(1R,2S)-(-)-2-<2-(tert-Butyldimethylsiloxy)-4-methylphenyl>-2-methyl-1-(triethylsiloxy)-1-vinylcyclobutanol | 154699-10-2

• 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: (1R,2S)-(-)-2-<2-(tert-Butyldimethylsiloxy)-4-methylphenyl>-2-methyl-1-(triethylsiloxy)-1-vinylcyclobutanol
• 英文别名: tert-butyl-[2-[(1S,2R)-2-ethenyl-1-methyl-2-triethylsilyloxycyclobutyl]-5-methylphenoxy]-dimethylsilane
• CAS: 154699-10-2
• 化学式: C₂₆H₄₆O₂Si₂
• 分子量: 446.821
• InChiKey: ONDLYNYLJSOZEL-UIOOFZCWSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  8.38
• 重原子数：
  30
• 可旋转键数：
  10
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.69
• 拓扑面积：
  18.5
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  (1R,2S)-(-)-2-<2-(tert-Butyldimethylsiloxy)-4-methylphenyl>-2-methyl-1-(triethylsiloxy)-1-vinylcyclobutanol 在 palladium diacetate 、 cerium(III) chloride 、 三苯胂 作用下， 以 四氢呋喃 、 乙醚 、 二氯甲烷 为溶剂， 反应 6.0h， 生成 (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 、 cerium(III) chloride 、 三丁基膦 、 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 40.5h， 生成 (1R,2S)-(-)-2-<2-(tert-Butyldimethylsiloxy)-4-methylphenyl>-2-methyl-1-(triethylsiloxy)-1-vinylcyclobutanol
  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.