(3R)-(-)-3-<2-(tert-Butyldimethylsiloxy)-4-methylphenyl>-3-methyl-2-methylidenecyclopentanone | 154699-11-3

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: (3R)-(-)-3-<2-(tert-Butyldimethylsiloxy)-4-methylphenyl>-3-methyl-2-methylidenecyclopentanone
• 英文别名: (3S)-3-[2-[tert-butyl(dimethyl)silyl]oxy-4-methylphenyl]-3-methyl-2-methylidenecyclopentan-1-one
• CAS: 154699-11-3
• 化学式: C₂₀H₃₀O₂Si
• 分子量: 330.543
• InChiKey: LRIKTZJIMLWHLR-HXUWFJFHSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.56
• 重原子数：
  23
• 可旋转键数：
  4
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.55
• 拓扑面积：
  26.3
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  甲基锂 、 (3R)-(-)-3-<2-(tert-Butyldimethylsiloxy)-4-methylphenyl>-3-methyl-2-methylidenecyclopentanone 在 cerium(III) chloride 作用下， 以 四氢呋喃 、 乙醚 为溶剂， 生成 (1R,3R)-3-<2-(tert-Butyldimethylsiloxy)-4-methylphenyl>-1,3-dimethyl-2-methylidenecyclopentanol 、 (1S,3R)-3-<2-(tert-Butyldimethylsiloxy)-4-methylphenyl>-1,3-dimethyl-2-methylidenecyclopentanol
  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：

  1-(甲氧基甲氧基)-3-甲基苯 在 三(3,6-二氧杂庚基)胺 吡啶 、 咪唑 、 2,6-二甲基吡啶 、 4-二甲氨基吡啶 、 palladium diacetate 、 cerium(III) chloride 、 三丁基膦 、 三苯胂 、 Raney Ni(W₂) 、 三氟化硼乙醚 、 四丁基氟化铵 、 叔丁基锂 、 sodium hydride 、 二异丁基氢化铝 、 间氯过氧苯甲酸 、 乙硫醇 作用下， 以 四氢呋喃 、 乙醚 、 正己烷 、 二氯甲烷 、 N,N-二甲基甲酰胺 、 丙酮 为溶剂， 反应 43.5h， 生成 (3R)-(-)-3-<2-(tert-Butyldimethylsiloxy)-4-methylphenyl>-3-methyl-2-methylidenecyclopentanone
  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.