1-(tert-butyldimethylsilyl)-3-(trimethylsilyl)prop-2-yn-1-one | 1586869-88-6

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 1-(tert-butyldimethylsilyl)-3-(trimethylsilyl)prop-2-yn-1-one
• 英文别名: 1-[Tert-butyl(dimethyl)silyl]-3-trimethylsilylprop-2-yn-1-one
• CAS: 1586869-88-6
• 化学式: C₁₂H₂₄OSi₂
• 分子量: 240.493
• InChiKey: REFACYJWPYMLNR-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.48
• 重原子数：
  15
• 可旋转键数：
  3
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.75
• 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：

  1-(tert-butyldimethylsilyl)-3-(trimethylsilyl)prop-2-yn-1-one 在 正丁基锂 、 (S)-2,2-dimethyl-N-(2-(4-methylpiperazin-1-yl)-1-phenylethyl)propan-1-amine 、 四氯化钛 、 三乙胺 作用下， 以 四氢呋喃 、 正己烷 、 二氯甲烷 为溶剂， 反应 7.5h， 生成 N-(1-(tert-butyldimethylsilyl)-3-(trimethylsilyl)prop-2-yn-1-yl)-p-toluenesulfonamide
  参考文献：
  名称：

  Enantioselective Synthesis of α-Silylamines by Meerwein–Ponndorf–Verley-Type Reduction of α-Silylimines by a Chiral Lithium Amide

  摘要：

  Meerwein-Ponndorf-Verley-type reduction of N-tosylsilylimines with chiral lithium amide 2 affords alpha-silylamines in high enantioselectivity. Since the enantioselectivity observed was inconsistent with our previously proposed chairlike six-membered transition structure, we performed density functional theory (DFT) calculations on transition states leading to (S)- and (R)-7a and (S)- and (R)-7e using an N-phenylsulfonyl derivatives 12 and 13 as model systems. Results of the calculations showed that the structures are considerably deformed from the chairlike form with steric repulsions between the 1'-methylene group and the imine-carbon substituents playing an important role in the control of the, enantioselectivity.

  DOI：

  10.1021/jo500441a
• 作为产物：
  描述：

  1-(tert-butyldimethylsilyl)-3-(trimethylsilyl)-2-propyn-1-ol 在 Jones reagent 作用下， 以 丙酮 为溶剂， 反应 0.17h， 以85%的产率得到1-(tert-butyldimethylsilyl)-3-(trimethylsilyl)prop-2-yn-1-one
  参考文献：
  名称：

  Enantioselective Synthesis of α-Silylamines by Meerwein–Ponndorf–Verley-Type Reduction of α-Silylimines by a Chiral Lithium Amide

  摘要：

  Meerwein-Ponndorf-Verley-type reduction of N-tosylsilylimines with chiral lithium amide 2 affords alpha-silylamines in high enantioselectivity. Since the enantioselectivity observed was inconsistent with our previously proposed chairlike six-membered transition structure, we performed density functional theory (DFT) calculations on transition states leading to (S)- and (R)-7a and (S)- and (R)-7e using an N-phenylsulfonyl derivatives 12 and 13 as model systems. Results of the calculations showed that the structures are considerably deformed from the chairlike form with steric repulsions between the 1'-methylene group and the imine-carbon substituents playing an important role in the control of the, enantioselectivity.

  DOI：

  10.1021/jo500441a