(R,Z)-4-(tert-butyldimethylsilyl)-2-((tert-butyldimethylsilyl)oxy)-4-hydroxybut-2-enenitrile | 1443780-18-4

• 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: (R,Z)-4-(tert-butyldimethylsilyl)-2-((tert-butyldimethylsilyl)oxy)-4-hydroxybut-2-enenitrile
• 英文别名: (Z,4R)-4-[tert-butyl(dimethyl)silyl]-2-[tert-butyl(dimethyl)silyl]oxy-4-hydroxybut-2-enenitrile
• CAS: 1443780-18-4
• 化学式: C₁₆H₃₃NO₂Si₂
• 分子量: 327.615
• InChiKey: ZRAASINOODKXSJ-YBEMTRGBSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.82
• 重原子数：
  21
• 可旋转键数：
  6
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.81
• 拓扑面积：
  53.2
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  (R,Z)-4-(tert-butyldimethylsilyl)-2-((tert-butyldimethylsilyl)oxy)-4-hydroxybut-2-enenitrile 在 lithium aluminium tetrahydride 、 三乙胺 、 lithium tert-butoxide 、 叔丁醇 作用下， 以 四氢呋喃 、 正己烷 、 二氯甲烷 为溶剂， 反应 0.83h， 生成 (S,E)-tert-butyl (4-((tert-butyldimethylsilyl)oxy)-2-hydroxybut-3-en-1-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
• 作为产物：
  描述：

  (R)-2-((2R,3R)-3-(tert-butyldimethylsilyl)oxiran-2-yl)-2-((tert-butyldimethylsilyl)oxy)acetonitrile 在 lithium diisopropyl amide 、 溶剂黄146 作用下， 以 乙醚 为溶剂， 反应 0.33h， 以46%的产率得到(R,Z)-4-(tert-butyldimethylsilyl)-2-((tert-butyldimethylsilyl)oxy)-4-hydroxybut-2-enenitrile
  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