tert-butyl-dimethyl-[(1-methyl-3,4-dihydro-2H-pyridin-6-yl)oxy]silane | 1136235-67-0

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡啶及其衍生物
• 英文名称: tert-butyl-dimethyl-[(1-methyl-3,4-dihydro-2H-pyridin-6-yl)oxy]silane
• CAS: 1136235-67-0
• 化学式: C₁₂H₂₅NOSi
• 分子量: 227.422
• InChiKey: VSVPQNATSIKRJW-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.58
• 重原子数：
  15
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.83
• 拓扑面积：
  12.5
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  tert-butyl-dimethyl-[(1-methyl-3,4-dihydro-2H-pyridin-6-yl)oxy]silane 、 N-2,4,6-trimethylphenylsulfonylbenzaldimine 在 triethylammonium triflate 、 三氟甲烷磺酸亚铜(I)苯联合体 (2:1) 作用下， 以 二氯甲烷 为溶剂， 反应 24.0h， 以16%的产率得到1-methyl-3-[phenyl(2,4,6-mesitylenesulfonylamino)methyl]piperidin-2-one
  参考文献：
  名称：

  Catalytic Silicon-Mediated Carbon−Carbon Bond-Forming Reactions of Unactivated Amides

  摘要：

  In the presence of catalytic amounts of trialkylsilyl triflate and triethylamine, unactivated amides react with imines to afford the corresponding Mannich-type adducts in high yields with high anti selectivities. While silicon enolates have been widely used in organic synthesis for four decades, this is the first example of the catalytic use of the silicon species, to the best of our knowledge. Moreover, it is noteworthy that unactivated simple amides bearing a-protons that are less acidic than those of ketones and aldehydes can be successfully used in catalytic direct-type addition reactions. Finally, a preliminary trial of an asymmetric catalytic version was conducted and showed promising enantioselectivity of the desired product.

  DOI：

  10.1021/ja108764d
• 作为产物：
  描述：

  1-甲基-2-哌啶酮 、 叔丁基二甲基氯硅烷 在 lithium diisopropyl amide 作用下， 生成 tert-butyl-dimethyl-[(1-methyl-3,4-dihydro-2H-pyridin-6-yl)oxy]silane
  参考文献：
  名称：

  Catalytic Silicon-Mediated Carbon−Carbon Bond-Forming Reactions of Unactivated Amides

  摘要：

  In the presence of catalytic amounts of trialkylsilyl triflate and triethylamine, unactivated amides react with imines to afford the corresponding Mannich-type adducts in high yields with high anti selectivities. While silicon enolates have been widely used in organic synthesis for four decades, this is the first example of the catalytic use of the silicon species, to the best of our knowledge. Moreover, it is noteworthy that unactivated simple amides bearing a-protons that are less acidic than those of ketones and aldehydes can be successfully used in catalytic direct-type addition reactions. Finally, a preliminary trial of an asymmetric catalytic version was conducted and showed promising enantioselectivity of the desired product.

  DOI：

  10.1021/ja108764d

文献信息

• Diastereoselective and Enantioselective Synthesis of Tertiary α-Hydroxy Phosphonates through Hydrogen-Bond Catalysis
  作者：Vijaya Bhasker Gondi、Koji Hagihara、Viresh H. Rawal

  DOI：10.1002/anie.200804244

  日期：2009.1.12

  Hydrogen‐bond activation by a diol promotes enantioselective Mukaiyama aldol reactions of acyl phosphonates. This mild and general method gives α‐hydroxy phosphonate products having two chiral centers, one tertiary and one quaternary, formed with high diastereo‐ and enantioselectivity.

  二醇的氢键活化促进酰基膦酸酯的对映选择性Mukaiyama羟醛反应。这种温和且通用的方法产生具有两个手性中心（一个叔中心和一个季中心）的 α-羟基膦酸酯产物，形成具有高非对映和对映选择性。