tert-butyl-[(E)-ethoxy(oxolan-2-ylidene)methoxy]-dimethylsilane | 131237-50-8

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 氧唑烯
• 英文名称: tert-butyl-[(E)-ethoxy(oxolan-2-ylidene)methoxy]-dimethylsilane
• CAS: 131237-50-8
• 化学式: C₁₃H₂₆O₃Si
• 分子量: 258.433
• InChiKey: JVWRRGHLDXBEKP-VAWYXSNFSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.02
• 重原子数：
  17
• 可旋转键数：
  5
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.85
• 拓扑面积：
  27.7
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为产物：
  描述：

  2-四氢糠酸乙酯 、 叔丁基二甲基氯硅烷 在 lithium diisopropyl amide 作用下， 生成 tert-butyl-[(Z)-ethoxy(oxolan-2-ylidene)methoxy]-dimethylsilane 、 tert-butyl-[(E)-ethoxy(oxolan-2-ylidene)methoxy]-dimethylsilane
  参考文献：
  名称：

  Stereochemical control in the ester enolate Claisen rearrangement. 1. Stereoselectivity in silyl ketene acetal formation

  摘要：

  Methods for the stereoselective deprotonation and silylation of esters were systematically investigated. A kinetically controlled enolization in combination with a kinetic resolution process accounts for the selective formation of (E)- and (Z)-silyl ketene acetals in THF and THF/dipolar solvent systems with bases such as LDA, LHMDS, and KHMDS. A thermodynamic equilibration mechanism seems to be of minor significance with ester enolates. Improved reaction conditions were exemplified in a highly stereoselective Claisen rearrangement in THF/45% DMPU.

  DOI：

  10.1021/jo00002a030

文献信息

• IRELAND, ROBERT E.;WIPF, PETER;ARMSTRONG, JOSEPH D. III, J. ORG. CHEM., 56,(1991) N, C. 650-657
  作者：IRELAND, ROBERT E.、WIPF, PETER、ARMSTRONG, JOSEPH D. III

  DOI：——

  日期：——
• Stereochemical control in the ester enolate Claisen rearrangement. 1. Stereoselectivity in silyl ketene acetal formation
  作者：Robert E. Ireland、Peter Wipf、Joseph D. Armstrong

  DOI：10.1021/jo00002a030

  日期：1991.1

  Methods for the stereoselective deprotonation and silylation of esters were systematically investigated. A kinetically controlled enolization in combination with a kinetic resolution process accounts for the selective formation of (E)- and (Z)-silyl ketene acetals in THF and THF/dipolar solvent systems with bases such as LDA, LHMDS, and KHMDS. A thermodynamic equilibration mechanism seems to be of minor significance with ester enolates. Improved reaction conditions were exemplified in a highly stereoselective Claisen rearrangement in THF/45% DMPU.