(tert-Butyldiphenylsiloxy)methyl 2-<(methoxymethyl)oxy>-4-methylphenyl ketone | 154698-94-9

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (tert-Butyldiphenylsiloxy)methyl 2-<(methoxymethyl)oxy>-4-methylphenyl ketone
• 英文别名: 2-[Tert-butyl(diphenyl)silyl]oxy-1-[2-(methoxymethoxy)-4-methylphenyl]ethanone
• CAS: 154698-94-9
• 化学式: C₂₇H₃₂O₄Si
• 分子量: 448.634
• InChiKey: OHTPBGXNTMRUEQ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.74
• 重原子数：
  32
• 可旋转键数：
  10
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.3
• 拓扑面积：
  44.8
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  (tert-Butyldiphenylsiloxy)methyl 2-<(methoxymethyl)oxy>-4-methylphenyl ketone 在 三(3,6-二氧杂庚基)胺 吡啶 、 4-二甲氨基吡啶 、 三氟化硼乙醚 、 四丁基氟化铵 、 sodium hydride 、 间氯过氧苯甲酸 、 乙硫醇 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 反应 40.25h， 生成 2-(Hydroxymethyl)-2-<2-<(p-toluenesulfonyl)oxy>-4-methylphenyl>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 三甲基铝 、 叔丁基锂 作用下， 以 乙醚 、 正己烷 、 二氯甲烷 为溶剂， 反应 6.08h， 生成 (tert-Butyldiphenylsiloxy)methyl 2-<(methoxymethyl)oxy>-4-methylphenyl ketone
  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.