具体实施方式

依据实施例对本发明进一步说明，但本发明不仅限于这些实施例。

实施例1

制备化合物1名称为：(2R,3R,4S,5R,7S,8S,9S,11S,12S,13S,14S,15R)-14-苯甲酰氧基-15-羟基-11,12-环氧-5,7-二异丁酰氧基-2,3,8,9-四乙酰氧基-假白榄烷-6(17)-烯：

将ES3为14β-苯甲酰氧基-15β-羟基-5α,7β-二异丁酰氧基-2α,3β,8α,9α-四乙酰氧基-假白榄烷-6(17),11E-二烯81mg,0.10mmol溶于二氯甲烷2mL，加入间氯过氧苯甲酸41mg,0.20mmol，85％，室温搅拌反应6天，饱和硫代硫酸钠淬灭，乙酸乙酯萃取，依次用饱和碳酸氢钠、水、饱和氯化钠洗涤，无水硫酸钠干燥，有机相乙酸乙酯浓缩后，再通过硅胶柱200-300目梯度洗脱，洗脱剂为体积比3:1的石油醚和乙酸乙酯，即得白色固体化合物1名称为：(2R,3R,4S,5R,7S,8S,9S,11S,12S,13S,14S,15R)-14-苯甲酰氧基-15-羟基-11,12-环氧-5,7-二异丁酰氧基-2,3,8,9-四乙酰氧基-假白榄烷-6(17)-烯40mg,产率48％；

质谱及核磁数据为：ESI(+)MS m/z 853.3832[M+Na]⁺，分子式为C₄₃H₅₈O₁₆.¹H NMR(400MHz,CDCl₃)δppm:3.68(1H,d,J＝16.5Hz,H-1α),2.18(1H,d,J＝16.5Hz,H-1β),5.31(1H,d,J＝3.2Hz,H-3),2.94(1H,dd,J＝11.0,3.3Hz,H-4),6.15(1H,d,J＝11.0Hz,H-5),5.36(1H,d,J＝6.7Hz,H-7),5.60(1H,d,J＝5.6Hz,H-8),5.24(1H,d,J＝7.7Hz,H-9),3.02(1H,d,J＝1.8Hz,H-11),3.25(1H,dd,J＝7.9,1.9Hz,H-12),1.47(1H,m,H-13),5.59(1H,brs,H-14),1.53(3H,s,H₃-16),5.61(1H,s,H-17α),5.54(1H,s,H-17β),1.03(3H,s,H₃-18),0.57(3H,s,H₃-19),1.24(3H,d,J＝7.2Hz,H₃-20),15-OH:3.98(1H,s)；2-OAc:2.38(3H,s)；3-OAc:2.23(3H,s)；8-OAc:1.67(3H,s)；9-OAc:2.03(3H,s)；5-OiBu:2.30(1H,m,H-2'),1.02(3H,d,J＝7.0Hz,H-3'),1.00(3H,d,J＝7.0Hz,H-4')；7-OiBu:2.40(1H,m,H-2'),1.02(3H,d,J＝6.9Hz,H-3'),1.12(3H,d,J＝7.1Hz,H-4')；14-OBz:7.97(2H,d,J＝7.7Hz,H-3',7'),7.43(2H,t,J＝7.7Hz,H-4',6'),7.56(1H,t,J＝7.6Hz,H-5').¹³C NMR(100MHz,CDCl₃)δppm:50.6(C-1),86.9(C-2),79.9(C-3),50.9(C-4),66.0(C-5),141.9(C-6),72.9(C-7),68.9(C-8),78.8(C-9),39.0(C-10),60.3(C-11),59.6(C-12),43.2(C-13),74.9(C-14),82.5(C-15),19.8(C-16),125.6(C-17),25.3(C-18),16.4(C-19),13.7(C-20),2-OAc:169.8(CO),21.3(C-2')；3-OAc:169.9(CO),21.3(C-2')；8-OAc:170.1(CO),22.7(C-2')；9-OAc:169.9(CO),21.4(C-2')；5-OiBu:173.9(CO),34.1(C-2'),18.6(C-3'),18.8(C-4')；7-OiBu:176.0(CO),33.8(C-2'),19.0(C-3'),19.3(C-4')；14-OBz:165.1(CO),130.2(C-2'),129.7(C-3',7'),128.8(C-4',6'),133.6(C-5')。

实施例2

制备化合物2名称为：(2R,3R,5S,7S,8S,9S,13S,14S)-14-苯甲酰氧基-5,7-二异丁酰氧基-2,3,8,9-四乙酰氧基-假白榄烷-6(17),4E,11E-三烯：

将ES3为14β-苯甲酰氧基-15β-羟基-5α,7β-二异丁酰氧基-2α,3β,8α,9α-四乙酰氧基-假白榄烷-6(17),11E-二烯46mg,0.056mmol溶于甲苯3mL，加入二氯亚砜0.1mL，氮气保护，加热至70℃反应搅拌反应1小时，加入饱和碳酸氢钠淬灭，乙酸乙酯萃取，依次用水、饱和氯化钠洗，无水硫酸钠干燥，有机相乙酸乙酯浓缩后，再通过硅胶柱200-300目梯度洗脱，洗脱剂为体积比5:1的石油醚和乙酸乙酯，即得无色晶体2名称为：(2R,3R,5S,7S,8S,9S,13S,14S)-14-苯甲酰氧基-5,7-二异丁酰氧基-2,3,8,9-四乙酰氧基-假白榄烷-6(17),4E,11E-三烯40mg,产率89％；

质谱及核磁数据为：ESI(+)MS m/z 819.3570[M+Na]⁺，分子式为C₄₃H₅₆O₁₄.¹H NMR(400MHz,CDCl₃)δppm:3.13(1H,d,J＝16.8Hz,H-1α),3.00(1H,d,J＝16.8Hz,H-1β),5.76(1H,s,H-3),5.23(1H,br s,H-5),5.81(1H,s,H-7),5.24(1H,s,H-8),5.04(1H,s,H-9),5.91(1H,s,H-11),5.91(1H,s,H-12),2.71(1H,m,H-13),5.96(1H,br s,H-14),1.45(3H,s,H₃-16),5.08(1H,s,H-17α),4.73(1H,s,H-17β),0.95(3H,s,H₃-18),1.45(3H,s,H₃-19),1.14(3H,d,J＝7.0Hz,H₃-20)；2-OAc:2.03(3H,s)；3-OAc:1.94(3H,s)；8-OAc:2.00(3H,s)；9-OAc:2.00(3H,s)；5-OiBu:1.63(1H,m,H-2'),0.54(3H,d,J＝7.0Hz,H-3'),0.69(3H,d,J＝7.1Hz,H-4')；7-OiBu:2.57(1H,m,H-2'),1.18(3H,d,J＝7.0Hz,H-3'),1.22(3H,d,J＝7.1Hz,H-4')；14-OBz:7.99(2H,d,J＝7.6Hz,H-3',7'),7.43(2H,t,J＝7.6Hz,H-4',6'),7.53(1H,t,J＝7.5Hz,H-5').¹³C NMR(100MHz,CDCl₃)δppm:48.2(C-1),88.0(C-2),84.5(C-3),147.6(C-4),78.4(C-5),144.6(C-6),67.0(C-7),71.4(C-8),80.0(C-9),40.4(C-10),136.7(C-11),129.2(C-12),40.6(C-13),67.7(C-14),147.6(C-15),20.0(C-16),111.2(C-17),26.6(C-18),24.3(C-19),22.1(C-20)；2-OAc:170.8(CO),22.3(C-2')；3-OAc:169.4(CO),21.1(C-2')；8-OAc:170.1(CO),21.0(C-2')；9-OAc:170.0(CO),20.9(C-2')；5-OiBu:174.1(CO),33.7(C-2'),18.3(C-3'),18.6(C-4')；7-OiBu:175.4(CO),34.2(C-2'),18.7(C-3'),19.3(C-4')；14-OBz:165.8(CO),128.1(C-2'),130.2(C-3',7'),128.9(C-4',6'),133.5(C-5')。

实施例3

制备化合物3名称为：14β-苯甲酰氧基-2α,7β,8α,9α,15β-五羟基-5α-异丁酰氧基-3β-乙酰氧基-假白榄烷-6(17),11E-二烯

将ES3为14β-苯甲酰氧基-15β-羟基-5α,7β-二异丁酰氧基-2α,3β,8α,9α-四乙酰氧基-假白榄烷-6(17),11E-二烯842mg,1.03mmol溶于甲醇10mL，加入1,8-二氮杂二环十一碳-7-烯318mg,2.09mmol，室温搅拌3.5小时，加入盐酸1mmol/L,3mL淬灭，乙酸乙酯萃取3次，依次用水、饱和碳酸氢钠、饱和氯化钠洗涤，无水硫酸钠干燥，有机相乙酸乙酯浓缩后，再通过硅胶柱200-300目梯度洗脱，洗脱剂为体积比1:2的石油醚和乙酸乙酯，即得白色固体化合物3名称为14β-苯甲酰氧基-2α,7β,8α,9α,15β-五羟基-5α-异丁酰氧基-3β-乙酰氧基-假白榄烷-6(17),11E-二烯400mg,产率63％；

质谱及核磁数据为：ESI(+)MS m/z 641.2943[M+Na]⁺，分子式为C₃₃H₄₆O₁₁.¹H NMR(400MHz,CDCl₃)δppm:2.15(1H,d,J＝14.8Hz,H-1α),2.07(1H,d,J＝14.8Hz,H-1β),5.10(1H,d,J＝4.6Hz,H-3),3.03(1H,m,H-4),5.68(1H,d,J＝2.9Hz,H-5),4.38(1H,s,H-7),4.08(1H,s,H-8),3.74(1H,s,H-9),5.86(1H,d,J＝16.0Hz,H-11),5.70(1H,dd,J＝16.0,6.2Hz,H-12),2.77(1H,m,H-13),5.35(1H,s,H-14),1.31(3H,s,H₃-16),5.13(1H,s,H-17α),4.64(1H,s,H-17β),1.08(3H,s,H₃-18),1.22(3H,s,H₃-19),1.07(3H,d,J＝6.2Hz,H₃-20),2-OH:3.47(1H,s)；7-OH:4.08(1H,s)；8-OH:4.08(1H,s)；9-OH:4.09(1H,s)；15-OH:4.09(1H,s)；3-OAc:2.05(3H,s)；5-OiBu:2.09(1H,m,H-2'),0.67(3H,d,J＝7.0Hz,H-3'),0.82(3H,d,J＝7.0Hz,H-4')；14-OBz:7.95(2H,d,J＝7.5Hz,H-3',7'),7.43(2H,t,J＝7.7Hz,H-4',6'),7.53(1H,t,J＝7.4Hz,H-5').¹³C NMR(100MHz,CDCl₃)δppm:54.3(C-1),84.0(C-2),84.1(C-3),44.1(C-4),72.5(C-5),148.0(C-6),67.6(C-7),70.7(C-8),84.7(C-9),40.5(C-10),134.9(C-11),130.1(C-12),37.7(C-13),79.5(C-14),78.5(C-15),24.6(C-16),107.5(C-17),27.6(C-18),14.0(C-19),23.8(C-20),3-OAc:171.4(CO),21.5(C-2')；5-OiBu:174.9(CO),34.1(C-2'),18.2(C-3'),18.4(C-4')；14-OBz:166.4(CO),129.8(C-2'),130.0(C-3',7'),128.8(C-4',6'),133.3(C-5')。

实施例4

制备化合物4名称为：14β-苯甲酰氧基-2α,9α,15β-三羟基-5α-异丁酰氧基-3β,7β,8α-三乙酰氧基-假白榄烷-6(17),11E-二烯：

将化合物3名称为14β-苯甲酰氧基-2α,7β,8α,9α,15β-五羟基-5α-异丁酰氧基-3β-乙酰氧基-假白榄烷-6(17),11E-二烯22mg,0.035mmol溶于二氯甲烷2mL,加入三乙胺0.05mL,0.35mmol，乙酸酐10mg,0.098mmol，室温搅拌10小时，加入饱和碳酸氢钠淬灭，乙酸乙酯萃取，依次用水、饱和碳酸氢钠、饱和氯化钠洗涤，无水硫酸钠干燥，有机相乙酸乙酯浓缩后，再通过硅胶柱200-300目梯度洗脱，洗脱剂为体积比1.5:1的石油醚和乙酸乙酯，即得白色固体化合物4名称为：14β-苯甲酰氧基-2α,9α,15β-三羟基-5α-异丁酰氧基-3β,7β,8α-三乙酰氧基-假白榄烷-6(17),11E-二烯8mg,产率32％；

该化合物质谱及核磁数据为：ESI(+)MS m/z 725.3162[M+Na]⁺，分子式为C₃₇H₅₀O₁₃.¹H NMR(400MHz,CDCl₃)δppm:2.23(1H,d,J＝15.0Hz,H-1α),2.11(1H,d,J＝15.2Hz,H-1β),5.31(1H,d,J＝3.6Hz,H-3),3.38(1H,m,H-4),5.70(1H,d,J＝3.0Hz,H-5),5.54(1H,s,H-7),5.20(1H,s,H-8),3.66(1H,s,H-9),5.87(1H,s,H-11),5.86(1H,d,J＝8.3Hz,H-12),2.88(1H,m,H-13),5.41(1H,s,H-14),1.28(3H,s,H₃-16),4.98(1H,s,H-17α),4.62(1H,s,H-17β),1.07(3H,s,H₃-18),1.30(3H,s,H₃-19),1.13(3H,d,J＝7.1Hz,H₃-20),2-OH:4.92(1H,s)；9-OH:4.80(1H,s)；15-OH:3.39(1H,s)；3-OAc:2.02(3H,s)；7-OAc:2.15(3H,s)；8-OAc:2.09(3H,s)；5-OiBu:2.14(1H,m,H-2'),0.80(3H,d,J＝7.0Hz,H-3'),0.70(3H,d,J＝7.0Hz,H-4')；14-OBz:8.01(2H,d,J＝7.0Hz,H-3',7'),7.47(2H,t,J＝7.3Hz,H-4',6'),7.53(1H,t,J＝7.3Hz,H-5').¹³C NMR(100MHz,CDCl₃)δppm:54.6(C-1),83.5(C-2),82.9(C-3),43.9(C-4),71.7(C-5),144.8(C-6),69.1(C-7),73.3(C-8),81.8(C-9),41.3(C-10),134.3(C-11),131.1(C-12),37.1(C-13),79.5(C-14),78.0(C-15),24.3(C-16),109.4(C-17),27.5(C-18),24.0(C-19),24.0(C-20),3-OAc:169.6(CO),21.4(C-2')；7-OAc:170.4(CO),21.4(C-2')；8-OAc:170.3(CO),21.2(C-2')；5-OiBu:174.0(CO),34.2(C-2'),18.5(C-3'),18.7(C-4')；14-OBz:166.6(CO),129.8(C-2'),130.2(C-3',7'),128.8(C-4',6'),133.2(C-5')。

实施例5

制备化合物5名称为：14β-苯甲酰氧基-2α,8α,9α,15β,17-五羟基-5α-异丁酰氧基-3β-三乙酰氧基-6,7环氧-假白榄烷-11E-烯：

将化合物3名称为14β-苯甲酰氧基-2α,7β,8α,9α,15β-五羟基-5α-异丁酰氧基-3β-乙酰氧基-假白榄烷-6(17),11E-二烯30mg,0.049mmol溶于二氯甲烷2mL，加入间氯过氧苯甲酸17mg，0.073mmol，75％，室温搅拌反应24小时，饱和硫代硫酸钠淬灭，乙酸乙酯萃取，依次用饱和碳酸氢钠、水、饱和氯化钠洗涤，无水硫酸钠干燥，有机相乙酸乙酯浓缩后，再通过硅胶柱200-300目梯度洗脱，洗脱剂为体积比1:1的石油醚和乙酸乙酯，即得白色固体化合物5名称为：14β-苯甲酰氧基-2α,8α,9α,15β,17-五羟基-5α-异丁酰氧基-3β-三乙酰氧基-6,7环氧-假白榄烷-11E-烯15mg,产率49％；

核磁数据为：¹H NMR(400MHz,CDCl₃)δppm:2.17(1H,s,H-1α),2.13(1H,s,H-1β),5.32(1H,d,J＝3.6Hz,H-3),3.18(1H,m,H-4),5.83(1H,d,J＝3.2Hz,H-5),2.21(1H,m,H-6),4.19(1H,s,H-7),4.39(1H,s,H-8),3.61(1H,s,H-9),5.88(1H,d,J＝16.1Hz,H-11),5.77(1H,d,J＝9.3Hz,H-12),2.82(1H,m,H-13),5.41(1H,s,H-14),1.32(3H,s,H₃-16),3.33(2H,m,H-17),1.11(3H,s,H₃-18),1.24(3H,s,H₃-19),1.12(3H,d,J＝7.7Hz,H₃-20),2-OH:ND；3-OH:ND；7-OH:ND；8-OH:3.00(1H,d,J＝5.2Hz)；9-OH:3.16(1H,br s)；15-OH:ND；17-OH:ND；3-OAc:2.08(3H,s)；5-OiBu:2.12(1H,m,H-2'),0.67(3H,d,J＝7.0Hz,H-3'),0.80(3H,d,J＝7.0Hz,H-4')；14-OBz:8.05(2H,d,J＝7.1Hz,H-3',7'),7.46(2H,t,J＝7.6Hz,H-4',6'),7.55(1H,t,J＝7.4Hz,H-5').¹³C NMR(100MHz,CDCl₃)δppm:54.4(C-1),78.4(C-2),83.2(C-3),42.6(C-4),67.2(C-5),44.9(C-6),64.3(C-7),71.2(C-8),83.5(C-9),40.9(C-10),135.3(C-11),130.3(C-12),37.1(C-13),79.3(C-14),84.0(C-15),24.3(C-16),63.2(C-17),27.1(C-18),23.7(C-19),23.9(C-20),3-OAc:170.4(CO),21.6(C-2')；5-OiBu:174.8(CO),34.0(C-2'),18.2(C-3'),18.7(C-4')；14-OBz:166.9(CO),129.7(C-2'),130.4(C-3',7'),128.6(C-4',6'),133.2(C-5')。

实施例6

制备化合物6名称为：14β-苯甲酰氧基-2α,7β,9α,15β-四羟基-5α-异丁酰氧基-3β-乙酰氧基-8α-3’-甲基-苯甲酰氧基-假白榄烷-6(17),11E-二烯：

将化合物3名称为14β-苯甲酰氧基-2α,7β,8α,9α,15β-五羟基-5α-异丁酰氧基-3β-乙酰氧基-假白榄烷-6(17),11E-二烯65mg,0.11mmol溶于吡啶2mL，加入3-甲基苯甲酰氯32mg,0.21mmol，室温搅拌1小时后，加入饱和碳酸氢钠淬灭，乙酸乙酯萃取，依次用水、饱和氯化钠洗涤，无水硫酸钠干燥，有机相乙酸乙酯浓缩后，再通过硅胶柱200-300目梯度洗脱，洗脱剂为体积比1:1的石油醚和乙酸乙酯，即得白色固体化合物6名称为：14β-苯甲酰氧基-2α,7β,9α,15β-四羟基-5α-异丁酰氧基-3β-乙酰氧基-8α-3’-甲基-苯甲酰氧基-假白榄烷-6(17),11E-二烯51mg,产率66％；

核磁数据为：¹H NMR(400MHz,CDCl₃)δppm:2.19(1H,d,J＝14.9Hz,H-1α),2.12(1H,d,J＝14.8Hz,H-1β),5.24(1H,d,J＝4.7Hz,H-3),3.21(1H,m,H-4),5.82(1H,br s,H-5),4.71(1H,s,H-7),5.50(1H,s,H-8),3.83(1H,s,H-9),6.11(1H,d,J＝16.0Hz,H-11),5.87(1H,m,H-12),2.88(1H,m,H-13),5.40(1H,s,H-14),1.33(3H,s,H₃-16),5.22(1H,s,H-17α),4.66(1H,s,H-17β),1.13(3H,s,H₃-18),1.42(3H,s,H₃-19),1.12(3H,d,J＝6.4Hz,H₃-20),2-OH:ND；7-OH:4.19(1H,s)；9-OH:4.26(1H,s)；15-OH:3.55(1H,s)；3-OAc:2.06(3H,s)；5-OiBu:2.10(1H,m,H-2'),0.76(3H,d,J＝7.0Hz,H-3'),0.69(3H,d,J＝7.0Hz,H-4')；14-OBz:8.05(2H,d,J＝7.1Hz,H-3',7'),7.51(2H,t,J＝7.3Hz,H-4',6'),7.56(1H,t,J＝7.3Hz,H-5')；8-3’-CH₃-BzO:7.92(1H,s,H-2'),7.34(1H,d,J＝7.5Hz,H-4'),7.29(1H,t,J＝7.8Hz,H-5'),7.92(1H,d,J＝7.3Hz,H-6'),2.37(3H,s,H-7').¹³C NMR(100MHz,CDCl₃)δppm:54.2(C-1),78.8(C-2),83.8(C-3),44.0(C-4),71.9(C-5),147.6(C-6),67.9(C-7),74.1(C-8),82.7(C-9),41.2(C-10),135.1(C-11),130.6(C-12),37.6(C-13),79.6(C-14),83.9(C-15),24.7(C-16),108.5(C-17),27.8(C-18),24.1(C-19),23.8(C-20),3-OAc:171.2(CO),21.5(C-2')；5-OiBu:173.6(CO),34.2(C-2'),18.5(C-3'),18.5(C-4')；14-OBz:166.7(CO),129.7(C-2'),130.2(C-3',7'),128.9(C-4',6'),133.3(C-5')；8-3’-CH₃-BzO:165.6(CO),130.6(C-1'),130.6(C-2'),138.3(C-3'),133.9(C-4'),128.4(C-5'),127.2(C-6'),21.5(C-7').

实施例7

制备化合物7名称为：14β-苯甲酰氧基-2α,8α,9α,15β-四羟基-5α-异丁酰氧基-3β-乙酰氧基-7β-3’-甲基苯甲酰氧基-假白榄烷-6(17),11E-二烯：

将化合物6名称为：14β-苯甲酰氧基-2α,7β,9α,15β-四羟基-5α-异丁酰氧基-3β-乙酰氧基-8α-3’-甲基-苯甲酰氧基-假白榄烷-6(17),11E-二烯在甲醇水溶液中放置6天，浓缩，再通过200-300目硅胶柱梯度洗脱，洗脱剂为体积比1:1的石油醚和乙酸乙酯，得到白色固体化合物7名称为14β-苯甲酰氧基-2α,8α,9α,15β-四羟基-5α-异丁酰氧基-3β-乙酰氧基-7β-3’-甲基苯甲酰氧基-假白榄烷-6(17),11E-二烯产率19％；

核磁数据为：¹H NMR(600MHz,CDCl₃)δppm:2.27(1H,d,J＝15.0Hz,H-1α),2.14(1H,d,J＝15.0Hz,H-1β),5.42(1H,d,J＝3.4Hz,H-3),3.45(1H,m,H-4),5.75(1H,d,J＝2.4Hz,H-5),5.65(1H,s,H-7),4.25(1H,d,J＝4.1Hz,H-8),3.75(1H,s,H-9),5.95(1H,d,J＝16.1Hz,H-11),5.80(1H,m,H-12),2.89(1H,m,H-13),5.43(1H,s,H-14),1.32(3H,s,H₃-16),5.11(1H,s,H-17α),4.69(1H,s,H-17β),1.06(3H,s,H₃-18),1.25(3H,s,H₃-19),1.14(3H,d,J＝7.0Hz,H₃-20),2-OH:2.60(1H,s)；8-OH:2.49(1H,s)；9-OH:ND；15-OH:3.44(1H,s)；3-OAc:2.00(3H,s)；5-OiBu:2.16(1H,m,H-2'),0.85(3H,d,J＝7.0Hz,H-3'),0.68(3H,d,J＝7.0Hz,H-4')；14-OBz:8.00(2H,d,J＝7.8Hz,H-3',7'),7.46(2H,t,J＝7.6Hz,H-4',6'),7.56(1H,t,J＝7.4Hz,H-5')；7-3’-CH₃-BzO:7.89(1H,s,H-2'),7.38(1H,d,J＝7.4Hz,H-4'),7.32(1H,t,J＝7.8Hz,H-5'),7.88(1H,d,J＝7.5Hz,H-6'),2.39(3H,s,H-7').¹³CNMR(150MHz,CDCl₃)δppm:54.5(C-1),78.1(C-2),83.2(C-3),44.0(C-4),72.2(C-5),145.3(C-6),70.2(C-7),70.9(C-8),83.8(C-9),41.0(C-10),134.7(C-11),130.5(C-12),37.2(C-13),79.6(C-14),83.6(C-15),24.4(C-16),108.9(C-17),27.2(C-18),23.9(C-19),24.0(C-20),3-OAc:169.5(CO),21.4(C-2')；5-OiBu:175.0(CO),34.1(C-2'),18.3(C-3'),18.6(C-4')；14-OBz:166.5(CO),129.8(C-2'),130.1(C-3',7'),128.8(C-4',6'),133.2(C-5')；7-3’-CH₃-BzO:165.6(CO),130.0(C-1'),130.5(C-2'),138.6(C-3'),134.5(C-4'),128.7(C-5'),127.2(C-6'),21.5(C-7').

实施例8

制备化合物8名称为：14β-苯甲酰氧基-2α,15β-二羟基-5α-异丁酰氧基-3β,7β,8α,9α-四乙酰氧基-假白榄烷-6(17),11E-二烯：

将化合物3名称为14β-苯甲酰氧基-2α,7β,8α,9α,15β-五羟基-5α-异丁酰氧基-3β-乙酰氧基-假白榄烷-6(17),11E-二烯35mg,0.057mmol溶于二氯甲烷2mL，加入三乙胺0.05mL,0.35mmol，乙酸酐30mg,0.29mmol，4-二甲氨基吡啶1mg,0.008mmol室温搅拌2小时，加入饱和碳酸氢钠淬灭，乙酸乙酯萃取，依次用水、饱和氯化钠洗涤，无水硫酸钠干燥，有机相乙酸乙酯浓缩后，再通过硅胶柱200-300目梯度洗脱，洗脱剂为体积比1:1的石油醚和乙酸乙酯，即得白色固体化合物8名称为：14β-苯甲酰氧基-2α,15β-二羟基-5α-异丁酰氧基-3β,7β,8α,9α-四乙酰氧基-假白榄烷-6(17),11E-二烯37mg,产率88％；

质谱及核磁数据为：ESI(+)MS m/z 767.3250[M+Na]⁺，分子式为C₃₉H₅₂O₁₄.¹H NMR(400MHz,CDCl₃)δppm:2.22(1H,d,J＝14.9Hz,H-1α),2.12(1H,d,J＝15.0Hz,H-1β),5.28(1H,d,J＝3.6Hz,H-3),3.36(1H,t,J＝3.5Hz,H-4),5.70(1H,d,J＝2.0Hz,H-5),5.57(1H,s,H-7),5.30(1H,s,H-8),5.01(1H,s,H-9),5.83(1H,d,J＝16.1Hz,H-11),5.90(1H,dd,J＝16.2,8.7Hz,H-12),2.89(1H,m,H-13),5.42(1H,s,H-14),1.29(3H,s,H₃-16),4.98(1H,s,H-17α),4.61(1H,s,H-17β),0.91(3H,s,H₃-18),1.41(3H,s,H₃-19),1.13(3H,d,J＝7.0Hz,H₃-20),2-OH:5.28(1H,br s)；15-OH:3.41(1H,s)；3-OAc:2.02(3H,s)；7-OAc:2.15(3H,s)；8-OAc:2.07(3H,s)；9-OAc:2.04(3H,s)；5-OiBu:2.14(1H,m,H-2'),0.69(3H,d,J＝7.0Hz,H-3'),0.78(3H,d,J＝7.0Hz,H-4')；14-OBz:8.01(2H,d,J＝7.1Hz,H-3',7'),7.47(2H,t,J＝7.4Hz,H-4',6'),7.54(1H,t,J＝7.3Hz,H-5').¹³C NMR(100MHz,CDCl₃)δppm:54.5(C-1),78.2(C-2),82.8(C-3),43.8(C-4),71.5(C-5),144.6(C-6),68.6(C-7),70.9(C-8),80.9(C-9),41.0(C-10),134.1(C-11),131.8(C-12),37.2(C-13),79.4(C-14),83.6(C-15),24.4(C-16),109.6(C-17),27.0(C-18),23.8(C-19),23.9(C-20),3-OAc:169.7(CO),21.4(C-2')；7-OAc:170.3(CO),21.4(C-2')；8-OAc:170.1(CO),21.0(C-2')；9-OAc:169.9(CO),20.8(C-2')；5-OiBu:173.8(CO),34.1(C-2'),18.4(C-3'),18.6(C-4')；14-OBz:166.6(CO),129.7(C-2'),130.2(C-3',7'),128.9(C-4',6'),133.3(C-5')。

实施例9

制备化合物9名称为：14β-苯甲酰氧基-15β-羟基-5α-异丁酰氧基-2α,3β,7β,8α,9α-五乙酰氧基-假白榄烷-6(17),11E-二烯：

将化合物8名称为：14β-苯甲酰氧基-2α,15β-二羟基-5α-异丁酰氧基-3β,7β,8α,9α-四乙酰氧基-假白榄烷-6(17),11E-二烯40mg,0.054mmol溶于吡啶2mL，加入乙酸酐30mg,0.29mmol，4-二甲氨基吡啶1mg,0.008mmol，回流搅拌24小时，加入饱和碳酸氢钠淬灭，乙酸乙酯萃取，依次用水、饱和氯化钠洗涤，无水硫酸钠干燥，有机相乙酸乙酯浓缩后，再通过硅胶柱200-300目梯度洗脱，洗脱剂为体积比2:1的石油醚和乙酸乙酯，即得白色固体化合物9名称为：14β-苯甲酰氧基-15β-羟基-5α-异丁酰氧基-2α,3β,7β,8α,9α-五乙酰氧基-假白榄烷-6(17),11E-二烯21mg,产率50％；

质谱及核磁数据为：ESI(+)MS m/z 809.3353[M+Na]⁺，分子式为C₄₁H₅₄O₁₅.¹H NMR(400MHz,CDCl₃)δppm:2.62(1H,d,J＝14.9Hz,H-1α),2.22(1H,d,J＝14.9Hz,H-1β),5.28(1H,d,J＝5.6Hz,H-3),3.23(1H,dd,J＝5.2,3.5Hz,H-4),5.71(1H,d,J＝2.0Hz,H-5),5.56(1H,s,H-7),5.33(1H,s,H-8),5.02(1H,s,H-9),5.89(1H,d,J＝16.0Hz,H-11),5.89(1H,dd,J＝16.0,8.5Hz,H-12),2.70(1H,m,H-13),5.40(1H,s,H-14),1.48(3H,s,H₃-16),4.98(1H,s,H-17α),4.58(1H,s,H-17β),0.92(3H,s,H₃-18),1.42(3H,s,H₃-19),1.11(3H,d,J＝7.0Hz,H₃-20),15-OH:3.46(1H,s)；2-OAc:2.12(3H,s)；3-OAc:2.00(3H,s)；7-OAc:2.10(3H,s)；8-OAc:2.05(3H,s)；9-OAc:2.04(3H,s)；5-OiBu:2.09(1H,m,H-2'),0.68(3H,d,J＝7.0Hz,H-3'),0.78(3H,d,J＝7.0Hz,H-4')；14-OBz:7.99(2H,d,J＝7.5Hz,H-3',7'),7.47(2H,t,J＝7.5Hz,H-4',6'),7.54(1H,t,J＝7.2Hz,H-5').¹³C NMR(100MHz,CDCl₃)δppm:51.6(C-1),87.9(C-2),80.5(C-3),44.4(C-4),71.6(C-5),144.4(C-6),67.7(C-7),71.3(C-8),80.7(C-9),41.0(C-10),134.4(C-11),131.4(C-12),38.0(C-13),79.0(C-14),84.0(C-15),21.9(C-16),109.6(C-17),27.0(C-18),23.8(C-19),23.9(C-20),2-OAc:170.7(CO),22.5(C-2')；3-OAc:169.3(CO),21.3(C-2')；7-OAc:169.1(CO),21.2(C-2')；8-OAc:170.2(CO),21.0(C-2')；9-OAc:169.9(CO),20.8(C-2')；5-OiBu:173.7(CO),34.1(C-2'),18.4(C-3'),18.5(C-4')；14-OBz:166.5(CO),129.5(C-2'),130.2(C-3',7'),128.9(C-4',6'),133.4(C-5')。

实施例10

制备化合物10名称为：14β-苯甲酰氧基-15β-羟基-5α-异丁酰氧基-3β,7β,8α,9α-四乙酰氧基-2α-3’-甲基-苯甲酰氧基-假白榄烷-6(17),11E-二烯：

将化合物8名称为：14β-苯甲酰氧基-2α,15β-二羟基-5α-异丁酰氧基-3β,7β,8α,9α-四乙酰氧基-假白榄烷-6(17),11E-二烯50mg,0.067mmol溶于吡啶2mL，加入3-甲基苯甲酰氯31mg,0.20mmol，4-二甲氨基吡啶1mg,0.008mmol，回流搅拌24小时，加入饱和碳酸氢钠淬灭，乙酸乙酯萃取，依次用水、饱和氯化钠洗涤，无水硫酸钠干燥，有机相乙酸乙酯浓缩后，再通过硅胶柱200-300目梯度洗脱，洗脱剂为体积比2:1的石油醚和乙酸乙酯，即得白色固体化合物10名称为：14β-苯甲酰氧基-15β-羟基-5α-异丁酰氧基-3β,7β,8α,9α-四乙酰氧基-2α-3’-甲基-苯甲酰氧基-假白榄烷-6(17),11E-二烯30mg,产率52％；

质谱及核磁数据为：ESI(+)MS m/z 885.3671[M+Na]⁺，分子式为C₄₇H₅₈O₁₅.¹H NMR(400MHz,CDCl₃)δppm:2.63(1H,d,J＝15.4Hz,H-1α),2.52(1H,d,J＝15.2Hz,H-1β),5.83(1H,d,J＝5.0Hz,H-3),3.19(1H,dd,J＝5.5,3.5Hz,H-4),5.76(1H,s,H-5),5.56(1H,s,H-7),5.36(1H,s,H-8),5.02(1H,s,H-9),5.76(1H,d,J＝15.8Hz,H-11),5.88(1H,dd,J＝16.8,9.8Hz,H-12),2.59(1H,m,H-13),5.42(1H,s,H-14),1.65(3H,s,H₃-16),5.01(1H,s,H-17α),4.63(1H,s,H-17β),0.86(3H,s,H₃-18),1.43(3H,s,H₃-19),1.06(3H,d,J＝7.0Hz,H₃-20),15-OH:3.50(1H,s)；2-3’-CH₃-BzO:8.13(1H,s,H-2'),7.36(1H,d,J＝7.6Hz,H-4'),7.30(1H,t,J＝7.6Hz,H-5'),8.04(1H,d,J＝7.6Hz,H-6'),2.40(3H,s,H-7')；3-OAc:2.04(3H,s)；7-OAc:2.18(3H,s)；8-OAc:2.07(3H,s)；9-OAc:2.03(3H,s)；5-OiBu:2.12(1H,m,H-2'),0.72(3H,d,J＝7.0Hz,H-3'),0.79(3H,d,J＝7.0Hz,H-4')；14-OBz:7.99(2H,d,J＝7.1Hz,H-3',7'),7.48(2H,t,J＝7.4Hz,H-4',6'),7.55(1H,t,J＝7.3Hz,H-5').¹³C NMR(100MHz,CDCl₃)δppm:52.2(C-1),88.8(C-2),80.9(C-3),44.3(C-4),71.6(C-5),144.5(C-6),68.1(C-7),71.3(C-8),80.8(C-9),41.0(C-10),134.3(C-11),131.5(C-12),38.1(C-13),79.0(C-14),84.1(C-15),21.1(C-16),109.4(C-17),27.0(C-18),23.9(C-19),23.8(C-20),2-3’-CH₃-BzO:166.2(CO),131.2(C-1'),131.0(C-2'),138.1(C-3'),133.8(C-4'),128.2(C-5'),127.5(C-6'),21.4(C-7')；3-OAc:169.6(CO),21.4(C-2')；7-OAc:169.3(CO),21.2(C-2')；8-OAc:170.2(CO),21.0(C-2')；9-OAc:169.8(CO),20.8(C-2')；5-OiBu:173.8(CO),34.2(C-2'),18.5(C-3'),18.5(C-4')；14-OBz:166.4(CO),129.5(C-2'),130.2(C-3',7'),129.0(C-4',6'),133.4(C-5')。

实施例11

制备化合物11名称为：14β-苯甲酰氧基-15β-羟基-5α-异丁酰氧基-3β,7β,8α,9α-四乙酰氧基-2α-异烟酰氧基-假白榄烷-6(17),11E-二烯：

将化合物8名称为：14β-苯甲酰氧基-2α,15β-二羟基-5α-异丁酰氧基-3β,7β,8α,9α-四乙酰氧基-假白榄烷-6(17),11E-二烯55mg,0.074mmol溶于吡啶2mL，加入异烟酰氯31mg,0.22mmol，4-二甲氨基吡啶1mg,0.008mmol，回流搅拌4小时，加入饱和碳酸氢钠淬灭，乙酸乙酯萃取，依次用水、饱和氯化钠洗涤，无水硫酸钠干燥，有机相乙酸乙酯浓缩后，再通过硅胶柱200-300目梯度洗脱，洗脱剂为体积比1:2的石油醚和乙酸乙酯，即得白色固体化合物11名称为：14β-苯甲酰氧基-15β-羟基-5α-异丁酰氧基-3β,7β,8α,9α-四乙酰氧基-2α-异烟酰氧基-假白榄烷-6(17),11E-二烯46mg,产率73％；

质谱及核磁数据为：ESI(+)MS m/z 872.3452[M+Na]⁺，分子式为C₄₅H₅₅NO₁₅.¹H NMR(400MHz,CDCl₃)δppm:2.60(1H,d,J＝14.8Hz,H-1α),2.51(1H,d,J＝15.0Hz,H-1β),5.80(1H,d,J＝6.5Hz,H-3),3.20(1H,dd,J＝5.7,3.4Hz,H-4),5.75(1H,d,J＝3.8Hz,H-5),5.54(1H,s,H-7),5.34(1H,s,H-8),5.02(1H,s,H-9),5.77(1H,d,J＝16.4Hz,H-11),5.89(1H,dd,J＝16.2,9.2Hz,H-12),2.59(1H,m,H-13),5.43(1H,s,H-14),1.64(3H,s,H₃-16),5.01(1H,s,H-17α),4.62(1H,s,H-17β),0.86(3H,s,H₃-18),1.43(3H,s,H₃-19),1.07(3H,d,J＝7.0Hz,H₃-20),15-OH:3.47(1H,s)；2-OiNic:8.10(2H,d,J＝6.0Hz,H-2',6’),8.77(2H,d,J＝5.9Hz,H-3',5’)；3-OAc:2.04(3H,s)；7-OAc:2.16(3H,s)；8-OAc:2.07(3H,s)；9-OAc:2.04(3H,s)；5-OiBu:2.11(1H,m,H-2'),0.71(3H,d,J＝7.0Hz,H-3'),0.78(3H,d,J＝7.0Hz,H-4')；14-OBz:7.98(2H,d,J＝7.2Hz,H-3',7'),7.48(2H,t,J＝7.5Hz,H-4',6'),7.55(1H,t,J＝7.3Hz,H-5').¹³C NMR(100MHz,CDCl₃)δppm:52.0(C-1),90.2(C-2),80.5(C-3),44.3(C-4),71.4(C-5),144.6(C-6),68.0(C-7),71.2(C-8),80.8(C-9),41.0(C-10),134.4(C-11),131.3(C-12),38.3(C-13),78.8(C-14),84.0(C-15),21.2(C-16),109.5(C-17),27.0(C-18),23.8(C-19),23.9(C-20),2-OiNic:164.3(CO),138.9(C-1'),123.8(C-2',6’),150.3(C-3',5’)；3-OAc:169.8(CO),21.3(C-2')；7-OAc:169.7(CO),21.3(C-2')；8-OAc:170.2(CO),21.0(C-2')；9-OAc:169.6(CO),20.8(C-2')；5-OiBu:173.8(CO),34.2(C-2'),18.4(C-3'),18.5(C-4')；14-OBz:166.4(CO),129.4(C-2'),130.1(C-3',7'),129.0(C-4',6'),133.5(C-5')。

实施例12

制备化合物12名称为：14β-苯甲酰氧基-15β-羟基-5α-异丁酰氧基-3β,7β,8α,9α-四乙酰氧基-2α-新戊酰氧基-假白榄烷-6(17),11E-二烯：

将化合物8名称为14β-苯甲酰氧基-2α,15β-二羟基-5α-异丁酰氧基-3β,7β,8α,9α-四乙酰氧基-假白榄烷-6(17),11E-二烯155mg,0.21mmol溶于吡啶3mL，加入特戊酰氯51mg,0.42mmol，4-二甲氨基吡啶3mg,0.025mmol，回流搅拌18小时，加入饱和碳酸氢钠淬灭，乙酸乙酯萃取，依次用水、饱和氯化钠洗涤，无水硫酸钠干燥，有机相乙酸乙酯浓缩后，再通过硅胶柱200-300目梯度洗脱，洗脱剂为体积比3:1的石油醚和乙酸乙酯，即得白色固体化合物12名称为：14β-苯甲酰氧基-15β-羟基-5α-异丁酰氧基-3β,7β,8α,9α-四乙酰氧基-2α-新戊酰氧基-假白榄烷-6(17),11E-二烯80mg,产率46％；

质谱及核磁数据为：ESI(+)MS m/z 851.3829[M+Na]⁺，分子式为C₄₄H₆₀O₁₅.¹H NMR(400MHz,CDCl₃)δppm:2.56(1H,d,J＝15.1Hz,H-1α),2.29(1H,d,J＝15.1Hz,H-1β),5.64(1H,d,J＝5.7Hz,H-3),3.18(1H,dd,J＝5.5,3.7Hz,H-4),5.71(1H,d,J＝2.8Hz,H-5),5.52(1H,s,H-7),5.34(1H,s,H-8),5.00(1H,s,H-9),5.84(1H,d,J＝16.4Hz,H-11),5.90(1H,dd,J＝16.4,7.8Hz,H-12),2.64(1H,m,H-13),5.39(1H,s,H-14),1.48(3H,s,H₃-16),4.96(1H,s,H-17α),4.58(1H,s,H-17β),0.91(3H,s,H₃-18),1.43(3H,s,H₃-19),1.11(3H,d,J＝7.0Hz,H₃-20),15-OH:3.51(1H,s)；2-OPiv:1.26(9H,s,H-3',4’,5’)；3-OAc:2.00(3H,s)；7-OAc:2.09(3H,s)；8-OAc:2.07(3H,s)；9-OAc:2.03(3H,s)；5-OiBu:2.09(1H,m,H-2'),0.69(3H,d,J＝7.0Hz,H-3'),0.77(3H,d,J＝7.0Hz,H-4')；14-OBz:7.99(2H,d,J＝7.0Hz,H-3',7'),7.48(2H,t,J＝7.3Hz,H-4',6'),7.55(1H,t,J＝7.3Hz,H-5').¹³C NMR(100MHz,CDCl₃)δppm:51.7(C-1),87.7(C-2),80.7(C-3),44.4(C-4),71.7(C-5),144.2(C-6),67.8(C-7),71.2(C-8),80.9(C-9),41.0(C-10),134.3(C-11),131.6(C-12),38.2(C-13),79.1(C-14),84.1(C-15),21.3(C-16),109.4(C-17),27.1(C-18),23.8(C-19),23.9(C-20),2-OPiv:178.0(CO),39.5(C-2'),27.2(C-3',4’,5’)；3-OAc:169.4(CO),21.3(C-2')；7-OAc:168.7(CO),21.1(C-2')；8-OAc:170.1(CO),21.0(C-2')；9-OAc:169.8(CO),20.7(C-2')；5-OiBu:173.7(CO),34.2(C-2'),18.4(C-3'),18.5(C-4')；14-OBz:166.5(CO),129.5(C-2'),130.2(C-3',7'),129.0(C-4',6'),133.4(C-5')。

实施例13

制备化合物13名称为：14β-苯甲酰氧基-2α,7β,9α,15β-四羟基-5α-异丁酰氧基-3β-乙酰氧基-8α-新戊酰氧基-假白榄烷-6(17),11E-二烯：

将化合物3名称为14β-苯甲酰氧基-2α,7β,8α,9α,15β-五羟基-5α-异丁酰氧基-3β-乙酰氧基-假白榄烷-6(17),11E-二烯65mg,0.11mmol溶于吡啶2mL，加入特戊酰氯25mg,0.21mmol，室温搅拌2小时后，加入饱和碳酸氢钠淬灭，乙酸乙酯萃取，依次用水、饱和氯化钠洗涤，无水硫酸钠干燥，有机相乙酸乙酯浓缩后，再通过硅胶柱200-300目梯度洗脱，洗脱剂为体积比1:1的石油醚和乙酸乙酯，即得白色固体化合物13名称为：14β-苯甲酰氧基-2α,7β,9α,15β-四羟基-5α-异丁酰氧基-3β-乙酰氧基-8α-新戊酰氧基-假白榄烷-6(17),11E-二烯44mg,产率60％；

核磁数据为：¹H NMR(400MHz,CDCl₃)δppm:2.17(1H,d,J＝15.0Hz,H-1α),2.11(1H,d,J＝14.9Hz,H-1β),5.15(1H,d,J＝5.3Hz,H-3),3.11(1H,m,H-4),5.71(1H,d,J＝2.3Hz,H-5),4.55(1H,s,H-7),5.20(1H,s,H-8),3.68(1H,s,H-9),5.93(1H,d,J＝16.0Hz,H-11),5.79(1H,dd,J＝16.0,9.4Hz,H-12),2.83(1H,dd,J＝8.9,7.3Hz,H-13),5.37(1H,s,H-14),1.32(3H,s,H₃-16),5.16(1H,s,H-17α),4.66(1H,s,H-17β),1.10(3H,s,H₃-18),1.32(3H,s,H₃-19),1.12(3H,d,J＝7.0Hz,H₃-20),2-OH:ND；7-OH:3.89(1H,br s)；9-OH:4.22(1H,s)；15-OH:3.52(1H,s)；3-OAc:2.05(3H,s)；5-OiBu:2.11(1H,m,H-2'),0.66(3H,d,J＝7.0Hz,H-3'),0.79(3H,d,J＝7.0Hz,H-4')；8-OPiv:1.19(9H,s,H-3',4’,5’)；14-OBz:8.01(2H,d,J＝7.2Hz,H-3',7'),7.47(2H,t,J＝7.4Hz,H-4',6'),7.53(1H,t,J＝7.3Hz,H-5').¹³C NMR(100MHz,CDCl₃)δppm:54.1(C-1),78.6(C-2),83.7(C-3),44.2(C-4),72.0(C-5),147.3(C-6),68.5(C-7),73.1(C-8),82.5(C-9),41.3(C-10),135.0(C-11),130.8(C-12),37.5(C-13),79.7(C-14),83.8(C-15),24.6(C-16),108.5(C-17),27.4(C-18),24.3(C-19),23.9(C-20),3-OAc:171.0(CO),21.5(C-2')；5-OiBu:173.6(CO),34.1(C-2'),18.5(C-3'),18.6(C-4')；8-OPiv:176.9(CO),39.4(C-2'),27.4(C-3',4’,5’)；14-OBz:166.7(CO),129.6(C-2'),130.2(C-3',7'),128.9(C-4',6'),133.3(C-5')。

实施例14

制备化合物14名称为：14β-苯甲酰氧基-2α,15β-二羟基-5α-异丁酰氧基-3β,7β,9α-三乙酰氧基-8α-3’-甲基-苯甲酰氧基-假白榄烷-6(17),11E-二烯：

将化合物6名称为：14β-苯甲酰氧基-2α,7β,9α,15β-四羟基-5α-异丁酰氧基-3β-乙酰氧基-8α-3’-甲基-苯甲酰氧基-假白榄烷-6(17),11E-二烯30mg,0.041mmol溶于二氯甲烷2mL，加入三乙胺0.05mL,0.35mmol，乙酸酐20mg,2.04mmol，4-二甲氨基吡啶1mg,0.008mmol室温搅拌2小时，加入饱和碳酸氢钠淬灭，乙酸乙酯萃取，依次用水、饱和氯化钠洗涤，无水硫酸钠干燥，有机相乙酸乙酯浓缩后，再通过硅胶柱200-300目梯度洗脱，洗脱剂为体积比1:1的石油醚和乙酸乙酯，即得白色固体化合物14名称为：14β-苯甲酰氧基-2α,15β-二羟基-5α-异丁酰氧基-3β,7β,9α-三乙酰氧基-8α-3’-甲基-苯甲酰氧基-假白榄烷-6(17),11E-二烯28mg,产率84％；

该化合物核磁数据为：¹H NMR(400MHz,CDCl₃)δppm:2.24(1H,d,J＝15.0Hz,H-1α),2.14(1H,d,J＝14.9Hz,H-1β),5.29(1H,d,J＝3.9Hz,H-3),3.39(1H,t,J＝3.6Hz,H-4),5.78(1H,d,J＝3.0Hz,H-5),5.68(1H,s,H-7),5.52(1H,s,H-8),5.16(1H,s,H-9),5.91(1H,d,J＝16.1Hz,H-11),5.95(1H,d,J＝16.0Hz,H-12),2.91(1H,m,H-13),5.44(1H,s,H-14),1.30(3H,s,H₃-16),5.02(1H,s,H-17α),4.60(1H,s,H-17β),0.94(3H,s,H₃-18),1.53(3H,s,H₃-19),1.14(3H,d,J＝7.0Hz,H₃-20),2-OH:ND；15-OH:3.43(1H,s)；3-OAc:2.00(3H,s)；7-OAc:2.22(3H,s)；9-OAc:2.06(3H,s)；5-OiBu:2.09(1H,m,H-2'),0.66(3H,d,J＝7.0Hz,H-3'),0.74(3H,d,J＝7.0Hz,H-4')；14-OBz:8.03(2H,d,J＝7.3Hz,H-3',7'),7.50(2H,t,J＝7.5Hz,H-4',6'),7.55(1H,t,J＝7.3Hz,H-5')；8-3’-CH₃-BzO:7.88(1H,s,H-2'),7.35(1H,d,J＝7.5Hz,H-4'),7.31(1H,t,J＝7.6Hz,H-5'),7.84(1H,d,J＝7.6Hz,H-6'),2.38(3H,s,H-7').¹³C NMR(100MHz,CDCl₃)δppm:54.7(C-1),78.2(C-2),82.9(C-3),43.8(C-4),71.3(C-5),144.8(C-6),68.7(C-7),71.6(C-8),80.8(C-9),41.0(C-10),134.2(C-11),131.7(C-12),37.3(C-13),79.2(C-14),83.6(C-15),24.5(C-16),109.9(C-17),27.3(C-18),23.7(C-19),23.9(C-20),3-OAc:169.8(CO),21.4(C-2')；7-OAc:170.2(CO),21.3(C-2')；9-OAc:169.7(CO),20.8(C-2')；5-OiBu:173.8(CO),34.1(C-2'),18.4(C-3'),18.5(C-4')；14-OBz:166.6(CO),129.7(C-2'),130.2(C-3',7'),128.9(C-4',6'),133.3(C-5')；8-3’-CH₃-BzO:165.7(CO),130.2(C-1'),130.8(C-2'),138.3(C-3'),134.0(C-4'),128.5(C-5'),127.2(C-6'),21.6(C-7')。

实施例15

制备化合物15名称为：14β-苯甲酰氧基-15β-羟基-5α-异丁酰氧基-2α,3β,7β,9α-四乙酰氧基-8α-3’-甲基-苯甲酰氧基-假白榄烷-6(17),11E-二烯：

将化合物14名称为14β-苯甲酰氧基-2α,15β-二羟基-5α-异丁酰氧基-3β,7β,9α-三乙酰氧基-8α-3’-甲基-苯甲酰氧基-假白榄烷-6(17),11E-二烯51mg,0.062mmol溶于吡啶3mL，加入乙酸酐20mg,0.196mmol，4-二甲氨基吡啶1mg,0.008mmol，回流搅拌48小时，加入饱和碳酸氢钠淬灭，乙酸乙酯萃取，依次用水、饱和氯化钠洗涤，无水硫酸钠干燥，有机相乙酸乙酯浓缩后，再通过硅胶柱200-300目梯度洗脱，洗脱剂为体积比2:1的石油醚和乙酸乙酯，即得白色固体化合物15名称为：14β-苯甲酰氧基-15β-羟基-5α-异丁酰氧基-2α,3β,7β,9α-四乙酰氧基-8α-3’-甲基-苯甲酰氧基-假白榄烷-6(17),11E-二烯26mg,产率48％；

核磁数据为：¹H NMR(400MHz,CDCl₃)δppm:2.63(1H,d,J＝14.8Hz,H-1α),2.26(1H,d,J＝14.8Hz,H-1β),5.60(1H,d,J＝5.7Hz,H-3),3.28(1H,dd,J＝5.4,3.5Hz,H-4),5.81(1H,br s,H-5),5.68(1H,s,H-7),5.56(1H,s,H-8),5.18(1H,s,H-9),5.98(1H,m,H-11),5.98(1H,m,H-12),2.76(1H,m,H-13),5.43(1H,s,H-14),1.49(3H,s,H₃-16),5.03(1H,s,H-17α),4.58(1H,s,H-17β),0.96(3H,s,H₃-18),1.55(3H,s,H₃-19),1.13(3H,d,J＝7.0Hz,H₃-20),15-OH:3.47(1H,s)；2-OAc:2.13(3H,s)；3-OAc:1.98(3H,s)；7-OAc:2.17(3H,s)；9-OAc:2.06(3H,s)；5-OiBu:2.05(1H,m,H-2'),0.67(3H,d,J＝7.0Hz,H-3'),0.74(3H,d,J＝7.0Hz,H-4')；14-OBz:8.02(2H,d,J＝7.2Hz,H-3',7'),7.50(2H,t,J＝7.6Hz,H-4',6'),7.56(1H,t,J＝7.3Hz,H-5')；8-3’-CH₃-BzO:7.87(1H,s,H-2'),7.34(1H,d,J＝7.5Hz,H-4'),7.30(1H,t,J＝7.6Hz,H-5'),7.84(1H,d,J＝7.6Hz,H-6'),2.38(3H,s,H-7').¹³C NMR(100MHz,CDCl₃)δppm:51.8(C-1),88.0(C-2),80.5(C-3),44.4(C-4),71.4(C-5),144.6(C-6),67.8(C-7),71.9(C-8),80.7(C-9),41.0(C-10),134.5(C-11),131.4(C-12),38.0(C-13),78.9(C-14),84.0(C-15),22.0(C-16),109.9(C-17),27.2(C-18),23.7(C-19),23.9(C-20),2-OAc:170.7(CO),22.6(C-2')；3-OAc:169.4(CO),21.3(C-2')；7-OAc:168.9(CO),21.2(C-2')；9-OAc:169.7(CO),20.8(C-2')；5-OiBu:173.7(CO),34.1(C-2'),18.4(C-3'),18.4(C-4')；14-OBz:166.5(CO),129.6(C-2'),130.2(C-3',7'),129.0(C-4',6'),133.4(C-5')；8-3’-CH₃-BzO:165.7(CO),130.2(C-1'),130.7(C-2'),138.2(C-3'),133.9(C-4'),128.4(C-5'),127.2(C-6'),21.6(C-7')。

实施例16

制备化合物16名称为：14β-苯甲酰氧基-2α,15β-二羟基-5α-异丁酰氧基-3β,7β,9α-三乙酰氧基-8α-新戊酰氧基-假白榄烷-6(17),11E-二烯：

将化合物13名称为14β-苯甲酰氧基-2α,7β,9α,15β-四羟基-5α-异丁酰氧基-3β-乙酰氧基-8α-新戊酰氧基-假白榄烷-6(17),11E-二烯42mg,0.060mmol溶于二氯甲烷2mL，加入三乙胺0.05mL,0.35mmol，乙酸酐24mg,0.24mmol，4-二甲氨基吡啶1mg,0.008mmol室温搅拌2小时，加入饱和碳酸氢钠淬灭，乙酸乙酯萃取，依次用水、饱和氯化钠洗涤，无水硫酸钠干燥，有机相乙酸乙酯浓缩后，再通过硅胶柱200-300目梯度洗脱，洗脱剂为体积比1:1的石油醚和乙酸乙酯，即得白色固体化合物16名称为：14β-苯甲酰氧基-2α,15β-二羟基-5α-异丁酰氧基-3β,7β,9α-三乙酰氧基-8α-新戊酰氧基-假白榄烷-6(17),11E-二烯40mg,产率85％；

该化合物核磁数据为：¹H NMR(400MHz,CDCl₃)δppm:2.21(1H,d,J＝14.9Hz,H-1α),2.12(1H,d,J＝14.8Hz,H-1β),5.26(1H,d,J＝3.9Hz,H-3),3.33(1H,t,J＝3.7Hz,H-4),5.70(1H,d,J＝2.7Hz,H-5),5.56(1H,s,H-7),5.21(1H,s,H-8),5.02(1H,s,H-9),5.88(1H,d,J＝16.1Hz,H-11),5.88(1H,d,J＝16.0Hz,H-12),2.87(1H,dd,J＝8.8,7.3Hz,H-13),5.41(1H,s,H-14),1.28(3H,s,H₃-16),4.97(1H,s,H-17α),4.61(1H,s,H-17β),0.91(3H,s,H₃-18),1.44(3H,s,H₃-19),1.12(3H,d,J＝7.0Hz,H₃-20),2-OH:ND；15-OH:3.41(1H,s)；3-OAc:2.00(3H,s)；7-OAc:2.13(3H,s)；9-OAc:2.03(3H,s)；5-OiBu:2.12(1H,m,H-2'),0.66(3H,d,J＝7.0Hz,H-3'),0.78(3H,d,J＝7.0Hz,H-4')；14-OBz:7.99(2H,d,J＝7.2Hz,H-3',7'),7.47(2H,t,J＝7.6Hz,H-4',6'),7.53(1H,t,J＝7.4Hz,H-5')；8-OPiv:1.18(9H,s,H-3',4’,5’).¹³C NMR(100MHz,CDCl₃)δppm:54.5(C-1),78.2(C-2),82.9(C-3),43.8(C-4),71.4(C-5),145.1(C-6),68.9(C-7),70.8(C-8),80.5(C-9),40.9(C-10),134.3(C-11),131.7(C-12),37.2(C-13),79.3(C-14),83.6(C-15),24.4(C-16),109.4(C-17),27.1(C-18),23.8(C-19),23.9(C-20),3-OAc:169.7(CO),21.4(C-2')；7-OAc:170.2(CO),21.2(C-2')；9-OAc:169.6(CO),20.8(C-2')；5-OiBu:173.8(CO),34.0(C-2'),18.4(C-3'),18.5(C-4')；14-OBz:166.6(CO),129.7(C-2'),130.1(C-3',7'),128.9(C-4',6'),133.3(C-5')；8-OPiv:177.3(CO),39.3(C-2'),27.3(C-3',4’,5’)。

实施例17

制备化合物17名称为：14β-苯甲酰氧基-15β-羟基-5α-异丁酰氧基-2α,3β,7β,9α-四乙酰氧基-8α-新戊酰氧基-假白榄烷-6(17),11E-二烯

将化合物16名称为14β-苯甲酰氧基-2α,15β-二羟基-5α-异丁酰氧基-3β,7β,9α-三乙酰氧基-8α-新戊酰氧基-假白榄烷-6(17),11E-二烯40mg,0.051mmol溶于吡啶3mL，加入乙酸酐16mg,0.157mmol，4-二甲氨基吡啶1mg,0.008mmol，回流搅拌48小时，加入饱和碳酸氢钠淬灭，乙酸乙酯萃取，依次用水、饱和氯化钠洗涤，无水硫酸钠干燥，有机相乙酸乙酯浓缩后，再通过硅胶柱200-300目梯度洗脱，洗脱剂为体积比2:1的石油醚和乙酸乙酯，即得白色固体化合物17名称为：14β-苯甲酰氧基-15β-羟基-5α-异丁酰氧基-2α,3β,7β,9α-四乙酰氧基-8α-新戊酰氧基-假白榄烷-6(17),11E-二烯19mg,产率45％；

核磁数据为：¹H NMR(400MHz,CDCl₃)δppm:2.60(1H,d,J＝14.9Hz,H-1α),2.23(1H,d,J＝14.9Hz,H-1β),5.57(1H,d,J＝5.8Hz,H-3),3.21(1H,dd,J＝5.3,3.6Hz,H-4),5.72(1H,d,J＝2.1Hz,H-5),5.56(1H,s,H-7),5.27(1H,s,H-8),5.04(1H,s,H-9),5.91(1H,m,H-11),5.91(1H,m,H-12),2.71(1H,br s,H-13),5.40(1H,s,H-14),1.48(3H,s,H₃-16),4.98(1H,s,H-17α),4.59(1H,s,H-17β),0.93(3H,s,H₃-18),1.47(3H,s,H₃-19),1.12(3H,d,J＝7.0Hz,H₃-20),15-OH:3.44(1H,s)；2-OAc:2.12(3H,s)；3-OAc:2.00(3H,s)；7-OAc:2.09(3H,s)；9-OAc:2.04(3H,s)；5-OiBu:2.08(1H,m,H-2'),0.66(3H,d,J＝7.0Hz,H-3'),0.77(3H,d,J＝7.0Hz,H-4')；14-OBz:7.99(2H,d,J＝7.5Hz,H-3',7'),7.47(2H,t,J＝7.6Hz,H-4',6'),7.54(1H,t,J＝7.3Hz,H-5')；8-OPiv:1.17(9H,s,H-3',4’,5’).¹³C NMR(100MHz,CDCl₃)δppm:51.7(C-1),87.9(C-2),80.6(C-3),44.4(C-4),71.5(C-5),144.8(C-6),68.0(C-7),71.1(C-8),80.4(C-9),41.0(C-10),134.5(C-11),131.4(C-12),37.9(C-13),78.9(C-14),83.9(C-15),21.9(C-16),109.4(C-17),27.0(C-18),23.9(C-19),24.0(C-20),2-OAc:170.7(CO),22.5(C-2')；3-OAc:169.3(CO),21.3(C-2')；7-OAc:168.9(CO),21.1(C-2')；9-OAc:169.7(CO),20.7(C-2')；5-OiBu:173.8(CO),34.1(C-2'),18.4(C-3'),18.5(C-4')；14-OBz:166.5(CO),129.6(C-2'),130.2(C-3',7'),129.0(C-4',6'),133.4(C-5')；8-OPiv:177.3(CO),39.3(C-2'),27.3(C-3',4’,5’)。

实施例18

将实施例1-17得到的化合物1-17逆转肿瘤多药耐药活性测试：

本实验选择17个新型假白榄烷型二萜衍生物与抗肿瘤药阿霉素(DOX)联用，检测联用前后对耐药细胞的生长抑制，进行多药耐药逆转活性测试；

实验方法：将处于对数生长期的MCF7/ADR细胞以5000个/孔的密度接种于96孔微量培养板(每孔100μL)，在温度37℃培养箱中孵育24h后加入阿霉素和供试单体化合物或阳性对照药维拉帕米VRP和ES3，每孔100μL，设7个浓度梯度，设6个复孔，并设空白对照组和溶剂二甲基亚砜(DMSO)对照组；肿瘤细胞在温度37℃、浓度5％CO₂条件下培养48h后弃去上清液，加入噻唑蓝(MTT)液(5mg/mL，用生理盐水配制，以1:9的比例与完全培养基混匀，每孔100μL)，在温度37℃，浓度5％CO₂条件下继续培养4h后弃去上清液，每孔加入150μL二甲基亚砜(DMSO)，待甲臜溶解后，用酶标仪检测各孔570nm的吸光度值(A)，按下列公式计算供试单体化合物对肿瘤细胞生长的抑制率：抑制率(％)＝(A对照组－A给药组)/A对照组×100％；逆转倍数(RF)＝IC₅₀(阿霉素)/IC₅₀(阿霉素+化合物)；

实验结果：化合物1-17与阿霉素联用对MCF7/ADR细胞的半数生长抑制率及其逆转倍数见表1：

表1化合物1-17与阿霉素联用对耐阿霉素人乳腺癌细胞MCF7/ADR的半数生长抑制率及逆转倍数RF值

由表1可知，阿霉素分别与化合物1、2、6、7、8、9、10、11、12、14、15、16、17联用后与阿霉素单独作用相比，IC₅₀值显著降低；在相同浓度(10μM)下，化合物1、10、11、12、14、15、16、17具有较强的多药耐药逆转活性，其逆转倍数均高于阳性对照药维拉帕米，除此之外，化合物2、6、7、8、9与抗肿瘤药物阿霉素联用时，也具有一定多药耐药逆转活性。这些化合物可用作多药耐药逆转药物以辅助肿瘤化疗。