ethyl N-(ethoxycarbonylamino)-N-(1-trimethylsilylhex-1-yn-3-yl)carbamate | 1239969-25-5

• 分子结构分类: 有机化合物 - 有机金属化合物 - 有机类金属化合物
• 英文名称: ethyl N-(ethoxycarbonylamino)-N-(1-trimethylsilylhex-1-yn-3-yl)carbamate
• CAS: 1239969-25-5
• 化学式: C₁₅H₂₈N₂O₄Si
• 分子量: 328.484
• InChiKey: KLWSKNAHYRNDSS-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.16
• 重原子数：
  22.0
• 可旋转键数：
  5.0
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.73
• 拓扑面积：
  67.87
• 氢给体数：
  1.0
• 氢受体数：
  4.0

反应信息

• 作为产物：
  描述：

  1-三甲基硅烷-1-己炔 、 偶氮二甲酸二乙酯 在 N-羟基邻苯二甲酰亚胺 作用下， 以 1,2-二氯乙烷 为溶剂， 反应 48.0h， 以66%的产率得到ethyl N-(ethoxycarbonylamino)-N-(1-trimethylsilylhex-1-yn-3-yl)carbamate
  参考文献：
  名称：

  Radical Amination of C(sp³)–H Bonds Using N-Hydroxyphthalimide and Dialkyl Azodicarboxylate

  摘要：

  A direct conversion of C(sp(3))-H bonds to C(sp3)-N bonds has been achieved by utilizing catalytic N-hydroxyphthalimide (NHPI) and stoichiometric dialkyl azodicarboxylate. NHPI functions as a precursor of the electron-deficient phthalimide N-oxyl radical (PINO) to abstract hydrogens, and dialkyl azodicarboxylate acts as a trapping agent of the resultant carbon radical to generate the hydrazine derivatives. This C-H amination proceeds in a highly chemoselective manner with a wide applicability to functionalize benzylic, propargylic, and aliphatic C-H bonds. Furthermore, the obtained hydrazine compounds were readily converted to the corresponding carbamates or amines. Hence, the present protocol for direct introduction of the nitrogen functionality serves as a powerful tool for efficient construction of nitrogen-substituted natural products and pharmaceuticals.

  DOI：

  10.1021/jo301840e

文献信息

• Selective Propargylation of Azo Compounds with Barium Reagents
  作者：Akira Yanagisawa、Takanori Koide、Kazuhiro Yoshida

  DOI：10.1055/s-0029-1219944

  日期：2010.6

  A Barbier-type propargylation of azo compounds with γ-trialkylsilylated propargylic bromides has been achieved using reactive barium as a low-valent metal in THF. Corresponding propargylated hydrazines (α-adducts) were exclusively formed not only from azobenzenes (diaryldiazenes) but also from dialkyl azodicarboxylates. This method is also applicable to γ-alkylated or γ-phenylated propargylic bromides

  已经使用活性钡作为 THF 中的低价金属实现了偶氮化合物与 γ-三烷基甲硅烷基化炔丙基溴的 Barbier 型炔丙基化。相应的炔丙基化肼（α-加合物）不仅由偶氮苯（二芳基二氮烯）而且还由偶氮二羧酸二烷基酯形成。该方法也适用于 γ-烷基化或 γ-苯基化炔丙基溴，仅提供所需的炔丙基化产物。