[(1R,3R,4S,5R)-4-Benzyloxy-3-(tert-butyl-dimethyl-silanyloxy)-5-methoxy-cyclohexyl]-acetic acid methyl ester | 143900-32-7

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: [(1R,3R,4S,5R)-4-Benzyloxy-3-(tert-butyl-dimethyl-silanyloxy)-5-methoxy-cyclohexyl]-acetic acid methyl ester
• 英文别名: methyl 2-[(1R,3R,4S,5R)-3-[tert-butyl(dimethyl)silyl]oxy-5-methoxy-4-phenylmethoxycyclohexyl]acetate
• CAS: 143900-32-7
• 化学式: C₂₃H₃₈O₅Si
• 分子量: 422.637
• InChiKey: NZWKCCMWZYGDDY-VMBXEPDQSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.95
• 重原子数：
  29
• 可旋转键数：
  10
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.7
• 拓扑面积：
  54
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为产物：
  描述：

  (E)-(5R,6S,7S)-6-Benzyloxy-8-bromo-7-(tert-butyl-dimethyl-silanyloxy)-5-methoxy-oct-2-enoic acid methyl ester 在 偶氮二异丁腈 三正丁基氢锡 作用下， 以 甲苯 为溶剂， 以253 mg的产率得到[(1S,3R,4S,5R)-4-Benzyloxy-3-(tert-butyl-dimethyl-silanyloxy)-5-methoxy-cyclohexyl]-acetic acid methyl ester
  参考文献：
  名称：

  Stereoelectronic effects in the 6-exo free radical cyclization of acyclic sugar derivatives: synthesis of branched chain cyclitols

  摘要：

  The synthesis and free radical carbocyclization (BU3SnH + AIBN) of acyclic sugar derivatives 1-12 is reported. The yields of these 6-exo cyclization processes are good and the diastereomeric excesses are from moderate to excellent. The resulting cyclohexanes are polyoxygenated, enantiomerically pure building blocks for the synthesis of complex branched chain cyclitols. The results obtained in the cyclization of radical precursors 1, 4, 6, and 8 are in sharp contrast with the results observed in the ring closure of compounds 2, 3, 5, and 7. An electron-attracting group (acetate or mesylate), located in a vicinal position to the carbon-centered radical, modifies the conformation of the reacting species in the transition state and thus changes the stereochemical outcome of the cyclization. This allowed us to select the nature of the absolute configuration at the newly formed stereocenter by simply changing the type of the substituents at the vicinal carbon where the radical is generated.

  DOI：

  10.1021/jo00068a025

文献信息

• Synthesis of branched chain cyclitols: preparation of some useful chiral building blocks
  作者：José Marco-Contelles、Belén Sánchez、Carmen Pozuelo

  DOI：10.1016/s0957-4166(00)80501-7

  日期：1992.6

  The conveniently functionalized carbohydrate intermediates 1-4 and 9 undergo 6-exo free radical intramolecular cyclization giving branched chain cyclitols in good yield and low to good diastereoselectivity. These compounds are useful chiral building blocks for further manipulation.