N-benzyl-3-methylene-4-(2-(tert-butyldimethylsiloxy)-1(E)-propylidene)pyrrolidine | 120545-14-4

• 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: N-benzyl-3-methylene-4-(2-(tert-butyldimethylsiloxy)-1(E)-propylidene)pyrrolidine
• 英文别名: [(1Z)-1-(1-benzyl-4-methylidenepyrrolidin-3-ylidene)propan-2-yl]oxy-tert-butyl-dimethylsilane
• CAS: 120545-14-4
• 化学式: C₂₁H₃₃NOSi
• 分子量: 343.585
• InChiKey: QHALDWPEDXGMJV-DEDYPNTBSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.4
• 重原子数：
  24
• 可旋转键数：
  6
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.52
• 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：

  N-苯基马来酰亚胺 、 N-benzyl-3-methylene-4-(2-(tert-butyldimethylsiloxy)-1(E)-propylidene)pyrrolidine 以 苯 为溶剂， 反应 48.0h， 以84%的产率得到(3aR,8R,8aS)-6-benzyl-8-[(1R)-1-[tert-butyl(dimethyl)silyl]oxyethyl]-2-phenyl-3a,4,5,7,8,8a-hexahydropyrrolo[3,4-f]isoindole-1,3-dione
  参考文献：
  名称：

  Pd-Catalyzed Cycloisomerization to 1,2-Dialkylidenecycloalkanes. 2. Alternative Catalyst System

  摘要：

  The mechanisms by which palladium complexes may catalyze the cycloisomerization of 1,6- and 1,7-enynes to dialkylidenecycloalkanes were probed by exploring a catalyst system different than a ligated palladium acetate which previously has proven to be successful. Although carboxylic acids showed no discernible interaction with palladium(0) complexes, this combination proved to be a powerful catalyst system to effect this cycloisomerization. The fact that the two catalyst systems do not have the same reactivity profile suggests this new catalyst system may operate by a different mechanism. Evidence supporting a pathway invoking formation of a hydridopalladium acetate followed by hydropalladation as initiation is presented. Steric and electronic effects direct the regioselectivity of the termination step to form either 1,3- or 1,4-diene products. The 1,3-diene products participate exceedingly well in Diels-Alder reactions, both inter- and intramolecularly. The presence of an oxygen substituent at the position allylic to the diene served as both a regiochemical control element for the palladium-catalyzed cycloisomerization and a diastereochemical control element for the Diels-Alder reaction. The net result of these two steps, the first of which is a catalyzed isomerization and the second an addition, is a highly efficient approach to complex polycycles in terms of both selectivity and atom economy.

  DOI：

  10.1021/ja00089a016
• 作为产物：
  描述：

  N-benzyl-N-propargyl-4-hydroxy-2-pentynamine 在 咪唑 、 lithium aluminium tetrahydride 、 Pd₂(dibenzylideneacetone)2*CHCl₃ 、 溶剂黄146 、 三苯基膦 作用下， 以 四氢呋喃 、 二氯甲烷 、 氘代苯 为溶剂， 反应 44.5h， 生成 N-benzyl-3-methylene-4-(2-(tert-butyldimethylsiloxy)-1(E)-propylidene)pyrrolidine
  参考文献：
  名称：

  Pd-Catalyzed Cycloisomerization to 1,2-Dialkylidenecycloalkanes. 2. Alternative Catalyst System

  摘要：

  The mechanisms by which palladium complexes may catalyze the cycloisomerization of 1,6- and 1,7-enynes to dialkylidenecycloalkanes were probed by exploring a catalyst system different than a ligated palladium acetate which previously has proven to be successful. Although carboxylic acids showed no discernible interaction with palladium(0) complexes, this combination proved to be a powerful catalyst system to effect this cycloisomerization. The fact that the two catalyst systems do not have the same reactivity profile suggests this new catalyst system may operate by a different mechanism. Evidence supporting a pathway invoking formation of a hydridopalladium acetate followed by hydropalladation as initiation is presented. Steric and electronic effects direct the regioselectivity of the termination step to form either 1,3- or 1,4-diene products. The 1,3-diene products participate exceedingly well in Diels-Alder reactions, both inter- and intramolecularly. The presence of an oxygen substituent at the position allylic to the diene served as both a regiochemical control element for the palladium-catalyzed cycloisomerization and a diastereochemical control element for the Diels-Alder reaction. The net result of these two steps, the first of which is a catalyzed isomerization and the second an addition, is a highly efficient approach to complex polycycles in terms of both selectivity and atom economy.

  DOI：

  10.1021/ja00089a016

文献信息

• Hydroxy group as a regio- and stereochemical control element for sequential metal-catalyzed and thermal cyclizations
  作者：Barry M. Trost、Donna C. Lee

  DOI：10.1021/jo00271a006

  日期：1989.5