[(E)-3-[tert-butyl(dimethyl)silyl]-3-hydroxy-1-(4-methylphenyl)sulfonylprop-1-enyl] N,N-di(propan-2-yl)carbamate | 1443780-17-3

• 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: [(E)-3-[tert-butyl(dimethyl)silyl]-3-hydroxy-1-(4-methylphenyl)sulfonylprop-1-enyl] N,N-di(propan-2-yl)carbamate
• CAS: 1443780-17-3
• 化学式: C₂₃H₃₉NO₅SSi
• 分子量: 469.718
• InChiKey: YBCOZPMXGVWQRQ-RCCKNPSSSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.27
• 重原子数：
  31
• 可旋转键数：
  9
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.61
• 拓扑面积：
  92.3
• 氢给体数：
  1
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  [(E)-3-[tert-butyl(dimethyl)silyl]-3-hydroxy-1-(4-methylphenyl)sulfonylprop-1-enyl] N,N-di(propan-2-yl)carbamate 在 Chiralpak AD-H 作用下， 以 正己烷 、 醋酸异丙酯 为溶剂， 以124 mg的产率得到(E)-3-(tert-butyldimethylsilyl)-3-hydroxy-1-tosylallyl diisopropylcarbamate
  参考文献：
  名称：

  Chirality transfer in Brook rearrangement-mediated SE2′ solvolytic protonation and its use in estimation of the propensity for racemization of the α-lithiocarbanions of the substituents

  摘要：

  Chirality transfer from an alpha-silylalcohol to alpha-carbmoyloxy- and alpha-siloxyallyl-carbanions was investigated using a Brook rearrangement-mediated S(E)2' protonation in gamma-carbamoyloxy- and gamma-siloxy-alpha-silylallyl alcohols. We proposed a hypothesis that the reaction proceeds along one of two pathways that involves (1) a concerted protonation of a silicate intermediate and (2) a concerted lithiation of the intermediate followed by protonation with retention or by protonation after racemization. Comparison of the extent of the chirality transfer provides a new method for semi-quantitative evaluation of the propensity for racemization of lithiocarbanions next to a conjugative electron-withdrawing group. (C) 2013 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2013.05.043
• 作为产物：
  描述：

  (E)-3-(tert-butyldimethylsilyl)allyl diisopropylcarbamate 在 四氧化锇 、 正丁基锂 、 四甲基乙二胺 、 对甲苯磺酸 、 N-甲基吗啉氧化物 、 lithium diisopropyl amide 作用下， 以 四氢呋喃 、 乙醚 、 正己烷 、 二氯甲烷 、 水 、 丙酮 、 乙腈 为溶剂， 反应 3.0h， 生成 [(E)-3-[tert-butyl(dimethyl)silyl]-3-hydroxy-1-(4-methylphenyl)sulfonylprop-1-enyl] N,N-di(propan-2-yl)carbamate
  参考文献：
  名称：

  Chirality transfer in Brook rearrangement-mediated SE2′ solvolytic protonation and its use in estimation of the propensity for racemization of the α-lithiocarbanions of the substituents

  摘要：

  Chirality transfer from an alpha-silylalcohol to alpha-carbmoyloxy- and alpha-siloxyallyl-carbanions was investigated using a Brook rearrangement-mediated S(E)2' protonation in gamma-carbamoyloxy- and gamma-siloxy-alpha-silylallyl alcohols. We proposed a hypothesis that the reaction proceeds along one of two pathways that involves (1) a concerted protonation of a silicate intermediate and (2) a concerted lithiation of the intermediate followed by protonation with retention or by protonation after racemization. Comparison of the extent of the chirality transfer provides a new method for semi-quantitative evaluation of the propensity for racemization of lithiocarbanions next to a conjugative electron-withdrawing group. (C) 2013 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2013.05.043

文献信息

• Chirality transfer in Brook rearrangement-mediated SE2′ solvolytic protonation and its use in estimation of the propensity for racemization of the α-lithiocarbanions of the substituents
  作者：Michiko Sasaki、Misato Fujiwara、Yuri Kotomori、Masatoshi Kawahata、Kentaro Yamaguchi、Kei Takeda

  DOI：10.1016/j.tet.2013.05.043

  日期：2013.7

  Chirality transfer from an alpha-silylalcohol to alpha-carbmoyloxy- and alpha-siloxyallyl-carbanions was investigated using a Brook rearrangement-mediated S(E)2' protonation in gamma-carbamoyloxy- and gamma-siloxy-alpha-silylallyl alcohols. We proposed a hypothesis that the reaction proceeds along one of two pathways that involves (1) a concerted protonation of a silicate intermediate and (2) a concerted lithiation of the intermediate followed by protonation with retention or by protonation after racemization. Comparison of the extent of the chirality transfer provides a new method for semi-quantitative evaluation of the propensity for racemization of lithiocarbanions next to a conjugative electron-withdrawing group. (C) 2013 Elsevier Ltd. All rights reserved.