(S)-(R,E)-1-(tert-butyldimethylsilyl)-3-(diethoxyphosphoryl)-3-((diisopropylcarbamoyl)oxy)allyl 2-(4-methylphenylsulfonamido)-3-phenylpropanoate | 1443780-23-1

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 英文名称: (S)-(R,E)-1-(tert-butyldimethylsilyl)-3-(diethoxyphosphoryl)-3-((diisopropylcarbamoyl)oxy)allyl 2-(4-methylphenylsulfonamido)-3-phenylpropanoate
• CAS: 1443780-23-1
• 化学式: C₃₆H₅₇N₂O₉PSSi
• 分子量: 752.982
• InChiKey: HUALENMTANWLSZ-FSHPIHIKSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  8.21
• 重原子数：
  50.0
• 可旋转键数：
  17.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.56
• 拓扑面积：
  137.54
• 氢给体数：
  1.0
• 氢受体数：
  9.0

反应信息

• 作为产物：
  描述：

  [(E)-3-[tert-butyl(dimethyl)silyl]-1-[diethoxy(oxido)phosphaniumyl]-3-hydroxyprop-1-enyl] N,N-di(propan-2-yl)carbamate 在 吡啶 作用下， 以 四氢呋喃 、 乙醇 、 正己烷 、 醋酸异丙酯 为溶剂， 反应 192.0h， 生成 (S)-(R,E)-1-(tert-butyldimethylsilyl)-3-(diethoxyphosphoryl)-3-((diisopropylcarbamoyl)oxy)allyl 2-(4-methylphenylsulfonamido)-3-phenylpropanoate
  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