(1R,2R)-2-isothiocyanato-N,N-dipropylcyclohexanamine | 1003922-10-8

• 分子结构分类: 有机化合物 - 有机硫化合物
• 英文名称: (1R,2R)-2-isothiocyanato-N,N-dipropylcyclohexanamine
• CAS: 1003922-10-8
• 化学式: C₁₃H₂₄N₂S
• 分子量: 240.413
• InChiKey: MUJIOTPAHQBFRX-CHWSQXEVSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.52
• 重原子数：
  16.0
• 可旋转键数：
  6.0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.92
• 拓扑面积：
  15.6
• 氢给体数：
  0.0
• 氢受体数：
  3.0

反应信息

• 作为反应物：
  描述：

  (1R,2R)-2-isothiocyanato-N,N-dipropylcyclohexanamine 、 (S)-2-amino-N-methyl-propionamide 在 三乙胺 作用下， 以 二氯甲烷 为溶剂， 反应 48.0h， 以208 mg的产率得到(S)-2-(3-((1R,2R)-2-(dipropylamino)cyclohexyl)thioureido)-N-methylpropanamide
  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
• 作为产物：
  描述：

  (1R,2R)-N1,N1-二丙基环己烷-1,2-二胺 、 硫光气 在 碳酸氢钠 作用下， 以 二氯甲烷 为溶剂， 反应 0.42h， 以77%的产率得到(1R,2R)-2-isothiocyanato-N,N-dipropylcyclohexanamine
  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