methyl 5-(tert-butyldiphenylsilyloxy)-2-oxo-cyclohexan-1-carboxylate | 478798-39-9

• 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: methyl 5-(tert-butyldiphenylsilyloxy)-2-oxo-cyclohexan-1-carboxylate
• 英文别名: Methyl 5-[tert-butyl(diphenyl)silyl]oxy-2-oxocyclohexane-1-carboxylate
• CAS: 478798-39-9
• 化学式: C₂₄H₃₀O₄Si
• 分子量: 410.585
• InChiKey: WAHNKFPFKDMZOL-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.47
• 重原子数：
  29
• 可旋转键数：
  7
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.42
• 拓扑面积：
  52.6
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  2-(2-Bromophenoxy)ethyl-tert-butyl-diphenylsilane 、 methyl 5-(tert-butyldiphenylsilyloxy)-2-oxo-cyclohexan-1-carboxylate 在 正丁基锂 、 三丁基氯化锡 、 lead(IV) acetate 、 mercury(II) trifluoroacetate 、 吡啶 作用下， 以 四氢呋喃 、 1,2-二氯乙烷 为溶剂， 反应 21.0h， 以0.108 g的产率得到(1S,5R)-1-{2-[2-(tert-Butyl-diphenyl-silanyl)-ethoxy]-phenyl}-5-(tert-butyl-diphenyl-silanyloxy)-2-oxo-cyclohexanecarboxylic acid methyl ester
  参考文献：
  名称：

  叔丁基二苯基甲硅烷基乙基（“ TBDPSE”）：苯酚的实用保护基

  摘要：

  制备并研究了一种新的苯酚保护基，即2-（叔丁基二苯基甲硅烷基）乙基（TBDPSE）。各种取代苯酚的保护均以良好至极佳的收率进行。该基团对弱酸，碱，氢解条件以及受保护的苯酚上的锂/卤素交换稳定。去除可通过强酸或标准氟化物处理实现。

  DOI：

  10.1021/jo048192u
• 作为产物：
  描述：

  4-[[(1,1-二甲基乙基)二苯基甲硅烷基]氧基]-环己酮 、 碳酸二甲酯 在 sodium hydride 作用下， 以 四氢呋喃 为溶剂， 以78%的产率得到methyl 5-(tert-butyldiphenylsilyloxy)-2-oxo-cyclohexan-1-carboxylate
  参考文献：
  名称：

  Carbanion Stabilization by Distal Silyloxy Groups. Origin of the High Diastereoselectivity in the Formation of Quaternary Centers with Aryllead(IV) Triacetate Reagents

  摘要：

  [GRAPHICS]Derivatives of methyl 5-hydroxy-2-oxo-1-cyclohexanecarboxylate react with aryllead(IV) reagents in high yield and with wide variation in diastereoselectivity. Ab initio calculations are consistent with a heretofore unrecognized attraction between the carbanionic center of the beta-ketoester intermediate and the distal OSiR3 group. This attractive interaction stabilizes the silyl group in the axial conformation and leads to the excellent trans diastereoselection in the formation of quaternary centers.

  DOI：

  10.1021/ol026863+

文献信息

• <i>tert</i>-Buyldiphenylsilylethyl (“TBDPSE”):  A Practical Protecting Group for Phenols
  作者：Brian S. Gerstenberger、Joseph P. Konopelski

  DOI：10.1021/jo048192u

  日期：2005.2.1

  A new protection group for phenols, the 2-(tert-butyldiphenylsilyl)ethyl (TBDPSE) group, has been prepared and investigated. Protection of a variety of substituted phenols proceeds in good to excellent yield. The group is stable to mild acid, base, hydrogenolysis conditions, and lithium/halogen exchange on the protected phenol. Removal is achieved with strong acid or standard fluoride treatment.

  制备并研究了一种新的苯酚保护基，即2-（叔丁基二苯基甲硅烷基）乙基（TBDPSE）。各种取代苯酚的保护均以良好至极佳的收率进行。该基团对弱酸，碱，氢解条件以及受保护的苯酚上的锂/卤素交换稳定。去除可通过强酸或标准氟化物处理实现。
• Carbanion Stabilization by Distal Silyloxy Groups. Origin of the High Diastereoselectivity in the Formation of Quaternary Centers with Aryllead(IV) Triacetate Reagents
  作者：Joseph P. Konopelski、Jinzhen Lin、Philip J. Wenzel、Hongbo Deng、Gregory I. Elliott、Brian S. Gerstenberger

  DOI：10.1021/ol026863+

  日期：2002.11.1

  [GRAPHICS]Derivatives of methyl 5-hydroxy-2-oxo-1-cyclohexanecarboxylate react with aryllead(IV) reagents in high yield and with wide variation in diastereoselectivity. Ab initio calculations are consistent with a heretofore unrecognized attraction between the carbanionic center of the beta-ketoester intermediate and the distal OSiR3 group. This attractive interaction stabilizes the silyl group in the axial conformation and leads to the excellent trans diastereoselection in the formation of quaternary centers.