O-ehtyl-N-but-3-ynyl-N-(4-methylphenyl)sulfonylcarbamate | 349451-03-2

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: O-ehtyl-N-but-3-ynyl-N-(4-methylphenyl)sulfonylcarbamate
• 英文别名: ethyl N-but-3-ynyl-N-(4-methylphenyl)sulfonylcarbamate
• CAS: 349451-03-2
• 化学式: C₁₄H₁₇NO₄S
• 分子量: 295.359
• InChiKey: CZYOMHMOWXIGOL-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.6
• 重原子数：
  20
• 可旋转键数：
  6
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.36
• 拓扑面积：
  72.1
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  N-亚苄基-P,P-二苯基次膦酸酰胺 、 O-ehtyl-N-but-3-ynyl-N-(4-methylphenyl)sulfonylcarbamate 在 Schwartz's reagent 、 Dimethylzinc 作用下， 以 二氯甲烷 、 甲苯 为溶剂， 反应 12.16h， 以59%的产率得到O-ethyl-N-{5-[(diphenylphosphoryl)amino]-5-phenylpent-3-enyl}-N-(4-methylphenyl)sulfonylcarbamate
  参考文献：
  名称：

  Dimethylzinc-Mediated Additions of Alkenylzirconocenes to Aldimines. New Methodologies for Allylic Amine and C-Cyclopropylalkylamine Syntheses

  摘要：

  Hydrozirconation of alkynes with zirconocene hydrochloride followed by in situ transmetalation to dimethylzinc provides access to reactive alkenyl organometallic reagents from readily available precursors. Upon addition of imines, 1,2-attack leads to synthetically useful allylic amine building blocks. In the presence of CH2I2 or CH2Cl2, the N-metalated allylic amide intermediate is cyclopropanated and C-cyclopropylalkylamines are formed in high yield and excellent diastereoselectivities favoring the anti products. The use of enynes as starting materials for this domino reaction provides conjugated biscyclopropanes and thus allows the stereoselective formation of five new carbon-carbon bonds. A transition state that explains the need for both zirconocene complex and alkyl zinc in the cyclopropanation reaction is proposed.

  DOI：

  10.1021/ja028092a
• 作为产物：
  描述：

  N-(4-甲基苯基)磺酰氨基甲酸乙酯 、 3-丁炔-1-醇 在 三苯基膦 、 偶氮二甲酸二乙酯 作用下， 以 四氢呋喃 为溶剂， 反应 16.0h， 以96%的产率得到O-ehtyl-N-but-3-ynyl-N-(4-methylphenyl)sulfonylcarbamate
  参考文献：
  名称：

  Dimethylzinc-Mediated Additions of Alkenylzirconocenes to Aldimines. New Methodologies for Allylic Amine and C-Cyclopropylalkylamine Syntheses

  摘要：

  Hydrozirconation of alkynes with zirconocene hydrochloride followed by in situ transmetalation to dimethylzinc provides access to reactive alkenyl organometallic reagents from readily available precursors. Upon addition of imines, 1,2-attack leads to synthetically useful allylic amine building blocks. In the presence of CH2I2 or CH2Cl2, the N-metalated allylic amide intermediate is cyclopropanated and C-cyclopropylalkylamines are formed in high yield and excellent diastereoselectivities favoring the anti products. The use of enynes as starting materials for this domino reaction provides conjugated biscyclopropanes and thus allows the stereoselective formation of five new carbon-carbon bonds. A transition state that explains the need for both zirconocene complex and alkyl zinc in the cyclopropanation reaction is proposed.

  DOI：

  10.1021/ja028092a

文献信息

• Transition-Metal-Mediated Cascade Reactions:  <i>C</i>,<i>C</i>-Dicyclopropylmethylamines by Way of Double C,C-σ-Bond Insertion into Bicyclobutanes
  作者：Peter Wipf、Corey R. J. Stephenson、Kazuo Okumura

  DOI：10.1021/ja038623a

  日期：2003.12.1

  The organometallic multicomponent reaction of alkenyl zirconocene, alkynyl imine, and zinc carbenoid in the presence of dimethylzinc leads to novel C,C-dicyclopropylmethylamines. The formation of intermediate bicyclo[1.1.0]butanes represents the first synthetically useful example of a double C,C-sigma-bond insertion, and the increase in structural complexity from starting materials is highlighted by the formation of nine new C,C-bonds in the final product.
• Three-Component Aldimine Addition−Cyclopropanation. An Efficient New Methodology for Amino Cyclopropane Synthesis
  作者：Peter Wipf、Christopher Kendall、Corey R. J. Stephenson

  DOI：10.1021/ja0157494

  日期：2001.5.1