(3aS,4R,8aR)-4-[(R)-1-(tert-Butyl-dimethyl-silanyloxy)-ethyl]-1,3-dioxo-2-phenyl-2,3,3a,4,5,7,8,8a-octahydro-1H-cyclopenta[f]isoindole-6,6-dicarboxylic acid dimethyl ester | 120545-03-1

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡咯烷类
• 英文名称: (3aS,4R,8aR)-4-[(R)-1-(tert-Butyl-dimethyl-silanyloxy)-ethyl]-1,3-dioxo-2-phenyl-2,3,3a,4,5,7,8,8a-octahydro-1H-cyclopenta[f]isoindole-6,6-dicarboxylic acid dimethyl ester
• 英文别名: dimethyl (3aR,8R,8aS)-8-[(1R)-1-[tert-butyl(dimethyl)silyl]oxyethyl]-1,3-dioxo-2-phenyl-3a,4,5,7,8,8a-hexahydrocyclopenta[f]isoindole-6,6-dicarboxylate
• CAS: 120545-03-1
• 化学式: C₂₉H₃₉NO₇Si
• 分子量: 541.717
• InChiKey: BCIOIHKVWRTXNV-ZZNFJVAJSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.65
• 重原子数：
  38.0
• 可旋转键数：
  6.0
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.59
• 拓扑面积：
  99.21
• 氢给体数：
  0.0
• 氢受体数：
  7.0

反应信息

• 作为反应物：
  描述：

  (3aS,4R,8aR)-4-[(R)-1-(tert-Butyl-dimethyl-silanyloxy)-ethyl]-1,3-dioxo-2-phenyl-2,3,3a,4,5,7,8,8a-octahydro-1H-cyclopenta[f]isoindole-6,6-dicarboxylic acid dimethyl ester 在 溶剂黄146 作用下， 以 四氢呋喃 为溶剂， 反应 18.0h， 以93%的产率得到dimethyl (1R,3aS,4R,8bR)-1-methyl-3-oxo-4-(phenylcarbamoyl)-3a,4,5,6,8,8b-hexahydro-1H-cyclopenta[e][2]benzofuran-7,7-dicarboxylate
  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：

  炔丙基丙二酸二甲酯 在 2,6-二甲基吡啶 、 Pd₂(dibenzylideneacetone)2*CHCl₃ 、 溶剂黄146 、 三苯基膦 、 pyridinium chlorochromate 作用下， 以 四氢呋喃 、 乙醚 、 二氯甲烷 、 苯 为溶剂， 反应 96.0h， 生成 (3aS,4R,8aR)-4-[(R)-1-(tert-Butyl-dimethyl-silanyloxy)-ethyl]-1,3-dioxo-2-phenyl-2,3,3a,4,5,7,8,8a-octahydro-1H-cyclopenta[f]isoindole-6,6-dicarboxylic acid dimethyl ester
  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
• TROST, BARRY M.;LEE, DONNA C., J. ORG. CHEM., 54,(1989) N0, C. 2271-2274
  作者：TROST, BARRY M.、LEE, DONNA C.

  DOI：——

  日期：——