(R,E)-diethyl 1,3-bis(tert-butyldimethylsiloxy)prop-2-enylphosphonate | 1443780-47-9

• 分子结构分类: 有机化合物 - 有机酸及其衍生物
• 英文名称: (R,E)-diethyl 1,3-bis(tert-butyldimethylsiloxy)prop-2-enylphosphonate
• CAS: 1443780-47-9
• 化学式: C₁₉H₄₃O₅PSi₂
• 分子量: 438.692
• InChiKey: AJXGNANTXQFEOX-INFVRCAFSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  7.14
• 重原子数：
  27.0
• 可旋转键数：
  10.0
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.89
• 拓扑面积：
  53.99
• 氢给体数：
  0.0
• 氢受体数：
  5.0

反应信息

• 作为反应物：
  描述：

  (R,E)-diethyl 1,3-bis(tert-butyldimethylsiloxy)prop-2-enylphosphonate 在 4-二甲氨基吡啶 、 sodium tetrahydroborate 、 溶剂黄146 、 三乙胺 作用下， 以 四氢呋喃 、 乙醇 、 二氯甲烷 、 水 为溶剂， 反应 6.25h， 生成
  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：

  diethyl (((2S,3R)-3-(tert-butyldimethylsilyl)oxiran-2-yl)((tert-butyldimethylsilyl)oxy)methyl)phosphonate 在 叔丁基锂 、 sodium t-butanolate 、 叔丁醇 作用下， 以 乙醚 、 正己烷 、 正戊烷 为溶剂， 反应 0.33h， 生成 (R,E)-diethyl 1,3-bis(tert-butyldimethylsiloxy)prop-2-enylphosphonate 、 (S,E)-diethyl 1,3-bis(tert-butyldimethylsiloxy)prop-2-enylphosphonate
  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