侧链c-3位改造的紫杉烷类似物及其制备方法_2

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4, 25.62, 26.57, 26.88, 27.12, 27.15, 28.84, 31.91, 33.91, 36.69, 38.57, 41.92, 42.24, 47.76, 65.32, 71.66, 72.05, 72.13, 74.32, 76.29, 81.12, 82.07, 83.67, 84.46, 100.81, 107.47, 127.47, 127.91, 128.46, 128.52, 128.60, 129.78, 132.36, 133.38, 133.63, 137.07, 138.95, 140.69, 164.96, 169.32, 170. 21. 9b:iHNMR(500MHz'CDCls) 5 (卵m) :I. 10 (s, 3H, (?),I. 17 (d, / = 12. 4Hz,IH), 1.27 (s, 3H,邸3),1.71 (s, 3H,邸3),1.81 (s, 3H,邸3),1.90 (d, / = 6.4Hz,IH), 2.01(s, 3H, ^),2.07 (s,IH), 2.12 (s,IH), 2.66-2.71 (m,IH), 2.83-2.87 (m, IH), 3.32 (d, / = 4. 5Hz,IH), 3.56 (s,IH), 3.70 (d, / = 2.6 Hz,lH),3.89(s,lH),4.12-4.16(m,2H),4.21(d,/=ll.細z,lH),4.31(d, /= 7. 3Hz,IH), 4.42-4.45 (m,IH), 4.48 (s,IH), 5.02 (d, / = 9. 7Hz,IH), 5. 12-5. 15 (m, IH), 5.82 (d, /=2.9Hz,IH), 5.92 (d, /=8. 3Hz,IH), 6.35(d ,/ = 9. 8Hz,IH),7. 06-7. 09 (m, 4H),7. 19 扣 / = 7.8Hz, 3H),7. 35 扣 / = 8. 2 Hz, IH), 7.41 扣 / = 7. 7Hz, 2H), 7. 53 (d, / = 7.4 Hz, IH), 7. 56 扣 / = 8.8Hz, 2H),8. 15 (d, /=7.4Hz, 2H)."C-NMR(125MHz,CDCI3)5 (ppm): 14. 17, 16. 03, 20. 36, 25. 61, 27. 23, 29. 71, 32. 90, 33. 42, 37. 79, 42. 43, 45. 18, 47. 44, 59.26, 65.07, 69.35, 71.08, 71.64, 72.56, 72.63, 74.29, 75.99, 78.87, 126.77, 126.99, 127.16, 128.02, 128.37, 128.51, 128.68, 129.80, 130.01, 130.05, 132.40, 133.44, 135.73, 140.28, 165.51, 170.12, 171.38. HR-MS:calcdforC50H57NO16S([M+ 化]+),982. 3290,found982. 3299; 实施例S:制备化合物3' -N-对漠苯横酷-7, 9, 10-去乙酷基-I-去径基己卡亭VI的 制备方法,该化合物的结构式为: 方法同示例一:
6c: Ihnmr(500MHz, CDCls) 5 (卵m): 3.68 (S, 1H), 3.79 (S, 3H), 4.38 化 /= 2. 2 Hz, 1H), 4.88 (dd, /= 2. 3 9.8Hz, 1H), 6. 36 (d, /= 9.8Hz, 1H), 7. 13 (d, /= 1.2Hz, 2H), 7. 19 (d, /= 3.0Hz, IH), 7. 37 (s, IH), 7. 38-7.41 (m, 3H), 7. 46 (d, /=6.8Hz,IH);"CNMR(125MHz,CDCI3) 5 (卵m): 29. 70,53. 16, 53.22, 59.12, 59.52, 74.41, 80.35, 125.94, 127.04, 127.94, 128.46, 128.49, 129.15, 129.33, 131.83, 136.87, 138.89, 139.54, 158.16, 168.83, 172.53; 7c:咱NMR(500MHz, CDCI3) 5 (卵m): 1.80 (s, 3H), 1.87 (s, 3H), 3.72 (s, 3H), 4. 52 (d, /= 5.4Hz,IH), 5. 18 (d, /= 5.4Hz, IH), 7. 13-7. 17 (m, 4H), 7. 19-7. 22 (m, IH), 7. 27-7. 34 (m, 4H);"CNMR (125MHz,CDCI3) 5(ppm): 27. 20, 28.59, 52.70, 65.11, 81.69, 100.64, 127.26, 127.81, 128.23, 128.53, 128.95, 131.58, 137.22, 139.84, 170.26; 8c:iHNMR600MHz,CDCl3)5(wm):1.24(s,3H),1.27(s,3H),1.54(s, 6H), 1.69 (s, 3H), 1.81 (s, 3H), 1.88 (s,6H), 1.94 (s, 3H), 2.00 (d, /=8.8 Hz, IH), 2.06 (d, /= 11.2Hz,IH), 2.34-2.40 (m,IH), 2.57-2.64 (m, IH), 2.68 (d, /= 5.4 Hz, IH), 4.08 (d, /= 8.2 Hz, IH), 4. 31 扣 / = 6.8Hz, 2H), 4. 52 (d, /= 6.3 Hz, IH), 4.58 (d, /= 9.7 Hz, IH), 4.89 (d, /= 8.9 Hz, IH), 5.02 (d, J= 9.9Hz, IH), 5.12 (s, IH), 5.25 (d, / =6. 2 Hz, IH), 5.77 (d, / = 2.4 Hz, IH), 6.02 (t, /=8.8Hz,IH), 7.15-7.20 (m, 4H), 7.24-7.26 (m, IH), 7.29 (d, /= 8.6Hz, 3H), 7.37 (d, /= 8.4 Hz, IH), 7.47 扣 / = 7.6 Hz, 2H), 7.61 (t, /= 7. 2Hz,IH),8. 02 (d, /= 7.6Hz, 2H);"CNMR(1化MHz,CDCI3) 5 (ppm): 12. 96,15. 25,21. 78,24. 93,25. 62,26. 57,26. 88,26. 90,27. 12,27. :M,28. 63, 29.70, 31.92, 33.93, 36.71, 38.59, 41.95, 42.27, 47.79, 65.24, 71.68, 72.13, 74.33, 76.31, 81.19, 82.09, 83.69, 84.48, 101.00, 107.48, 127.38, 128.10, 128.38, 128.60, 128.63, 128.99, 129.54, 129.79, 131.62, 133.62, 136.71, 138.83, 139.78, 164.96, 169.26, 170.11 9c:iHNMR(500MHz,CDCI3) 5 (卵m):I. 10 (s, 3H, (?), 1.27 (s, 3H, (?),I. 72 (s, 3H, CH3),I. 79 (s, 3H, CH3),1.84-1.89 (m, 2H), 2.02 (s, 3H,CH3),2.07 (s, IH), 2.14 (s, IH), 2.69-2.74 (m,IH), 3.31 (d, / = 4.6Hz,IH), 3.50-3.60 (m,IH),3.89 (s, IH), 4.04 (s,IH), 4. 12-4. 17 (m, 2H), 4. 23 (d, /= 11.8Hz, IH), 4.30 (d, J= 12.3Hz, IH), 4.41-4.44 (m, IH), 4.48 (s, IH), 4.77-4.80 (m, IH), 4.96 (d, J= 9.9Hz, IH), 5.01 (d,J=10.0 Hz,IH), 5.06 (s,IH), 5.13 (dd, /= 9. 5 2.4 Hz,IH), 5.80-5.83 (m,IH), 7.04 (s, 2H), 7.09 (d, /= 7.4 Hz,IH), 7.12-7.14 (m, IH), 7.14 (d, J= 7.0Hz,IH), 7.26 (d, / = 9.6Hz, IH), 7.29 (s, 2H), 7.35 (d, J=15.1Hz,IH), 7.39 (d, J= 8.7Hz,IH), 7.41 a, /= 11.4 Hz, 2H),8. 14 (d, /=8.0Hz, 2H);"CNMR(125MHz, CDCI3) 5 (ppm): 14.19, 14.24, 15.67, 16.11, 20.36, 21.06, 22.40, 22.70, 25.57, 26.13, 29. 70, 31. 93, 32. 07, 32. 94, 33. 29, 37. 74, 38. 02, 42. 57, 45. 15, 45. 22, 47. 50, 59.42, 60.45, 65.22, 69.30, 71.03, 71.10, 71.51, 72.45, 72.62, 74.46, 74.95, 76.00, 78.89, 127.16, 127.28, 127.32, 128.05, 128.18, 128.37, 128.45, 128.52, 129.77, 129.97, 130.02, 133.50, 134.55, 135.92, 139.17, 139.35, 139.57, 165.51, 165.71, 170.17, 171.18, 172.15. HR-MS:calcdforCsoHseBrNOieS([M+ 化]+),1060. 2395,found1060. 2415。
[0015] 实施例四:制备化合物3' -N-2-嚷吩横酷-7, 9, 10-去乙酷基-I-去径基己卡亭VI的 制备方法,该化合物的结构式为:
[001引 方法同示例一: 6d:咱NMR (500 MHz,CDCI3) 5(卵m):3. 79 (S, 3H), 4. 37 化 /= 2. 3 Hz, 1H), 4.93 (dd, /= 2.4 9.8 Hz, 1H), 5.53-5.55 (m, 1H), 6.33 (d, /=9.8 Hz, 1H), 6.82 (dd, /= 3.8 5.2 Hz, 1H), 7.17-7.19 (m, 5H), 7.31 (dd, /= 1.3 3.7 Hz, 1H), 7. 38 (dd, / = 1. 3 5.0 Hz, 1H) ; "C NMR (125 MHz, CDCI3) 5 (卵m): 22.15, 27.81, 33.15, 53.18, 59.53, 68.61, 74.42, 98.38, 126.83, 127.05, 127.88, 128.40, 131.71, 132.17, 137.14, 141.50, 172.43; 7d:iHNMR600MHz,CDCl3)5(wm):1.81(s,3H),1.87(s,3H),3.75(s, 3H), 4.60 (d, /= 4.6Hz, 1H), 5. 27 (d, / = 4.6Hz, 1H), 6.87 扣 / = 4. 2Hz, IH), 7.21 (d, /=2.9Hz,IH), 7.28 (s, 2H), 7.29 (s,IH), 7. 37 (d, /=5.6Hz, 2H), 7. 48 (d, /=4.6Hz, IH);"CNMR(125 MHz,CDCI3) 5 (卵m): 26. 66,29. 04, 52.70, 65.18, 81.65, 100.70, 126.75, 127.36, 128.21, 128.53, 131.95, 133.00, 138.27, 141.67, 170.29; 8d:咱NMR(500MHz,CDCI3) 5 (卵m) :I. 22 (s, 3H),I. 52 (s,6H),I.68(s, 3H), 1.80 (s, 3H), 1.82 (s, 3H), 1.85 (s, 3H), 1.88 (s, 3H), 1.89 (s, 3H), 1.98 扣 /=9. 3Hz, 2H), 2.04 (s, IH), 2. 34-2.41 (m,IH), 2. 55-2.61 (m, IH), 2.67 (d, /= 5. 4Hz, IH), 4.06 (d, / = 8. 2Hz, IH), 4.29 (d, / = 7.8Hz, 2H), 4. 56 (d, /= 5.4Hz, IH), 4.88 (d, /= 8.8Hz, IH), 5.00 (d, /= 9.9 Hz, IH), 5. 11 (s,IH), 5.29 (d, /= 5.7Hz,IH), 5.67 (d, /= 3.8Hz,IH),6.00 扣 / =8.6Hz,IH),6.86(t, / = 4. 2 Hz,IH), 7.21 (d,J= 3.0Hz, IH), 7.26-7.28 (m, 3H), 7. 35 (s, 2H), 7.44-7.49 (m, 3H), 7.60 扣 / = 7. 3 Hz, IH),8. Ol (d, / = 7.6Hz, 2H) ;"CNMR(125MHz,CDCI3) 5 (卵m) : 12. 94,15. 23,21. 80, 26.55, 26.71, 26.88, 27.11, 29.03, 31.90, 36.69, 38.57, 41.92, 42.24, 47.74, 65.34, 71.63, 72.08, 72.13, 74.13, 76.27, 81.13, 81.95, 83.67, 84.44, 100.90, 107.47, 126.83, 127.53, 128.63, 128.65, 129.78, 132.16, 133.12, 133.44, 133.66, 137.87, 138.90, 141.44, 164.97, 169.33, 170.06. 9d:咱NMR(500MHz, CDCI3) 5 (卵m): I. 11 (s, 3H), 1.27 (s, 3H), 1.74 (s, 3H), 1.82 (s, 3H), 1.90 (d, J= 7.6Hz, 2H), 2.02 (s, 3H), 2.07 (s, 2H), 2.31-2.37 (m,IH), 2.68-2.73 (m,IH), 2.85 (d,J=15.9Hz,IH), 3.32 (d,J=4.4Hz,IH), 3. 57 (s,IH), 3.66 扣 /=6.6Hz, IH),3.88 (s, IH), 4.09-4. 13 (m,IH), 4.24 (d, J= 11.8Hz, IH), 4.30 (d,J= 9.9Hz,IH), 4.42-4.44 (m, IH), 4.49 (s, IH), 5.02 (d, /= 10.0Hz,IH), 5.09-5. 17 (m,IH), 5.82 (s,IH), 5.94 (d, / = 9. 2Hz,IH),6. 54 (s,IH),6. 75 扣 / = 4. 3Hz,IH), 7. 17 (brs, 5H), 7.24 (d, /= 3.1 Hz,IH), 7.36 (d, /= 4.8Hz,IH), 7.43 (d, /= 7.6Hz, 2H), 7. 56(t, /= 7. 2Hz,IH),8. 15(d, /= 7.8Hz, 2H);"CNMR(125MHz,CDCI3) 5 (卵m): 14. 13, 16.02, 20. 38, 22. 70, 25. 60, 27. 21, 29. 71, 31.93, 32. 91, 37.77, 42.39, 45.16, 47.43, 59.44, 65.02, 69.31, 71.11, 71.61, 72.51, 72.61, 74.29, 75.96, 78.87, 126.85, 127.16, 128.13, 128.45, 128.52, 129.78, 130.09, 131.93, 132.54, 133.44, 134.64, 135.77, 139.53, 141.20, 165.51, 170.09, 171. 31. HR-MS:calcdforCa品sNOieSz([M+ 化]+),988. 2854,found988. 2882。
[0017] 实施例五:制备化合物3' -N-2, 3-二氨苯并巧喃-5-横酷-7, 9, 10-去乙酷基-I-去 径基己卡亭VI的制备方法,该化合物的结构式为: 方法同示例一:
6e:iHNMR600MHz,CDCl3)5(ppm):2.98-3.09 (m,2H),3.59(s,lH),3.81(S,3H),4. 37 化 / = 2. 1Hz, 1H),4. 57 扣 / =8.8Hz, 2H),4. 83 (dd, / = 2. 2 10.2Hz,IH), 6.01 (d,J= 9.9Hz,IH), 6.62 (d, / =8.4Hz,IH), 7.14-7.18 (m, 5H), 7. 36 (s,IH), 7.47 (dd, /= 1.38.4Hz,IH);NMR(125MHz,CDCI3) 5 (卵m) : 28. 84,53. 20,59. 35,72. 18,74. 43,109. 02,124. 45,127. 09,127. 71, 127.83, 128.26, 128.52, 131.93, 137.38, 163.43, 172.63; 7e:iHNMR600MHz,CDCl3)5(ppm):1.82(s,3H),1.88(s,3H),2.95-3.09 (m, 2H), 3.74 (s,甜),4.50 (d, /=5.6Hz, IH), 4. 57 (t, /=8.8Hz, 2H), 5. 14 (d, /=5.4Hz,IH), 6.59 (d, /=8.5Hz,IH), 7. 12 (s, IH), 7. 15-7. 19 (m, 5H), 7. 34 (dd, /= 1.48. 4Hz,IH);"CNMR(125MHz,CDCI3) 5 (卵m): 26. 89,28. 75, 28.80, 52.62, 65.07, 72.20, 81.79, 100.53, 125.11, 127.29, 127.75, 127.86, 128.19, 129.16, 132.32, 137.92, 163.44, 170.45. 8e:iHNMR600MHz,CDCl3)5(wm):1.14(s,3H),1.53(s,6H),1.68(s, 3H), 1.80 (s, 3H), 1.86 (s, 3H), 1.88 (s, 3H), 1.89 (s, 3H), 1.93 (s, 3H), 1.98 (d, /=8.6Hz,IH), 2.34-2.39 (m,IH), 2.56-2.62 (m,IH), 2.68 (d,J=5.4Hz,IH), 2.92-3.03 (m, IH), 3.04-3.11 (m,IH), 4.06 (d, / =8. 2Hz,IH), 4. 11-4. 15 (m,IH), 4. 28-4. 32 (m, 2H), 4.48 (d, /=6.6Hz,IH), 4. 59 扣 / =8.9Hz,甜),4.88(d, /= 8.9 Hz,IH), 5.02 (d, /= 10.0Hz, IH), 5. 12 (s, IH), 5. 19 (d,方6.6Hz, IH), 5.76 (d,方 3.6Hz,IH), 6. 10 扣 / =8.6Hz, IH), 6.60 (d, /=8.4 Hz,IH), 7. 13-7. 20 (m,6H), 7. 33 (dd, /= 1.28. 5 Hz,IH), 7.46 扣 / = 7.7 Hz, 2H), 7.60 扣 / = 7.4 Hz,IH), 8.01 (d, / = 7.4 Hz, 2H); "CNMR(125MHz,CDCI3) 5 (卵m) : 12. 95,14. 20,15. 24,26. 59,26. 88
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