(Z)-4-(2-Bromo-4,5-methylenedioxybenzyl)-3-(3,4,5-trimethoxybenzylidene)dihydro-2(3H)-furanone | 137047-04-2

• 分子结构分类: 有机化合物 - 木脂素、新木脂素和相关化合物
• 英文名称: (Z)-4-(2-Bromo-4,5-methylenedioxybenzyl)-3-(3,4,5-trimethoxybenzylidene)dihydro-2(3H)-furanone
• 英文别名: (Z)-α-benzylidene-β-(o-bromobenzyl)-γ-lactone
• CAS: 137047-04-2
• 化学式: C₂₂H₂₁BrO₇
• 分子量: 477.309
• InChiKey: BJLFPMWOXBGKKX-TVPGTPATSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.0
• 重原子数：
  30.0
• 可旋转键数：
  6.0
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.32
• 拓扑面积：
  72.45
• 氢给体数：
  0.0
• 氢受体数：
  7.0

反应信息

• 作为反应物：
  描述：

  (Z)-4-(2-Bromo-4,5-methylenedioxybenzyl)-3-(3,4,5-trimethoxybenzylidene)dihydro-2(3H)-furanone 在 bis-triphenylphosphine-palladium(II) chloride potassium carbonate 、 三苯基膦 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 反应 5.0h， 以75%的产率得到(dl)-5-(3,4,5-trimethoxyphenyl)-8a,9-dihydrofuro[3′,4’:6,7]-naphtho[2,3-d][1,3]dioxol-6(8H)-one
  参考文献：
  名称：

  Synthesis of podophyllotoxin derivatives by means of tributyltin hydride- or palladium-mediated cyclization of α-benzylidene-β-(o-bromobenzyl)-γ-lactones

  摘要：

  Synthesis of podophyllotoxin derivatives based on an aryl radical cyclization of alpha-benzylidene-beta-(o-bromobenzyl)-gamma-lactones 20 and 21 has been examined. Treatment of a mixture of the alcohols 18a and 18b (ca. 1:1), prepared from 6-bromopiperonal (10) in 7 steps, with methanesulfonyl chloride gave a ca. 3:1 mixture of the chlorides 19a and 19b, which was treated with DBU to give the (Z)- and (E)-alpha-benzylidene-gamma-lactones 20 and 21 in 64 and 22% yields, respectively. Thermolysis of the mixture of the sulfoxides 23a and 23b, prepared from 18a,b, afforded the E-isomer 21 as a major product. The Z-benzylidenelactone 20 when treated with Bu3SnH in the presence of AIBN gave the 6-endo-trig radical cyclization product, (+/-)-deoxyisopicropodophyllin (24), and the 5-exo-trig cyclization product 25 in 29 and 49% yields, respectively. The E-isomer 21, however, gave only the 5-exo cyclization product 25. On the other hand, treatment of 20 with PdCl2(PPh3)3 gave (+/-)-gamma-apopicropodophyllin (29) in 75% yield. Similar treatment of 21 afforded no cyclization product, but, in the presence of sodium formate (H- source), gave the 5-exo cyclization product 25 in 84% yield.

  DOI：

  10.1016/s0040-4020(01)85735-5
• 作为产物：
  描述：

  trans-4-(2-Bromo-4,5-methylenedioxybenzyl)-3-(α-chloro-3,4,5-trimethoxybenzyl)dihydro-2(3H)-furanone 在 1,8-二氮杂双环[5.4.0]十一碳-7-烯 作用下， 以 乙腈 为溶剂， 反应 5.0h， 以22%的产率得到(E)-4-(2-Bromo-4,5-methylenedioxybenzyl)-3-(3,4,5-trimethoxybenzylidene)dihydro-2(3H)-furanone
  参考文献：
  名称：

  Synthesis of podophyllotoxin derivatives by means of tributyltin hydride- or palladium-mediated cyclization of α-benzylidene-β-(o-bromobenzyl)-γ-lactones

  摘要：

  Synthesis of podophyllotoxin derivatives based on an aryl radical cyclization of alpha-benzylidene-beta-(o-bromobenzyl)-gamma-lactones 20 and 21 has been examined. Treatment of a mixture of the alcohols 18a and 18b (ca. 1:1), prepared from 6-bromopiperonal (10) in 7 steps, with methanesulfonyl chloride gave a ca. 3:1 mixture of the chlorides 19a and 19b, which was treated with DBU to give the (Z)- and (E)-alpha-benzylidene-gamma-lactones 20 and 21 in 64 and 22% yields, respectively. Thermolysis of the mixture of the sulfoxides 23a and 23b, prepared from 18a,b, afforded the E-isomer 21 as a major product. The Z-benzylidenelactone 20 when treated with Bu3SnH in the presence of AIBN gave the 6-endo-trig radical cyclization product, (+/-)-deoxyisopicropodophyllin (24), and the 5-exo-trig cyclization product 25 in 29 and 49% yields, respectively. The E-isomer 21, however, gave only the 5-exo cyclization product 25. On the other hand, treatment of 20 with PdCl2(PPh3)3 gave (+/-)-gamma-apopicropodophyllin (29) in 75% yield. Similar treatment of 21 afforded no cyclization product, but, in the presence of sodium formate (H- source), gave the 5-exo cyclization product 25 in 84% yield.

  DOI：

  10.1016/s0040-4020(01)85735-5

文献信息

• Ishibashi, Hiroyuki; Ito, Katsuhiro; Tabuchi, Masayo, Heterocycles, 1991, vol. 32, # 7, p. 1279 - 1282
  作者：Ishibashi, Hiroyuki、Ito, Katsuhiro、Tabuchi, Masayo、Ikeda, Masazumi

  DOI：——

  日期：——