[(1R,2R)-2-(tert-Butyl-dimethyl-silanyloxy)-4-oxo-cyclopentyl]-acetic acid ethyl ester | 130096-91-2

• 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: [(1R,2R)-2-(tert-Butyl-dimethyl-silanyloxy)-4-oxo-cyclopentyl]-acetic acid ethyl ester
• CAS: 130096-91-2
• 化学式: C₁₅H₂₈O₄Si
• 分子量: 300.47
• InChiKey: RGBKTMKHAZQNDW-DGCLKSJQSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.31
• 重原子数：
  20.0
• 可旋转键数：
  5.0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.87
• 拓扑面积：
  52.6
• 氢给体数：
  0.0
• 氢受体数：
  4.0

反应信息

• 作为反应物：
  描述：

  [(1R,2R)-2-(tert-Butyl-dimethyl-silanyloxy)-4-oxo-cyclopentyl]-acetic acid ethyl ester 在 L-Selectride 作用下， 以 四氢呋喃 为溶剂， 以91%的产率得到[(1R,2R,4S)-2-(tert-Butyl-dimethyl-silanyloxy)-4-hydroxy-cyclopentyl]-acetic acid ethyl ester
  参考文献：
  名称：

  On the diastereofacial selectivity of Lewis acid-catalyzed carbon-carbon bond forming reactions of conjugated cyclic enones bearing electron-withdrawing substituents at the .gamma.-position

  摘要：

  Lewis acid catalyzed reactions of several cyclic enones are described. The gamma-OTBS enones 1 and 2 give products where carbon-carbon bond formation at the beta carbon occurs with high stereoselectivity favoring attack syn to the resident OTBS group. In the case of enone 24 bearing an additional dioxolane ring, the products correspond to addition anti to the resident carbon-oxygen bond at the gamma carbon. The reaction of 24 with lithium dimethylcuprate also occurs in an anti sense. The starting materials in this study are available in quantity in optically pure form. Given the excellent stereoselectivity of the reactions, these compounds are useful intermediates for synthesis.

  DOI：

  10.1021/jo00001a070
• 作为产物：
  描述：

  ethyl (1RS,5SR)-<5-(tert-butyldimethylsiloxy)-3-(triethylsiloxy)-2-cyclopenten-1-yl>acetate 在 水 、 溶剂黄146 作用下， 以 四氢呋喃 为溶剂， 反应 0.67h， 以81%的产率得到[(1R,2R)-2-(tert-Butyl-dimethyl-silanyloxy)-4-oxo-cyclopentyl]-acetic acid ethyl ester
  参考文献：
  名称：

  On the diastereofacial selectivity of Lewis acid-catalyzed carbon-carbon bond forming reactions of conjugated cyclic enones bearing electron-withdrawing substituents at the .gamma.-position

  摘要：

  Lewis acid catalyzed reactions of several cyclic enones are described. The gamma-OTBS enones 1 and 2 give products where carbon-carbon bond formation at the beta carbon occurs with high stereoselectivity favoring attack syn to the resident OTBS group. In the case of enone 24 bearing an additional dioxolane ring, the products correspond to addition anti to the resident carbon-oxygen bond at the gamma carbon. The reaction of 24 with lithium dimethylcuprate also occurs in an anti sense. The starting materials in this study are available in quantity in optically pure form. Given the excellent stereoselectivity of the reactions, these compounds are useful intermediates for synthesis.

  DOI：

  10.1021/jo00001a070

文献信息

• Diastereocontrol in Lewis acid-catalyzed Michael reactions of 4-siloxycyclopentenone with ketene silyl acetals: Stereoelectronic vs. steric effect
  作者：Junzo Otera、Yukihiro Fujita、Shunichi Fukuzumi、Kei-ichi Hirai、Jin-Hua Gu、Takeshi Nakai

  DOI：10.1016/0040-4039(94)02174-a

  日期：1995.1

  are shown to proceed with sterically unfavorable syn preference (to the siloxy group) when steric demand of the acetals is trivial, whereas β-substitution of acetals results in reversal of diastereoselection. These results are discussed in terms of the stereoelectronic vs. steric effect.

  当乙缩醛的空间需求微不足道时，标题反应显示出在空间上不利的顺式（相对于甲硅烷氧基）的进行，而乙缩醛的β-取代导致非对映选择性的逆转。这些结果将根据立体电子与空间效应进行讨论。