.7,129.5,128.7,128.4,127.7,127.4,125.88,125.86,125.4,123.05,123.02,122.6,122.4,121.8,108.3,108.1,91.3,64.3,26.8,26.4.HRMS(ESI)m/z:[M+Na]+Calcdfor C30H22N2NaO3 481.1523；Found 481.1520.
(3R,3a'S,3b'R,9'S,10b'S,12a'S)-1,1”,12a'-Trimethyl-2',3',3a',3b',4',5',10b',11',12',12a'-decahydro-1'H-dispiro[indoline-3,8'-cyclopenta[7,8]phenanthro[2,3-b]furan-9',3”-indoline]-1',2,2”-trione(3r)
1H NMR(CDCl3,400MHz):δ7.28-7.20(m,2H),7.06(d,J＝6.8Hz,1H),6.99-6.96(m,1H),6.86(s,1H),6.81-6.80(m,2H),6.73-6.66(m,3H),3.11(s,3H),3.08(s,3H),2.96-2.94(m,2H),2.52-2.45(m,1H),2.26-2.16(m,3H),2.11-1.97(m,2H),1.85-1.82(m,1H),1.64-1.50(m,3H),1.48-1.37(m,3H),0.87(s,3H).13C{1H}NMR(CDCl3,150MHz):δ173.2,172.5,158.7,144.7,142.7,138.3,134.1,131.0,129.4,128.0,126.7,125.9,125.8,122.8,122.3,121.8,120.5,111.0,108.2,108.1,91.4,64.3,50.4,48.0,44.3,38.2,35.9,31.5,30.2,26.7,26.4,26.3,26.0,21.6,13.9.HRMS(ESI)m/z:[M+Na]+Calcd forC36H34N2NaO4 581.2411；Found 581.2397.
(3S,3a'S,3b'R,9'R,10b'S,12a'S)-1,1”,12a'-Trimethyl-2',3',3a',3b',4',5',10b',11',12',12a'-decahydro-1'H-dispiro[indoline-3,8'-cyclopenta[7,8]phenanthro[2,3-b]furan-9',3”-indoline]-1',2,2”-trione(3r')
1H NMR(CDCl3,400MHz):δ7.26-7.21(m,2H),6.99-6.91(m,2H),6.86-6.82(m,2H),6.76-6.71(m,3H),6.76(d,J＝7.6Hz,1H),3.12(s,3H),3.09(s,3H),2.96-2.92(m,2H),2.53-2.46(m,1H),2.176-2.05(m,3H),2.03-1.98(m,2H),1.88-1.84(m,1H),1.65-1.56(m,3H),1.48-1.32(m,3H),0.90(s,3H).13C{1H}NMR(CDCl3,150MHz):δ173.2,172.4,158.7,144.6,142.9,138.3,134.1,131.0,129.4,127.8,126.7,125.8,125.7,123.2,122.3,121.8,120.3,111.1,108.2,108.1,91.3,64.2,50.6,48.0,44.2,37.8,35.9,31.5,29.9,29.7,26.7,26.6,26.3,25.7,21.6,13.8.HRMS(ESI)m/z:[M+Na]+Calcd forC36H34N2NaO4581.2411；Found 581.2397.
6,6”-Difluoro-1,1”-dimethyldispiro[indoline-3,2'-benzofuran-3',3”-indoline]-2,2”-dione(3s)
1H NMR(CDCl3,400MHz):δ7.31(td,J1＝8.0Hz,J2＝1.2Hz,1H),7.12(d,J＝8.0Hz,1H),6.97(td,J1＝7.6Hz,J2＝0.8Hz,1H),6.92(dd,J1＝8.4Hz,J2＝5.6Hz,1H),6.87(dd,J1＝7.6Hz,J2＝1.2Hz,1H),6.79-6.75(m,1H),6.67-6.62(m,1H),6.50(dd,J1＝8.8Hz,J2＝2.4Hz,1H),6.47-6.42(m,2H),3.12(s,3H),3.08(s,3H).13C{1H}NMR(CDCl3,150MHz):δ173.1,172.2,164.8(d,1JC-F＝248.3Hz),163.8(d,1JC-F＝245.7Hz),160.3,146.6(d,3JC-F＝12.2Hz),144.5(d,3JC-F＝13.1Hz),130.0,128.7,127.1(d,3JC-F＝10.1Hz),126.9(d,3JC-F＝9.0Hz),123.7,122.8,122.77(d,4JC-F＝3.0Hz),118.2(d,4JC-F＝2.6Hz),111.3,108.7(d,2JC-F＝23.1Hz),108.2(d,2JC-F＝23.4Hz),97.32(d,2JC-F＝27.0Hz),97.29(d,2JC-F＝27.5Hz),90.7,63.8,26.9,26.5.19F NMR(376MHz,CDCl3)δ:-106.89(td,J1＝9.0Hz,J2＝5.6Hz),-109.39(td,J1＝9.8Hz,J2＝5.3Hz).HRMS(ESI)m/z:[M+Na]+Calcd forC24H16F2N2NaO3 441.1021；Found 441.1004.
6,6”-Dichloro-1,1”-dimethyldispiro[indoline-3,2'-benzofuran-3',3”-indoline]-2,2”-dione(3t)
1H NMR(CDCl3,600MHz):δ7.32-7.30(m,1H),7.12(d,J＝7.8Hz,1H),6.98-6.94(m,2H),6.90(d,J＝7.8Hz,1H),6.86(d,J＝7.2Hz,1H),6.77-6.74(m,3H),6.71(s,1H),3.13(s,3H),3.08(s,3H).13C{1H}NMR(CDCl3,150MHz):δ172.6,171.8,160.3,145.9,144.0,137.3,135.6,130.1,128.5,126.61,126.58,125.6,123.6,122.9,122.4,122.0,121.1,111.4,109.3,109.2,90.6,63.8,26.9,26.5.HRMS(ESI)m/z:[M+Na]+Calcd forC24H16Cl2N2NaO3 473.0430；Found 473.0412.
6,6”-Dibromo-1,1”-dimethyldispiro[indoline-3,2'-benzofuran-3',3”-indoline]-2,2''-dione(3u)
1H NMR(CDCl3,400MHz):δ7.30(td,J1＝8.0Hz,J2＝1.6Hz,1H),7.12-7.09(m,2H),6.98-6.91(m,3H),6.87-6.83(m,3H),6.69(d,J＝8.0Hz,1H),3.11(s,3H),3.07(s,3H).13C{1H}NMR(CDCl3,150MHz):δ172.5,171.7,160.3,145.9,144.1,130.1,128.4,126.94,126.86,126.2,125.4,125.3,124.9,123.6,123.5,122.9,121.6,112.1,112.0,111.4,90.5,63.8,27.0,26.6.HRMS(ESI)m/z:[M+Na]+Calcd for C24H16Br2N2NaO3560.9420；Found560.9414.
1,1”,5,5”-Tetramethyldispiro[indoline-3,2'-benzofuran-3',3”-indoline]-2,2”-dione(3v)
1H NMR(CDCl3,600MHz):δ7.29(td,J1＝7.8Hz,J2＝1.2Hz,1H),7.13(d,J＝7.8Hz,1H),7.05(dd,J1＝7.8Hz,J2＝0.6Hz,1H),7.02(dd,J1＝7.8Hz,J2＝0.6Hz,1H),6.96(t,J＝7.8Hz,1H),6.90(dd,J1＝7.2Hz,J2＝1.2Hz,1H),6.82(d,J＝0.6Hz,1H),6.61-6.60(m,2H),6.56(d,J＝7.8Hz,1H),3.08(s,3H),3.06(s,3H),2.24(s,3H),2.06(s,3H).13C{1H}NMR(CDCl3,150MHz):δ172.9,172.3,160.7,142.2,140.4,131.7,131.2,131.1,129.60,129.58,129.3,127.7,126.8,126.5,123.8,122.8,122.6,111.1,108.0,107.8,91.5,64.4,26.8,26.4,21.0,20.9.HRMS(ESI)m/z:[M+Na]+Calcd for C26H22N2NaO3 433.1523；Found433.1517.
5,5”-Difluoro-1,1”-dimethyldispiro[indoline-3,2'-benzofuran-3',3”-indoline]-2,2”-dione(3w)
1H NMR(CDCl3,600MHz):δ7.33(td,J1＝7.8Hz,J2＝1.2Hz,1H),7.14(d,J＝7.8Hz,1H),7.02-6.97(m,3H),6.89(dd,J1＝7.8Hz,J2＝1.2Hz,1H),6.73(dd,J1＝7.8Hz,J2＝2.4Hz,1H),6.70(dd,J1＝8.4Hz,J2＝4.2Hz,1H),6.65(dd,J1＝9.0Hz,J2＝4.2Hz,1H),6.60(dd,J1＝8.4Hz,J2＝3.0Hz,1H),3.13(s,3H),3.08(s,3H).13C{1H}NMR(CDCl3,150MHz):δ172.3,171.6,160.3,158.9(d,1JC-F＝239.4Hz),158.3(d,1JC-F＝241.4Hz),140.6(d,4JC-F＝2.0Hz),138.9,130.1,128.42(d,3JC-F＝7.1Hz),128.40,124.1(d,3JC-F＝7.7Hz),123.7,123.0,117.6(d,2JC-F＝22.2Hz),116.2(d,2JC-F＝24.2Hz),113.7(d,2JC-F＝26.1Hz),113.6(d,2JC-F＝25.4Hz),111.5,109.1(d,3JC-F＝8.1Hz),109.0(d,3JC-F＝7.7Hz),90.9,64.4,26.9,26.6.19F NMR(565MHz,CDCl3)δ:-119.61(td,J1＝9.0Hz,J2＝4.0Hz),-119.97(td,J1＝9.6Hz,J2＝4.0Hz).HRMS(ESI)m/z:[M+Na]+Calcd for C24H16F2N2NaO3 441.1021；Found441.1017.
5,5”-Dibromo-1,1”-dimethyldispiro[indoline-3,2'-benzofuran-3',3”-indoline]-2,2''-dione(3x)
1H NMR(CDCl3,600MHz):δ7.43(dd,J1＝8.4Hz,J2＝1.8Hz,1H),7.39(dd,J1＝8.4Hz,J2＝1.8Hz,1H),7.34(td,J1＝7.8Hz,J2＝1.2Hz,1H),7.14(d,J＝8.4Hz,1H),7.09(d,J＝1.8Hz,1H),7.01-6.99(m,1H),6.94(d,J＝1.8Hz,1H),6.90(dd,J1＝7.2Hz,J2＝1.2Hz,1H),6.65(d,J＝8.4Hz,1H),6.59(d,J＝8.4Hz,1H),3.11(s,3H),3.06(s,3H).13C{1H}NMR(CDCl3,150MHz):δ172.1,171.4,160.3,143.5,141.7,134.0,132.6,130.3,129.04,128.98,128.7,127.8,124.4,123.9,123.1,115.1,114.5,111.4,110.0,109.8,90.8,64.4,26.9,26.5.HRMS(ESI)m/z:[M+Na]+Calcd for C24H16Br2N2NaO3 560.9420；Found 560.9408.
5,5”-Diiodo-1,1”-dimethyldispiro[indoline-3,2'-benzofuran-3',3”-indoline]-2,2”-dione(3y)
1H NMR(CDCl3,600MHz):δ7.62(dd,J1＝7.8Hz,J2＝1.8Hz,1H),7.56(dd,J1＝8.4Hz,J2＝1.8Hz,1H),7.34(td,J1＝8.4Hz,J2＝1.2Hz,1H),7.26-7.25(m,1H),7.15-7.11(m,2H),7.01-6.99(m,1H),6.91(dd,J1＝7.8Hz,J2＝1.2Hz,1H),6.54(d,J＝7.8Hz,1H),6.48(d,J＝7.8Hz,1H),3.09(s,3H),3.05(s,3H).13C{1H}NMR(CDCl3,150MHz):δ172.0,171.3,160.4,144.2,142.3,139.8,138.6,134.8,134.3,130.3,129.5,127.6,124.6,124.0,123.1,111.4,110.5,110.3,90.8,84.5,84.0,64.3,26.9,26.5.HRMS(ESI)m/z:[M+Na]+Calcd for C24H16I2N2NaO3 656.9142；Found 656.9129.
1,1”,5,5',5”-Pentamethyldispiro[indoline-3,2'-benzofuran-3',3”-indoline]-2,2”-dione(3z)
1H NMR(CDCl3,600MHz):δ7.08(dd,J1＝8.4Hz,J2＝1.2Hz,1H),7.05(d,J＝7.8Hz,1H),7.03-7.00(m,2H),6.86(s,1H),6.71(s,1H),6.61-6.60(m,2H),6.55(d,J＝7.8Hz,1H),3.08(s,3H),3.06(s,3H),2.26(s,3H),2.25(s,3H),2.06(s,3H).13C{1H}NMR(CDCl3,150MHz):δ173.0,172.5,158.5,142.3,140.3,132.0,131.7,131.1,131.0,130.0,129.5,129.1,128.0,126.8,126.6,124.3,122.8,110.6,108.0,107.7,91.5,64.4,26.7,26.3,21.0,20.9,20.8.HRMS(ESI)m/z:[M+Na]+Calcd for C27H24N2NaO3 447.1679；Found447.1666.
1,1”,7,7”-Tetramethyldispiro[indoline-3,2'-benzofuran-3',3”-indoline]-2,2”-dione(3aa)
1H NMR(CDCl3,400MHz):δ7.29-7.25(m,1H),7.11(d,J＝8.0Hz,1H),6.97-6.92(m,3H),6.88-6.79(m,3H),6.68(d,J＝6.8Hz,1H),6.60(t,J＝7.6Hz,1H),3.40(s,3H),3.37(s,3H),2.47(s,3H),2.45(s,3H).13C{1H}NMR(CDCl3,100MHz):δ173.7,173.3,160.6,142.4,140.5,134.8,133.1,129.9,129.5,128.2,124.0,123.8,123.6,123.4,122.5,122.1,121.7,119.7,119.6,111.1,90.9,63.9,30.1,29.8,19.1,19.0.HRMS(ESI)m/z:[M+Na]+Calcd for C26H22N2NaO3 433.1523；Found 433.1516.
7,7”-Dibromo-1,1”-dimethyldispiro[indoline-3,2'-benzofuran-3',3”-indoline]-2,2''-dione(3bb)
1H NMR(CDCl3,400MHz):δ7.37(dd,J1＝8.4Hz,J2＝0.8Hz,2H),7.32(td,J1＝8.0Hz,J2＝1.2Hz,1H),7.13(d,J＝8.0Hz,1H),6.98(td,J1＝7.6Hz,J2＝1.2Hz,1H),6.91-6.88(m,2H),6.82-6.75(m,2H),6.62-6.58(m,1H),3.53(s,3H),3.49(s,3H).13C{1H}NMR(CDCl3,150MHz):δ173.1,172.6,160.4,142.0,140.1,136.9,135.3,130.3,130.1,128.6,125.5,125.1,124.8,123.8,123.4,122.98,122.96,111.3,102.5,102.3,90.6,64.3,30.4,30.0.HRMS(ESI)m/z:[M+Na]+Calcd for C24H16Br2N2NaO3 560.9420；Found 560.9402.
1,1”-Diethyldispiro[indoline-3,2'-benzofuran-3',3”-indoline]-2,2”-dione(3cc)
1H NMR(CDCl3,600MHz):δ7.30(td,J1＝7.8Hz,J2＝1.2Hz,1H),7.25-7.19(m,2H),7.15(d,J＝7.8Hz,1H),6.97(t,J＝7.8Hz,1H),6.93-6.90(m,3H),6.74-6.67(m,4H),3.85-3.74(m,2H),3.51-3.46(m,2H),1.15(t,J＝7.2Hz,3H),1.00(t,J＝7.2Hz,3H).13C{1H}NMR(CDCl3,150MHz):δ172.4,171.8,161.0,143.6,142.0,130.9,129.7,129.4,128.6,127.7,125.9,125.7,123.9,123.1,122.6,122.0,121.5,111.1,108.1,108.0,91.6,64.5,34.9,34.7,12.3,12.2.HRMS(ESI)m/z:[M+Na]+Calcd for C26H22N2NaO3 433.1523；Found433.1530.
1,1”-Dibenzyldispiro[indoline-3,2'-benzofuran-3',3”-indoline]-2,2”-dione(3dd)
1H NMR(CDCl3,600MHz):δ7.35-7.32(m,1H),7.19(d,J＝7.8Hz,1H),7.13(t,J＝7.8Hz,2H),7.10-7.05(m,6H),7.02-6.96(m,5H),6.91(t,J＝7.8Hz,1H),6.77-6.75(m,3H),6.68(t,J＝7.8Hz,1H),6.53(t,J＝7.8Hz,2H),5.23(d,J＝16.2Hz,1H),5.13(d,J＝15.6Hz,1H),4.50(d,J＝15.6Hz,1H),4.44(d,J＝15.6Hz,1H).13C{1H}NMR(CDCl3,150MHz):δ173.1,172.3,160.9,144.0,142.1,135.1,135.0,131.0,129.9,129.6,129.0,128.62,128.59,127.5,127.4,127.32,127.27,126.6,125.92,125.87,124.0,122.82,122.77,122.4,122.0,111.3,109.6,109.5,91.6,64.5,44.1,43.9.HRMS(ESI)m/z:[M+Na]+Calcdfor C36H26N2NaO3 557.1836；Found 557.1824.
1,1”-Bis(4-methylbenzyl)dispiro[indoline-3,2'-benzofuran-3',3”-indoline]-2,2”-dione(3ee)
1H NMR(CDCl3,600MHz):δ7.34(td,J1＝8.4Hz,J2＝1.8Hz,1H),7.19(d,J＝8.4Hz,1H),7.15-7.12(m,2H),7.02-6.96(m,5H),6.90(td,J1＝7.8Hz,J2＝1.2Hz,1H),6.86(d,J＝7.8Hz,2H),6.80(d,J＝7.8Hz,2H),6.77(dd,J1＝7.8Hz,J2＝0.6Hz,1H),6.68(td,J1＝7.8Hz,J2＝1.2Hz,1H),6.65(d,J＝7.8Hz,2H),6.54-6.53(m,2H),5.18(d,J＝16.2Hz,1H),5.09(d,J＝15.6Hz,1H),4.49(d,J＝16.2Hz,1H),4.41(d,J＝16.2Hz,1H),2.20(s,3H),2.19(s,3H).13C{1H}NMR(CDCl3,150MHz):δ173.1,172.3,160.9,144.1,142.2,136.9,136.8,132.0,131.9,130.9,129.8,129.5,129.22,129.20,128.97,127.6,127.3,126.5,125.9,125.8,124.0,122.8,122.7,122.3,121.9,111.2,109.6,109.5,91.6,64.5,43.9,43.7,21.0.HRMS(ESI)m/z:[M+Na]+Calcd for C38H30N2NaO3 585.2149；Found 585.2137.
1,1”-Bis(3-methylbenzyl)dispiro[indoline-3,2'-benzofuran-3',3”-indoline]-2,2”-dione(3ff)
1H NMR(CDCl3,600MHz):δ7.34(td,J1＝8.4Hz,J2＝1.8Hz,1H),7.19(d,J＝8.4Hz,1H),7.14-7.11(m,2H),7.06(s,1H),7.02-6.96(m,4H),6.93-6.90(m,4H),6.87(t,J＝7.2Hz,1H),6.80-6.78(m,2H),6.68-6.66(m,1H),6.56(d,J＝7.8Hz,2H),6.51(d,J＝7.2Hz,1H),5.22(d,J＝15.6Hz,1H),5.17(d,J＝15.6Hz,1H),4.46(d,J＝15.6Hz,1H),4.36(d,J＝15.6Hz,1H),2.11(s,3H),2.08(s,3H).13C{1H}NMR(CDCl3,100MHz):δ173.1,172.3,160.8,144.1,142.1,138.5,138.3,135.1,135.0,131.1,129.8,129.5,129.2,128.5,128.4,128.2,128.16,128.13,127.6,127.5,125.87,125.86,124.4,123.9,123.7,122.8,122.7,122.4,122.0,111.3,109.6,109.5,91.5,64.3,44.2,44.1,21.2,21.1.HRMS(ESI)m/z:[M+Na]+Calcd for C38H30N2NaO3 585.2149；Found 585.2146.
1,1”-Bis(2-methylbenzyl)dispiro[indoline-3,2'-benzofuran-3',3”-indoline]-2,2”-dione(3gg)
1H NMR(CDCl3,400MHz):δ7.37-7.32(m,1H),7.21-7.03(m,5H),7.02-6.94(m,6H),6.86-6.84(m,1H),6.79-6.75(m,1H),6.59-6.52(m,3H),6.47(d,J＝7.6Hz,1H),6.41(d,J＝8.0Hz,1H),6.04(d,J＝7.6Hz,1H),5.17(d,J＝16.8Hz,1H),4.98(d,J＝16.8Hz,1H),4.56-4.50(m,2H),2.32(s,3H),2.30(s,3H).13C{1H}NMR(CDCl3,100MHz):δ173.2,172.4,160.9,144.3,142.5,135.15,135.07,132.5,132.4,131.2,130.25,130.15,129.8,129.6,129.0,127.4,127.0,126.3,126.1,126.0,125.91,125.88,125.0,124.0,122.9,122.8,122.5,122.1,111.3,109.7,109.6,91.7,64.6,41.9,41.7,19.24,19.18.HRMS(ESI)m/z:[M+Na]+Calcd for C38H30N2NaO3 585.2149；Found 585.2134.
1,1”-Diphenethyldispiro[indoline-3,2'-benzofuran-3',3”-indoline]-2,2”-dione(3hh)
1H NMR(CDCl3,400MHz):δ7.30(td,J1＝8.0Hz,J2＝1.6Hz,1H),7.26-7.13(m,11H),7.02-6.90(m,5H),6.82-6.79(m,2H),6.72(td,J1＝7.6Hz,J2＝0.4Hz,1H),6.54-6.48(m,2H),4.03-3.95(m,2H),3.75-3.67(m,1H),3.64-3.56(m,1H),2.98-2.91(m,1H),2.85-2.77(m,2H),2.73-2.66(m,1H).13C{1H}NMR(CDCl3,100MHz):δ172.7,172.2,160.7,144.0,142.1,138.5,138.2,131.0,129.7,129.4,129.1,128.9,128.8,128.69,128.67,127.6,126.62,126.59,126.1,125.9,123.8,122.8,122.6,122.1,121.7,111.2,108.5,108.2,91.2,64.3,42.07,42.05,33.9,33.8.HRMS(ESI)m/z:[M+Na]+Calcd for C38H30N2NaO3585.2149；Found 585.2136.
实施例4
本发明所合成的产物双吲哚酮[螺]苯并二氢呋喃类化合物3进行一系列反应，从而合成进一步的衍生物。例如：
向15mL耐压管中，依次加入3a(114.6mg,0.3mmol)、四氢呋喃(4.6mL)和LiAlH4(45.5mg,1.2mmol)，在氩气氛围中将反应管密封，并于80℃反应5h。反应结束后，加入水淬灭反应，乙酸乙酯萃取(10mL×3)。合并有机相，无水硫酸钠干燥，抽滤，旋干，过硅胶柱分离(石油醚/乙酸乙酯＝30/1)得黄色固体产物4(70.3mg,63％)。1H NMR(CDCl3,600MHz):δ7.35-7.32(m,1H),7.12-7.11(m,1H),7.08(t,J＝7.8Hz,1H),7.04-7.02(m,3H),6.93(d,J＝7.2Hz,1H),6.73(d,J＝7.2Hz,1H),6.55-6.50(m,2H),6.33(d,J＝8.4Hz,1H),6.26(d,J＝7.8Hz,1H),5.81(s,1H),5.76(s,1H),2.93(s,3H),2.85(s,3H).13C{1H}NMR(CDCl3,150MHz):δ159.6,150.3,149.8,130.6,129.8,129.3,128.7,127.6,125.7,125.6,125.4,123.3,121.8,117.3,117.2,111.1,110.0,108.6,106.3,106.2,105.7,71.0,32.1,31.9.HRMS(ESI)m/z:[M+Na]+Calcd for C24H20N2NaO2 391.1417；Found 391.1411.
向15mL耐压管中，依次加入3a(76.4mg,0.2mmol)、THF(2mL)和甲基溴化镁(13.3μL3mol/L乙醚溶液,0.4mmol)，将反应管密封，于25℃反应3h。反应结束后，加入饱和食盐水淬灭反应，乙酸乙酯萃取(10mL×3)。合并有机相，无水硫酸钠干燥，抽滤，旋干，过硅胶柱分离(石油醚/乙酸乙酯＝30/1)得黄色固体产物5(40.4mg,51％)。1H NMR(CDCl3,600MHz):δ7.34-7.31(m,1H),7.10-7.08(m,1H),7.04(d,J＝7.8Hz,1H),7.00-6.92(m,3H),6.72(d,J＝7.2Hz,1H),6.51-6.50(m,1H),6.38-6.33(m,2H),6.12(d,J＝7.8Hz,1H),6.06(d,J＝7.2Hz,1H),2.77(s,3H),2.70(s,3H),1.48(s,3H),1.35(s,3H).13C{1H}NMR(CDCl3,100MHz):δ160.7,149.0,130.1,129.7,129.1,128.1,126.8,126.2,125.4,125.1,123.6,121.2,116.07,116.06,110.7,109.7,109.3,108.0,104.6,104.1,74.3,27.6,27.4,19.4,18.3.HRMS(ESI)m/z:[M+H]+Calcd for C26H25N2O2 397.1911；Found 397.1901.
向15mL耐压管中，依次加入3a(76.5mg,0.2mmol)、THF(2mL)和BH3·Me2S(0.5mL,2.0mol/L四氢呋喃溶液,1.0mmol)，在空气条件下将反应管密封，室温条件下反应16h。反应结束后，加入水淬灭反应，乙酸乙酯萃取(10mL×3)。合并有机相，无水硫酸钠干燥，抽滤，旋干，过硅胶柱分离(石油醚/乙酸乙酯＝10/1)得黄色油状产物6(33.8mg,48％)。1H NMR(CDCl3,400MHz):δ7.99(d,J＝8.0Hz,1H),7.80-7.78(m,1H),7.59(s,1H),7.43(d,J＝8.0Hz,1H),7.36(d,J＝8.0Hz,1H),7.31(d,J＝8.4Hz,1H),7.28-7.23(m,2H),7.21-7.16(m,1H),7.14-7.08(m,2H),7.07-7.03(m,1H),7.02-6.99(m,1H),6.85(s,1H),3.81(s,3H),3.74(s,3H).13C{1H}NMR(CDCl3,150MHz):δ156.0,137.0,134.9,134.3,130.1,129.5,127.1,126.5,124.8,122.21,122.20,121.6,120.8,120.5,119.7,119.0,118.5,117.6,115.9,111.1,109.4,109.37,32.9,32.8.HRMS(ESI)m/z:[M+Na]+Calcd for C24H20N2NaO375.1468；Found 375.1459.
以上实施例描述了本发明的基本原理、主要特征及优点。本行业的技术人员应该了解，本发明不受上述实施例的限制，上述实施例和说明书中描述的只是说明本发明的原理，在不脱离本发明原理的范围下，本发明还会有各种变化和改进，这些变化和改进均落入本发明保护的范围内。
Claims (8)
1.双吲哚酮[螺]苯并二氢呋喃类化合物，其特征在于，结构通式为：
其中，R1为氢、C1-6链状烷基、C1-4取代烷基、C1-4烷氧基、苯基、取代苯基、C1-4烷氧羰基或卤素，R1为一元或二元取代，R2为C1-6链状烷基或卤素，R3为C1-4烷基、C1-4取代烷基、苯基或取代苯基，上述取代烷基的取代基为苯基、取代苯基或C1-4烷氧羰基，上述取代苯基苯环上的取代基为C1-4烷基。
2.如权利要求1所述双吲哚酮[螺]苯并二氢呋喃类化合物的合成方法，其特征在于，包括如下操作：以N-苯氧基乙酰胺类化合物1和重氮吲哚酮类化合物2为原料，在铑(III)催化剂和添加剂存在下，有机溶剂中升温反应，得到双吲哚酮[螺]苯并二氢呋喃类化合物3；反应方程式为：
其中，R1为氢、C1-6链状烷基、C1-4取代烷基、C1-4烷氧基、苯基、取代苯基、C1-4烷氧羰基或卤素，R1为一元或二元取代，R2为C1-6链状烷基或卤素，R3为C1-4烷基、C1-4取代烷基、苯基或取代苯基，上述取代烷基的取代基为苯基、取代苯基或C1-4烷氧羰基，上述取代苯基苯环上的取代基为C1-4烷基。
3.根据权利要求2所述双吲哚酮[螺]苯并二氢呋喃类化合物的合成方法，其特征在于：有机溶剂选自1,2-二氯乙烷、四氢呋喃或1,4-二氧六环。
4.根据权利要求2所述双吲哚酮[螺]苯并二氢呋喃类化合物的合成方法，其特征在于：所述铑(III)催化剂为[RhCp*Cl2]2。
5.根据权利要求2所述双吲哚酮[螺]苯并二氢呋喃类化合物的合成方法，其特征在于：所述添加剂为醋酸钠、醋酸铯或1-金刚烷甲酸。
6.根据权利要求2所述双吲哚酮[螺]苯并二氢呋喃类化合物的合成方法，其特征在于：所述N-苯氧基乙酰胺类化合物1、重氮吲哚酮类化合物2、铑(III)催化剂与添加剂摩尔比为1-1.2:1-3:0.05-0.08:0.05-1。
7.根据权利要求2所述双吲哚酮[螺]苯并二氢呋喃类化合物的合成方法，其特征在于：反应温度为30-60℃。
8.根据权利要求2-7任意一项所述双吲哚酮[螺]苯并二氢呋喃类化合物的合成方法，其特征在于：反应在空气氛围下进行。
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