1-(5-(tert-butyldimethylsilyl)-2,2-dimethyl-1,3-dioxolan-4-yl)-2-hydroxy-2-phenylethyl diisopropylcarbamate | 1443780-07-1

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 1-(5-(tert-butyldimethylsilyl)-2,2-dimethyl-1,3-dioxolan-4-yl)-2-hydroxy-2-phenylethyl diisopropylcarbamate
• CAS: 1443780-07-1
• 化学式: C₂₆H₄₅NO₅Si
• 分子量: 479.733
• InChiKey: RCNBPFMASOCASV-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.91
• 重原子数：
  33.0
• 可旋转键数：
  7.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.73
• 拓扑面积：
  68.23
• 氢给体数：
  1.0
• 氢受体数：
  5.0

反应信息

• 作为反应物：
  描述：

  1-(5-(tert-butyldimethylsilyl)-2,2-dimethyl-1,3-dioxolan-4-yl)-2-hydroxy-2-phenylethyl diisopropylcarbamate 在 manganese(IV) oxide 作用下， 以 二氯甲烷 为溶剂， 反应 2.5h， 以62%的产率得到1-(5-(tert-butyldimethylsilyl)-2,2-dimethyl-1,3-dioxolan-4-yl)-2-oxo-2-phenylethyl 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 作用下， 以 四氢呋喃 、 正己烷 、 二氯甲烷 、 丙酮 、 乙腈 为溶剂， 反应 4.08h， 生成 1-(5-(tert-butyldimethylsilyl)-2,2-dimethyl-1,3-dioxolan-4-yl)-2-hydroxy-2-phenylethyl 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