tert-butyl 3-cyano-3-(trimethylsilyloxy)butanoate | 1003922-15-3

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 脂肪酰基
• 英文名称: tert-butyl 3-cyano-3-(trimethylsilyloxy)butanoate
• 英文别名: tert-butyl (3S)-3-cyano-3-trimethylsilyloxybutanoate
• CAS: 1003922-15-3
• 化学式: C₁₂H₂₃NO₃Si
• 分子量: 257.405
• InChiKey: ZWBVZSXMUPXRFM-LBPRGKRZSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.85
• 重原子数：
  17
• 可旋转键数：
  6
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.83
• 拓扑面积：
  59.3
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为产物：
  描述：

  乙酰乙酸叔丁酯 、 三甲基氰硅烷 在 2,2,2-三氟乙醇 作用下， 以 二氯甲烷 、 甲苯 为溶剂， 反应 18.0h， 生成 tert-butyl 3-cyano-3-(trimethylsilyloxy)butanoate 、 tert-butyl (3R)-3-cyano-3-trimethylsilyloxybutanoate
  参考文献：
  名称：

  Cooperative Catalysis by Tertiary Amino-Thioureas:  Mechanism and Basis for Enantioselectivity of Ketone Cyanosilylation

  摘要：

  The mechanism of the enantioselective cyanosilylation of ketones catalyzed by tertiary aminothiourea derivatives was investigated using a combination of experimental and theoretical methods. The kinetic analysis is consistent with a cooperative mechanism in which both the thiourea and the tertiary amine of the catalyst are involved productively in the rate-limiting cyanide addition step. Density functional theory calculations were used to distinguish between mechanisms involving thiourea activation of ketone or of cyanide in the enantioselectivity-determining step. The strong correlation obtained between experimental and calculated ee's for a range of substrates and catalysts provides support for the most favorable calculated transition structures involving amine-bound HCN adding to thiourea-bound ketone. The calculations suggest that enantioselectivity arises from direct interactions between the ketone substrate and the amino-acid derived portion of the catalyst. On the basis of this insight, more enantioselective catalysts with broader substrate scope were prepared and evaluated experimentally.

  DOI：

  10.1021/ja0735352

文献信息

• Cooperative Catalysis by Tertiary Amino-Thioureas:  Mechanism and Basis for Enantioselectivity of Ketone Cyanosilylation
  作者：Stephan J. Zuend、Eric N. Jacobsen

  DOI：10.1021/ja0735352

  日期：2007.12.1

  The mechanism of the enantioselective cyanosilylation of ketones catalyzed by tertiary aminothiourea derivatives was investigated using a combination of experimental and theoretical methods. The kinetic analysis is consistent with a cooperative mechanism in which both the thiourea and the tertiary amine of the catalyst are involved productively in the rate-limiting cyanide addition step. Density functional theory calculations were used to distinguish between mechanisms involving thiourea activation of ketone or of cyanide in the enantioselectivity-determining step. The strong correlation obtained between experimental and calculated ee's for a range of substrates and catalysts provides support for the most favorable calculated transition structures involving amine-bound HCN adding to thiourea-bound ketone. The calculations suggest that enantioselectivity arises from direct interactions between the ketone substrate and the amino-acid derived portion of the catalyst. On the basis of this insight, more enantioselective catalysts with broader substrate scope were prepared and evaluated experimentally.