(Z)-2-bromo-3-trimethylsilyl-2-propenal | 147727-39-7

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (Z)-2-bromo-3-trimethylsilyl-2-propenal
• 英文别名: (Z)-2-bromo-3-(trimethylsilyl)propenal；(Z)-2-bromo-3-trimethylsilylprop-2-enal
• CAS: 147727-39-7
• 化学式: C₆H₁₁BrOSi
• 分子量: 207.142
• InChiKey: QKTQJEODWYQETE-WAYWQWQTSA-N

物化性质

• 沸点：
  197.2±30.0 °C(Predicted)
• 密度：
  1.238±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.34
• 重原子数：
  9
• 可旋转键数：
  2
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  17.1
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  (Z)-2-bromo-3-trimethylsilyl-2-propenal 在 二异丁基氢化铝 作用下， 以 正己烷 、 二氯甲烷 为溶剂， 反应 0.25h， 以78%的产率得到(Z)-2-bromo-3-(trimethylsilyl)propen-1-ol
  参考文献：
  名称：

  An intramolecular cyclization approach to optically active cyclopentenyl bromides

  摘要：

  The two antipodes of 1-bromo-3,3-dimethyl-4-[(tert-butyldimethylsilyl)oxy]cyclopentene, the dextrorotatory form of which (1) is regarded as a potential synthetic precursor to kalmanol, have been prepared in a state of high enantiomeric purity from propargyl alcohol. The key steps in the abbreviated synthetic pathway involve the bromination-dehydrobromination of aldehyde 12 to give 7, the conversion of alcohol 13 to the hydroxyl-substituted bromocyclopentene 18 by a novel tandem Claisen-Sakurai reaction sequence, and efficient enzymatic resolution of 18 via its chloroacetate ester. The absolute configurational assignments are based on H-1 NMR analyses of the (R)- and (S)-MTPA esters of (-)-20.

  DOI：

  10.1021/jo00062a011
• 作为产物：
  描述：

  trimethylsilylpropenal 在 溴 、 三乙胺 、 碘 作用下， 以 四氯化碳 、 苯 为溶剂， 反应 169.0h， 生成 (Z)-2-bromo-3-trimethylsilyl-2-propenal
  参考文献：
  名称：

  轴向手性Allenylsilanes的钯催化不对称合成及其与S应用è 2“手性转移反应

  摘要：

  将Pd催化的S N 2'反应和脱甲硅烷基化的S E 2'反应逐步应用到矛盾的2-溴-1-甲硅烷基-1,3-二烯上，为叔和季炔丙基的高对映选择性构建提供了一条新途径通过轴向手性烯基硅烷形成立体中心。

  DOI：

  10.1021/ol102554a

文献信息

• Palladium-Catalyzed Asymmetric Synthesis of Axially Chiral Allenylsilanes and Their Application to S_E2′ Chirality Transfer Reactions
  作者：Masamichi Ogasawara、Atsushi Okada、Velusamy Subbarayan、Sebastian Sörgel、Tamotsu Takahashi

  DOI：10.1021/ol102554a

  日期：2010.12.17

  desilylative SE2′ reaction to the ambivalent 2-bromo-1-silyl-1,3-dienes provides a novel route to the highly enantioselective construction of tertiary and quaternary propargylic stereogenic centers via axially chiral allenylsilanes.

  将Pd催化的S N 2'反应和脱甲硅烷基化的S E 2'反应逐步应用到矛盾的2-溴-1-甲硅烷基-1,3-二烯上，为叔和季炔丙基的高对映选择性构建提供了一条新途径通过轴向手性烯基硅烷形成立体中心。
• An intramolecular cyclization approach to optically active cyclopentenyl bromides
  作者：Stephane Borrelly、Leo A. Paquette

  DOI：10.1021/jo00062a011

  日期：1993.5

  The two antipodes of 1-bromo-3,3-dimethyl-4-[(tert-butyldimethylsilyl)oxy]cyclopentene, the dextrorotatory form of which (1) is regarded as a potential synthetic precursor to kalmanol, have been prepared in a state of high enantiomeric purity from propargyl alcohol. The key steps in the abbreviated synthetic pathway involve the bromination-dehydrobromination of aldehyde 12 to give 7, the conversion of alcohol 13 to the hydroxyl-substituted bromocyclopentene 18 by a novel tandem Claisen-Sakurai reaction sequence, and efficient enzymatic resolution of 18 via its chloroacetate ester. The absolute configurational assignments are based on H-1 NMR analyses of the (R)- and (S)-MTPA esters of (-)-20.