(+/-)-(1S*,5R*)-1-<(4'E)-5'-(Methoxycarbonyl)pent-4-enyl>bicyclo<3.1.0>hexan-2-one

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 脂肪酰基
• 英文名称: (+/-)-(1S*,5R*)-1-<(4'E)-5'-(Methoxycarbonyl)pent-4-enyl>bicyclo<3.1.0>hexan-2-one
• 英文别名: methyl (E)-6-[(1R,5S)-2-oxo-1-bicyclo[3.1.0]hexanyl]hex-2-enoate
• 化学式: C₁₃H₁₈O₃
• 分子量: 222.284
• InChiKey: ADJGDKIGRZHAHG-CXRSCHCNSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.8
• 重原子数：
  16
• 可旋转键数：
  6
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.69
• 拓扑面积：
  43.4
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  (+/-)-(1S*,5R*)-1-<(4'E)-5'-(Methoxycarbonyl)pent-4-enyl>bicyclo<3.1.0>hexan-2-one 在 三乙基硼 、 三正丁基氢锡 、 六甲基二硅氮烷 作用下， 以 正己烷 、 1,2-二氯乙烷 、 甲苯 为溶剂， 生成 Methyl (+/-)-(1R*,3S*,7R*,8S*)-8-Methyl-1-(trimethylsiloxy)tricyclo<5.3.0.0^3,7>decane-2-carboxylate
  参考文献：
  名称：

  Ring Contraction of Cyclobutanes and a Novel Cascade Reaction: Application to Synthesis of (.+-.)-Anthoplalone and (.+-.)-Lepidozene

  摘要：

  Two efficient and practical synthetic methodologies for the construction of small ring systems have been developed. The first method involves a novel rearrangement of cyclobutanes 10 and 14 leading to cyclopropanes 11 and 15 employing BF3.OEt(2) or POCl3 in the presence of pyridine or Raney nickel. The second method utilizes a novel cascade reaction of alpha,beta-unsaturated esters 25 and 36 possessing a cyclopropyl ketone moiety with TMSI in the presence of(TMS)(2)NH to afford polycyclic cyclobutane derivatives 26 and 38. A synthesis of(+/-)-anthoplalone (41) and a formal synthesis of (+/-)-lepidozene (42) were achieved utilizing 15, obtained by the above method.

  DOI：

  10.1021/jo00105a028
• 作为产物：
  描述：

  (+/-)-(1S*,5R*)-1-<4'-(Benzyloxy)but-1'-enyl>-2,2-(ethylenedioxy)bicyclo<3.1.0>hexane 在 platinum(IV) oxide 4 A molecular sieve 、 氨 、 氢气 、 sodium 、 溶剂黄146 、 pyridinium chlorochromate 作用下， 以 四氢呋喃 、 二氯甲烷 、 乙酸乙酯 、 乙腈 、 叔丁醇 为溶剂， -78.0~25.0 ℃ 、101.33 kPa 条件下， 反应 29.0h， 生成 (+/-)-(1S*,5R*)-1-<(4'E)-5'-(Methoxycarbonyl)pent-4-enyl>bicyclo<3.1.0>hexan-2-one
  参考文献：
  名称：

  Ring Contraction of Cyclobutanes and a Novel Cascade Reaction: Application to Synthesis of (.+-.)-Anthoplalone and (.+-.)-Lepidozene

  摘要：

  Two efficient and practical synthetic methodologies for the construction of small ring systems have been developed. The first method involves a novel rearrangement of cyclobutanes 10 and 14 leading to cyclopropanes 11 and 15 employing BF3.OEt(2) or POCl3 in the presence of pyridine or Raney nickel. The second method utilizes a novel cascade reaction of alpha,beta-unsaturated esters 25 and 36 possessing a cyclopropyl ketone moiety with TMSI in the presence of(TMS)(2)NH to afford polycyclic cyclobutane derivatives 26 and 38. A synthesis of(+/-)-anthoplalone (41) and a formal synthesis of (+/-)-lepidozene (42) were achieved utilizing 15, obtained by the above method.

  DOI：

  10.1021/jo00105a028

文献信息

• Ring Contraction of Cyclobutanes and a Novel Cascade Reaction: Application to Synthesis of (.+-.)-Anthoplalone and (.+-.)-Lepidozene
  作者：Masataka Ihara、Takahiko Taniguchi、Yuji Tokunaga、Keiichiro Fukumoto

  DOI：10.1021/jo00105a028

  日期：1994.12

  Two efficient and practical synthetic methodologies for the construction of small ring systems have been developed. The first method involves a novel rearrangement of cyclobutanes 10 and 14 leading to cyclopropanes 11 and 15 employing BF3.OEt(2) or POCl3 in the presence of pyridine or Raney nickel. The second method utilizes a novel cascade reaction of alpha,beta-unsaturated esters 25 and 36 possessing a cyclopropyl ketone moiety with TMSI in the presence of(TMS)(2)NH to afford polycyclic cyclobutane derivatives 26 and 38. A synthesis of(+/-)-anthoplalone (41) and a formal synthesis of (+/-)-lepidozene (42) were achieved utilizing 15, obtained by the above method.