(+/-)-(1S*,2S*,3S*)-1-Acetyl-1-((tert-butyldiphenylsiloxy)methyl)-3-<(3'E)-4'-(methoxycarbonyl)but-3'-enyl>-1-methylcyclopropane

• 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*,2S*,3S*)-1-Acetyl-1-((tert-butyldiphenylsiloxy)methyl)-3-<(3'E)-4'-(methoxycarbonyl)but-3'-enyl>-1-methylcyclopropane
• 英文别名: methyl (E)-5-[(1R,2R,3R)-2-acetyl-3-[[tert-butyl(diphenyl)silyl]oxymethyl]-2-methylcyclopropyl]pent-2-enoate
• 化学式: C₂₉H₃₈O₄Si
• 分子量: 478.704
• InChiKey: YZEHSMBPUWTKNJ-QKDWQAOKSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.91
• 重原子数：
  34
• 可旋转键数：
  12
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.45
• 拓扑面积：
  52.6
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  (+/-)-(1S*,2S*,3S*)-1-Acetyl-1-((tert-butyldiphenylsiloxy)methyl)-3-<(3'E)-4'-(methoxycarbonyl)but-3'-enyl>-1-methylcyclopropane 在 三乙基硼 、 三正丁基氢锡 、 六甲基二硅氮烷 作用下， 以 二氯甲烷 为溶剂， 反应 7.17h， 生成 (1R,2R,5R,6R,7S)-2-[2-(tert-Butyl-diphenyl-silanyloxy)-ethyl]-1,7-dimethyl-7-trimethylsilanyloxymethyl-bicyclo[3.2.0]heptane-6-carboxylic acid methyl ester
  参考文献：
  名称：

  通过环丙烷-Michael-aldol反应序列的连续三个反应开环构建与环丁烷稠合的多环体系

  摘要：

  具有环丙基酮功能的α，β-不饱和酯4和11与三甲基甲硅烷基碘在六甲基二硅氮烷存在下的反应引起依次的三个反应，即环丙烷-迈克尔-醛醇缩合反应序列的开环，从而提供了多环环丁烷衍生物7和13，分别。

  DOI：

  10.1016/s0040-4039(00)73191-1
• 作为产物：
  描述：

  (+/-)-(1S*,2S*,3S*)-1-Acetyl-2-((tert-butyldiphenylsiloxy)methyl)-3-(3',3'-dimethoxypropyl)-1-methylcyclopropane 在 溶剂黄146 作用下， 以 四氢呋喃 、 乙腈 为溶剂， 反应 22.0h， 生成 (+/-)-(1S*,2S*,3S*)-1-Acetyl-1-((tert-butyldiphenylsiloxy)methyl)-3-<(3'E)-4'-(methoxycarbonyl)but-3'-enyl>-1-methylcyclopropane
  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

• Stereocontrolled intramolecular michael-aldol reaction mediated with bu2botf and (tms)2nh
  作者：Masataka Ihara、Takahiko Taniguchi、Masami Yamada、Yuji Tokunaga、Keiichiro Fukumoto

  DOI：10.1016/0040-4039(95)01711-p

  日期：1995.10

  Treatment of keto-esters 1-5 with Bu(2)BOTf and (TMS)(2)NH caused a tandem Michael-aldol reaction to give polycyclic cyclobutanes 6-10 with high stereoselection. It was proved that the reaction was accelerated by the addition of Bu(4)NI.
• 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.
• Construction of polycyclic ring systems fused to cyclobutane by sequential three reactions ring opening of cyclopropane-Michael-aldol reaction sequence
  作者：Masataka Ihara、Takahiko Taniguchi、Keiichiro Fukumoto

  DOI：10.1016/s0040-4039(00)73191-1

  日期：1994.3

  4 and 11 possessing a cyclopropyl ketone function, with trimethylsilyl iodide in the presence of hexamethyldisilazane caused sequential three reactions, ring opening of cyclopropane-Michael-aldol reaction sequence, to provide polycyclic cyclobutane derivatives 7 and 13, respectively.

  具有环丙基酮功能的α，β-不饱和酯4和11与三甲基甲硅烷基碘在六甲基二硅氮烷存在下的反应引起依次的三个反应，即环丙烷-迈克尔-醛醇缩合反应序列的开环，从而提供了多环环丁烷衍生物7和13，分别。