(S)-(E)-(+)-6-Pivaloxy-1-(trimethylsilyl)-1-hexen-3-ol | 157035-95-5

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 英文名称: (S)-(E)-(+)-6-Pivaloxy-1-(trimethylsilyl)-1-hexen-3-ol
• 英文别名: [(E,4S)-4-hydroxy-6-trimethylsilylhex-5-enyl] 2,2-dimethylpropanoate
• CAS: 157035-95-5
• 化学式: C₁₄H₂₈O₃Si
• 分子量: 272.46
• InChiKey: AVYDOMSRXJMAAJ-ZKQHCESOSA-N

物化性质

• 沸点：
  336.1±42.0 °C(predicted)
• 密度：
  0.938±0.06 g/cm3(Temp: 20 °C; Press: 760 Torr)(predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.15
• 重原子数：
  18
• 可旋转键数：
  8
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.79
• 拓扑面积：
  46.5
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  (S)-(E)-(+)-6-Pivaloxy-1-(trimethylsilyl)-1-hexen-3-ol 在 氢碘酸 、 sodium hydride 作用下， 以 N,N-二甲基甲酰胺 、 甲苯 为溶剂， 反应 18.0h， 生成 (S)-(-)-3-(Benzyloxy)-6-pivaloxy-1-hexene
  参考文献：
  名称：

  Catalytic Asymmetric Addition of Polyfunctional Dialkylzincs to .beta.-Stannylated and .beta.-Silylated Unsaturated Aldehydes

  摘要：

  The addition of functionalized dialkylzincs to readily available beta-stannylated or beta-silylated unsaturated aldehydes in the presence of a catalytic amount of (1R,2R)-1,2-bis(trifluorosulfonamido)cyclohexane (8 mol%) provides chiral allylic alcohols in good yields (60-90%) and excellent enantioselectivity (usually in the range of 85-95% ee). The synthetic utility of these allylic alcohols as chiral building blacks is demonstrated. The gamma-stannylated allylic alcohols were submitted to a Stille coupling leading to polyfunctional allylic alcohols and gamma-alkoxy enones. A treatment with CuCN in N-methylpyrrolidone at 130 degrees C provided chiral unsaturated gamma-hydroxy nitriles. Finally, the desilylation of the gamma-silylated alcohols gave chiral allylic alcohols having a terminal double bond. The catalytic asymmetric addition was found to show an important inverse temperature dependance. A mechanism for this addition is proposed.

  DOI：

  10.1021/jo00094a027
• 作为产物：
  描述：

  反-3-(三甲基硅基)烯丙醇 在 manganese(IV) oxide 作用下， 以 二氯甲烷 为溶剂， 反应 8.0h， 生成 (S)-(E)-(+)-6-Pivaloxy-1-(trimethylsilyl)-1-hexen-3-ol
  参考文献：
  名称：

  Catalytic Asymmetric Addition of Polyfunctional Dialkylzincs to .beta.-Stannylated and .beta.-Silylated Unsaturated Aldehydes

  摘要：

  The addition of functionalized dialkylzincs to readily available beta-stannylated or beta-silylated unsaturated aldehydes in the presence of a catalytic amount of (1R,2R)-1,2-bis(trifluorosulfonamido)cyclohexane (8 mol%) provides chiral allylic alcohols in good yields (60-90%) and excellent enantioselectivity (usually in the range of 85-95% ee). The synthetic utility of these allylic alcohols as chiral building blacks is demonstrated. The gamma-stannylated allylic alcohols were submitted to a Stille coupling leading to polyfunctional allylic alcohols and gamma-alkoxy enones. A treatment with CuCN in N-methylpyrrolidone at 130 degrees C provided chiral unsaturated gamma-hydroxy nitriles. Finally, the desilylation of the gamma-silylated alcohols gave chiral allylic alcohols having a terminal double bond. The catalytic asymmetric addition was found to show an important inverse temperature dependance. A mechanism for this addition is proposed.

  DOI：

  10.1021/jo00094a027

文献信息

• Ostwald Roswitha, Chavant Pierre-Yves, Stadtmueller Heinz, Knochel Paul, J. Org. Chem., 59 (1994) N 15, S 4143-4153
  作者：Ostwald Roswitha, Chavant Pierre-Yves, Stadtmueller Heinz, Knochel Paul

  DOI：——

  日期：——
• Catalytic Asymmetric Addition of Polyfunctional Dialkylzincs to .beta.-Stannylated and .beta.-Silylated Unsaturated Aldehydes
  作者：Roswitha Ostwald、Pierre-Yves Chavant、Heinz Stadtmueller、Paul Knochel

  DOI：10.1021/jo00094a027

  日期：1994.7

  The addition of functionalized dialkylzincs to readily available beta-stannylated or beta-silylated unsaturated aldehydes in the presence of a catalytic amount of (1R,2R)-1,2-bis(trifluorosulfonamido)cyclohexane (8 mol%) provides chiral allylic alcohols in good yields (60-90%) and excellent enantioselectivity (usually in the range of 85-95% ee). The synthetic utility of these allylic alcohols as chiral building blacks is demonstrated. The gamma-stannylated allylic alcohols were submitted to a Stille coupling leading to polyfunctional allylic alcohols and gamma-alkoxy enones. A treatment with CuCN in N-methylpyrrolidone at 130 degrees C provided chiral unsaturated gamma-hydroxy nitriles. Finally, the desilylation of the gamma-silylated alcohols gave chiral allylic alcohols having a terminal double bond. The catalytic asymmetric addition was found to show an important inverse temperature dependance. A mechanism for this addition is proposed.