triethylsilyl((3-methylbutan-2-yl)oxy)silane

• 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: triethylsilyl((3-methylbutan-2-yl)oxy)silane
• 英文别名: triethyl(1,2-dimethyl-n-propoxy)silane；triethyl(3-methylbutan-2-yloxy)silane；1,2-Dimethylpropyl-triethylsilylether；Triethyl(3-methylbutan-2-yloxy)silane
• 化学式: C₁₁H₂₆OSi
• 分子量: 202.412
• InChiKey: BWANVEPAVYPOQI-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.05
• 重原子数：
  13
• 可旋转键数：
  6
• 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-甲基-2-丁酮 、 三乙基硅烷 在 [Re(O)(2-(2'-HO-Ph)-2-oxazoline(-))2][tetrakis(C₆F₅)borate] 作用下， 以76%的产率得到triethylsilyl((3-methylbutan-2-yl)oxy)silane
  参考文献：
  名称：

  金属氧合催化还原的机理：铼（V）氧合配合物催化有机羰基的氢化硅烷化

  摘要：

  铼氧配合物 [Re(O)(hoz)2][TFPB], 1（其中 hoz = 2-（2'-羟基苯基）-2-恶唑啉（-）和 TFPB = 四（五氟苯基）硼酸盐）催化硅氢化醛和酮在环境温度和气氛下。主要的有机产品是被保护的醇，如甲硅烷基醚。分离产率范围为 86% 至 57%。该反应需要较低的催化剂负载量 (0.1 mol%)，并且在 CH2Cl2 以及无溶剂的纯净状态下顺利进行。在后一种情况下，催化剂在反应结束时沉淀，便于分离和催化剂回收。制备了 Re(O)(hoz)(H), 3，并对其参与离子氢化硅烷化机制进行了评估。发现配合物 3 的氢化能力低于 Et3SiH，驳斥了其参与催化。一种与实验结果一致的可行机制，速率测量和动力学同位素效应（Et3SiH/Et3SiD = 1.3 和苯甲醛-H/苯甲醛-D = 1.0）被提出。有机硅烷通过与铼的 eta2 配位活化，有机羰基通过配位的 Si-H 键

  DOI：

  10.1021/ja055704t

文献信息

• Hydrosilylation of epoxides catalyzed by a cationic η1-silane iridium(iii) complex
  作者：Sehoon Park、Maurice Brookhart

  DOI：10.1039/c0cc05714b

  日期：——

  Cationic silane complex 2, catalyzes the hydrosilylation of epoxides and cyclic ethers to give the silyl-protected alcohols, regioselectively. A mechanistic study shows that the epoxide undergoes isomerization to the ketone, followed by hydrosilylation.

  阳离子硅烷络合物2，催化环氧化物和环醚的水解加硅反应，选择性地生成硅保护的醇类。机理研究表明，环氧化物首先发生异构化形成酮，随后进行水解加硅反应。
• A Convenient and Efficient Rhenium-Catalyzed Hydrosilylation of Ketones and Aldehydes
  作者：Hailin Dong、Heinz Berke

  DOI：10.1002/adsc.200900246

  日期：2009.8

  The easily available rhenium(I) complex [Re(CH3CN)3Br2(NO)] catalyzes the homogeneous hydrosilylation of a great variety of organic carbonyl compounds (ketones and aldehydes). The reaction is quite sensitive to the solvent applied. Chlorobenzene was found to be superior over all the other solvents used. Various aliphatic and aromatic silanes were tested. Excellent yields were achieved at 85 °C in chlorobenzene

  易于获得的rh（I）络合物[Re（CH 3 CN）3 Br 2（NO）]催化多种有机羰基化合物（酮和醛）的均相氢化硅烷化。该反应对所施加的溶剂非常敏感。发现氯苯优于所用的所有其他溶剂。测试了各种脂肪族和芳香族硅烷。使用三乙基硅烷，在85°C的氯苯中，获得了优异的收率，该反应的TOF值高达495 h -1。提出了可能的氢化硅烷化反应机理。
• Mechanism for Reduction Catalysis by Metal Oxo:  Hydrosilation of Organic Carbonyl Groups Catalyzed by a Rhenium(V) Oxo Complex
  作者：Elon A. Ison、Evan R. Trivedi、Rex A. Corbin、Mahdi M. Abu-Omar

  DOI：10.1021/ja055704t

  日期：2005.11.1

  evaluated. Complex 3 was found to be less hydridic than Et3SiH, refuting its participation in catalysis. A viable mechanism that is consistent with experimental findings, rate measurements, and kinetic isotope effects (Et3SiH/Et3SiD = 1.3 and benzaldehyde-H/benzaldehyde-D = 1.0) is proposed. Organosilane is activated via eta2-coordination to rhenium, and the organic carbonyl adds across the coordinated Si-H

  铼氧配合物 [Re(O)(hoz)2][TFPB], 1（其中 hoz = 2-（2'-羟基苯基）-2-恶唑啉（-）和 TFPB = 四（五氟苯基）硼酸盐）催化硅氢化醛和酮在环境温度和气氛下。主要的有机产品是被保护的醇，如甲硅烷基醚。分离产率范围为 86% 至 57%。该反应需要较低的催化剂负载量 (0.1 mol%)，并且在 CH2Cl2 以及无溶剂的纯净状态下顺利进行。在后一种情况下，催化剂在反应结束时沉淀，便于分离和催化剂回收。制备了 Re(O)(hoz)(H), 3，并对其参与离子氢化硅烷化机制进行了评估。发现配合物 3 的氢化能力低于 Et3SiH，驳斥了其参与催化。一种与实验结果一致的可行机制，速率测量和动力学同位素效应（Et3SiH/Et3SiD = 1.3 和苯甲醛-H/苯甲醛-D = 1.0）被提出。有机硅烷通过与铼的 eta2 配位活化，有机羰基通过配位的 Si-H 键
• Rhodium-Catalyzed, Efficient Deutero- and Tritiosilylation of Carbonyl Compounds from Hydrosilanes and Deuterium or Tritium
  作者：Miguel Rubio、Jesús Campos、Ernesto Carmona

  DOI：10.1021/ol202117t

  日期：2011.10.7

  A cationic rhodium compound which is an active catalyst for both the hydrogen isotope exchange in hydrosilanes and the hydrosilylation of carbonyl compounds permits, in a one-flask, two-step procedure, efficient deutero- and tritiosilylations using SiEt3H under D-2 (0.5 bar) or T-2, at low catalyst loadings (0.1-0.5 mol%).
• Controlled Hydrosilylation of Carbonyls and Imines Catalyzed by a Cationic Aluminum Alkyl Complex
  作者：Jürgen Koller、Robert G. Bergman

  DOI：10.1021/om2008277

  日期：2012.4.9

  The synthesis, characterization, and unprecedented catalytic activity of cationic aluminum alkyl complexes toward hydrosilylation are described. X-ray crystallographic analysis of Tp*AlMe2 (1) and [Tp*AlMe][I-3] (3) revealed the preference of Al for a tetrahedral coordination environment and the versatility of the Tp* ligand in stabilizing Al in bi- and tridentate coordination modes. [Tp*AlMe][MeB(C6F5)(3)] (2) is highly active toward the hydrosilylation of a wide variety of carbonyls and imines, thus providing an inexpensive and versatile alternative to late transition metal catalysts.