(1S*,5R*,6R*,7R*)-9-methano-7-(phenylsulfonyl)-5-((tert-butyldimethylsilyl)oxy)-2-oxobicyclo<4.3.0>nonane | 137871-80-8

• 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: (1S*,5R*,6R*,7R*)-9-methano-7-(phenylsulfonyl)-5-((tert-butyldimethylsilyl)oxy)-2-oxobicyclo<4.3.0>nonane
• 英文别名: (1R,3aR,7R,7aS)-1-(benzenesulfonyl)-7-[tert-butyl(dimethyl)silyl]oxy-3-methylidene-2,3a,5,6,7,7a-hexahydro-1H-inden-4-one
• CAS: 137871-80-8
• 化学式: C₂₂H₃₂O₄SSi
• 分子量: 420.645
• InChiKey: VAUKTCJWOLCPEM-NCYKPQTJSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.77
• 重原子数：
  28
• 可旋转键数：
  5
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.59
• 拓扑面积：
  68.8
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为产物：
  描述：

  2-(4-hydroxybutyl)-2-(1-((methoxycarbonyl)oxy)-2-((trimethylsilyl)methyl)-2-propenyl)-1,3-dithiane 在 palladium diacetate 、 三异丙基亚磷酸酯 哌啶 、 4-二甲氨基吡啶 、 N-氯代丁二酰亚胺 、 Celite 、 silver nitrate 、 pyridinium chlorochromate 作用下， 以 四氢呋喃 、 二氯甲烷 、 水 、 乙腈 为溶剂， 反应 14.67h， 生成 (1S*,5R*,6R*,7R*)-9-methano-7-(phenylsulfonyl)-5-((tert-butyldimethylsilyl)oxy)-2-oxobicyclo<4.3.0>nonane
  参考文献：
  名称：

  The acyl effect on intramolecular palladium-catalyzed trimethylenemethane cycloadditions

  摘要：

  Enhancing the generality of the intramolecular palladium-catalyzed [3 + 2] cycloaddition involving trimethylenemethane complexes as reactive intermediates is possible by incorporation of acyl substituents on the TMM unit. Such substituted TMM-PdL2 species greatly expand the scope such that bicyclo[3.3.0]octyl, bicyclo[4.3.0]nonyl, and bicyclo[5.3.0]decyl ring systems all can be created. Furthermore, the acyl-TMM chemistry permits incorporation of a bridgehead methyl substituent-the first example of a TMM-PdL2 cycloaddition in synthetically useful yields initiated by attack of a tertiary carbon in the first step to give a quaternary center. The requisite substrates are readily available using nucleophilic acylations via lithiated thioacetals. A general lynchpin strategy derives from bis(methylthio)methane onto which can be attached both the donor and acceptor partners of the cycloaddition. 2-((Trimethylsilyl)methyl)propenal serves as a convenient conjunctive reagent to introduce the donor partner. Alternatively 2-acyldithianes serve as a lynchpin to build substrates leading to bicycles bearing bridgehead substituents. In this case, 2-bromo-3-(trimethylsilyl)propene serves as a convenient conjunctive reagent to create the donor partner. The beneficial effect of acyl substitution derives from a combination of inhibiting side reactions derived from protodesilylation processes and facilitating the initial step of this nonconcerted cycloaddition. In addition to improving the generality of the intramolecular process, the ketone group that results in the product is a powerful functionality for further structural elaboration.

  DOI：

  10.1021/jo00028a052

文献信息

• The acyl effect on intramolecular palladium-catalyzed trimethylenemethane cycloadditions
  作者：Barry M. Trost、Timothy A. Grese

  DOI：10.1021/jo00028a052

  日期：1992.1

  Enhancing the generality of the intramolecular palladium-catalyzed [3 + 2] cycloaddition involving trimethylenemethane complexes as reactive intermediates is possible by incorporation of acyl substituents on the TMM unit. Such substituted TMM-PdL2 species greatly expand the scope such that bicyclo[3.3.0]octyl, bicyclo[4.3.0]nonyl, and bicyclo[5.3.0]decyl ring systems all can be created. Furthermore, the acyl-TMM chemistry permits incorporation of a bridgehead methyl substituent-the first example of a TMM-PdL2 cycloaddition in synthetically useful yields initiated by attack of a tertiary carbon in the first step to give a quaternary center. The requisite substrates are readily available using nucleophilic acylations via lithiated thioacetals. A general lynchpin strategy derives from bis(methylthio)methane onto which can be attached both the donor and acceptor partners of the cycloaddition. 2-((Trimethylsilyl)methyl)propenal serves as a convenient conjunctive reagent to introduce the donor partner. Alternatively 2-acyldithianes serve as a lynchpin to build substrates leading to bicycles bearing bridgehead substituents. In this case, 2-bromo-3-(trimethylsilyl)propene serves as a convenient conjunctive reagent to create the donor partner. The beneficial effect of acyl substitution derives from a combination of inhibiting side reactions derived from protodesilylation processes and facilitating the initial step of this nonconcerted cycloaddition. In addition to improving the generality of the intramolecular process, the ketone group that results in the product is a powerful functionality for further structural elaboration.