tert-Butyldimethyl(pent-3-yloxy)silane | 335355-65-2

• 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: tert-Butyldimethyl(pent-3-yloxy)silane
• 英文别名: tert-butyl-dimethyl-pentan-3-yloxysilane
• CAS: 335355-65-2
• 化学式: C₁₁H₂₆OSi
• 分子量: 202.412
• InChiKey: RWPYUHCRLKDIMB-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.2
• 重原子数：
  13
• 可旋转键数：
  5
• 环数：
  0.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  9.2
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为产物：
  描述：

  3-(tert-butyldimethylsiloxy)-1,4-pentadiene 在 [Rh(S,S-Dipamp)(NBD)]OTf 、 氢气 作用下， 以 甲醇 为溶剂， 21.0 ℃ 、162.13 kPa 条件下， 反应 0.17h， 生成 tert-Butyldimethyl(pent-3-yloxy)silane 、 (S)-3-tert-butyldimethylsiloxy-1-pentene 、 (R)-3-tert-butyldimethylsiloxy-1-pentene
  参考文献：
  名称：

  非共轭二烯在铑催化的还原反应中的立体选择性

  摘要：

  Abstractmagnified imageThe stereochemical course of rhodium‐catalysed addition of hydrogen and catecholborane to bicyclo[2.2.1]heptadiene, and of hydrogen to a range of cyclic dienes has been analysed. For hydroboration, the overall catalytic reaction possesses exo‐selectivity, but the initial step is endo‐selective. For hydrogenation (deuteration), the first step may occur with either exo‐ or endo‐ selectivity, depending on the structure of the diene. This enables a distinction to be made between pathways involving prior dissociation of the diene, and direct addition to the complexed diene without full dissociation. The relative ease of hydrogenation of the first and second double bonds varies markedly with reactant structure, and also depends on the choice of catalyst ligands. For dicyclopentadiene, hydrogenation of the cyclopentene double bond is accompanied by rapid alkene isomerisation, as revealed by deuterium addition. The asymmetric hydrogenation of acyclic skipped meso‐dienes is reported, demonstrating control of relative rates of the two sequential steps, with ees of up to 53% after the first reduction.

  DOI：

  10.1002/adsc.200900013

文献信息

• Stereoselectivity in the Rhodium-Catalysed Reductions of Non-Conjugated Dienes
  作者：Bao Nguyen、John M. Brown

  DOI：10.1002/adsc.200900013

  日期：2009.6

  Abstractmagnified imageThe stereochemical course of rhodium‐catalysed addition of hydrogen and catecholborane to bicyclo[2.2.1]heptadiene, and of hydrogen to a range of cyclic dienes has been analysed. For hydroboration, the overall catalytic reaction possesses exo‐selectivity, but the initial step is endo‐selective. For hydrogenation (deuteration), the first step may occur with either exo‐ or endo‐ selectivity, depending on the structure of the diene. This enables a distinction to be made between pathways involving prior dissociation of the diene, and direct addition to the complexed diene without full dissociation. The relative ease of hydrogenation of the first and second double bonds varies markedly with reactant structure, and also depends on the choice of catalyst ligands. For dicyclopentadiene, hydrogenation of the cyclopentene double bond is accompanied by rapid alkene isomerisation, as revealed by deuterium addition. The asymmetric hydrogenation of acyclic skipped meso‐dienes is reported, demonstrating control of relative rates of the two sequential steps, with ees of up to 53% after the first reduction.