1-(tert-Butyldiphenylsiloxy)-2-cyclopropylidene-2-<2-<(methoxymethyl)oxy>-4-methylphenyl>ethane | 154698-95-0

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯酚醚
• 英文名称: 1-(tert-Butyldiphenylsiloxy)-2-cyclopropylidene-2-<2-<(methoxymethyl)oxy>-4-methylphenyl>ethane
• 英文别名: Tert-butyl-[2-cyclopropylidene-2-[2-(methoxymethoxy)-4-methylphenyl]ethoxy]-diphenylsilane
• CAS: 154698-95-0
• 化学式: C₃₀H₃₆O₃Si
• 分子量: 472.7
• InChiKey: YQYYQVWDFAETBL-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.1
• 重原子数：
  34
• 可旋转键数：
  10
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.33
• 拓扑面积：
  27.7
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  1-(tert-Butyldiphenylsiloxy)-2-cyclopropylidene-2-<2-<(methoxymethyl)oxy>-4-methylphenyl>ethane 在 吡啶 、 咪唑 、 titanium(IV) isopropylate 、 叔丁基过氧化氢 、 4-二甲氨基吡啶 、 L-(+)-酒石酸二异丙酯 、 3 A molecular sieve 、 三氟化硼乙醚 、 四丁基氟化铵 、 二异丁基氢化铝 、 乙硫醇 作用下， 以 四氢呋喃 、 正己烷 、 二氯甲烷 、 N,N-二甲基甲酰胺 为溶剂， 反应 63.5h， 生成 (R)-(+)-2-<2-(tert-Butyldimethylsiloxy)-4-methylphenyl>-2-(hydroxymethyl)cyclobutanone
  参考文献：
  名称：

  A remarkable substituent effect on the enantioselectivity of tandem asymmetric epoxidation and enantiospecific ring expansion of cyclopropylidene alcohols: a new enantiocontrolled synthesis of (-)-debromoaplysin and (-)-aplysin

  摘要：

  A remarkable substituent effect by the tert-butyldimethylsiloxy group on the enantioselectivity of the tandem asymmetric epoxidation and enantiospecific ring expansion of 2-[2-(tert-butyldimethylsiloxy)-4-methylphenyl]-2-cyclopropylideneethanol (18), affording (S)-(-)-2-[2-(tert-butyldimethylsiloxy)-4-methylphenyl]-2-hydroxymethylcyclobutanone (21) in high yield and high enantiomeric excess, was observed. This enabled us to accomplish a concise and highly enantioselective total synthesis of (-)-debromoaplysin (2) and (-)-aplysin (1), providing a new and general strategy for the enantioselective synthesis of biologically important substances having the dihydrobenzofuran framework.

  DOI：

  10.1021/jo00080a014
• 作为产物：
  描述：

  2-((叔丁基二苯基甲硅烷基)氧基)乙酸甲酯 在 三(3,6-二氧杂庚基)胺 三甲基铝 、 叔丁基锂 、 sodium hydride 作用下， 以 四氢呋喃 、 乙醚 、 正己烷 、 二氯甲烷 为溶剂， 反应 17.08h， 生成 1-(tert-Butyldiphenylsiloxy)-2-cyclopropylidene-2-<2-<(methoxymethyl)oxy>-4-methylphenyl>ethane
  参考文献：
  名称：

  A remarkable substituent effect on the enantioselectivity of tandem asymmetric epoxidation and enantiospecific ring expansion of cyclopropylidene alcohols: a new enantiocontrolled synthesis of (-)-debromoaplysin and (-)-aplysin

  摘要：

  A remarkable substituent effect by the tert-butyldimethylsiloxy group on the enantioselectivity of the tandem asymmetric epoxidation and enantiospecific ring expansion of 2-[2-(tert-butyldimethylsiloxy)-4-methylphenyl]-2-cyclopropylideneethanol (18), affording (S)-(-)-2-[2-(tert-butyldimethylsiloxy)-4-methylphenyl]-2-hydroxymethylcyclobutanone (21) in high yield and high enantiomeric excess, was observed. This enabled us to accomplish a concise and highly enantioselective total synthesis of (-)-debromoaplysin (2) and (-)-aplysin (1), providing a new and general strategy for the enantioselective synthesis of biologically important substances having the dihydrobenzofuran framework.

  DOI：

  10.1021/jo00080a014

文献信息

• A remarkable substituent effect on the enantioselectivity of tandem asymmetric epoxidation and enantiospecific ring expansion of cyclopropylidene alcohols: a new enantiocontrolled synthesis of (-)-debromoaplysin and (-)-aplysin
  作者：Hideo Nemoto、Masatoshi Nagamochi、Hiroki Ishibashi、Keiichiro Fukumoto

  DOI：10.1021/jo00080a014

  日期：1994.1

  A remarkable substituent effect by the tert-butyldimethylsiloxy group on the enantioselectivity of the tandem asymmetric epoxidation and enantiospecific ring expansion of 2-[2-(tert-butyldimethylsiloxy)-4-methylphenyl]-2-cyclopropylideneethanol (18), affording (S)-(-)-2-[2-(tert-butyldimethylsiloxy)-4-methylphenyl]-2-hydroxymethylcyclobutanone (21) in high yield and high enantiomeric excess, was observed. This enabled us to accomplish a concise and highly enantioselective total synthesis of (-)-debromoaplysin (2) and (-)-aplysin (1), providing a new and general strategy for the enantioselective synthesis of biologically important substances having the dihydrobenzofuran framework.