(1-phenylethoxy)(diphenyl)silane | 79201-73-3

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: (1-phenylethoxy)(diphenyl)silane
• 英文别名: Diphenyl[(1S)-1-phenylethoxy]silane；diphenyl-[(1S)-1-phenylethoxy]silane
• CAS: 79201-73-3
• 化学式: C₂₀H₂₀OSi
• 分子量: 304.464
• InChiKey: OMJXBHDGPPKQFE-KRWDZBQOSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.3
• 重原子数：
  22
• 可旋转键数：
  5
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.1
• 拓扑面积：
  9.2
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  (1-phenylethoxy)(diphenyl)silane 在 吡啶 、 氢氟酸 作用下， 反应 1.0h， 生成 (S)-(-)-1-苯乙醇
  参考文献：
  名称：

  31P NMR assays for rapid determination of enantiomeric excess in catalytic hydrosilylations and transfer hydrogenations

  摘要：

  Chiral chlorophosphine (S)-(1,1'-binaphthalen-2,2'-dioxy)chlorophosphine (S)-2 was tested for its performance as a chiral-derivatizing agent (CDA) using solutions of various alcohols, amines, and N-BOC amino acids. Based on P-31 NMR spectroscopy, the enantiomeric excess was determined within less than 5 min per sample, reaching an accuracy of +/- 1%. One-pot procedures for a combination of the method with typical homogenous catalytic transformations of prochiral ketones were established. Hydrosilylation products may be analyzed after conversion into alcohols using HF bound to PS-vinyl pyridine co-polymer beads. Transfer hydrogenations simply require solvent evaporation prior to the use of the CDA. (C) 2009 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetasy.2009.01.022
• 作为产物：
  描述：

  二苯基硅烷 、 苯乙酮 在 C₄₉H₄₈ClCuN₂ 、 copper(l) chloride 、 sodium t-butanolate 作用下， 以 甲苯 为溶剂， 反应 0.33h， 生成 (1-phenylethoxy)(diphenyl)silane
  参考文献：
  名称：

  Design and Synthesis of C₂-Symmetric N-Heterocyclic Carbene Precursors and Metal Carbenoids

  摘要：

  Chiral, C-2-symmetric imidazolium and imidazolinium ions, as well as the corresponding copper- or silver-bound carbenoids, have been prepared. Structural study of these compounds by X-ray crystallography reveals a chiral pocket that surrounds the putative carbene site or the metal carbene bond, at carbon 2, in three of the four ligands prepared. Preliminary investigation into the application of these complexes has shown one of them to be highly enantioselective in the hydrosilylation of acetophenone.

  DOI：

  10.1021/jo2012434

文献信息

• Carbohydrate-based N-heterocyclic carbenes for enantioselective catalysis
  作者：Alexander S. Henderson、John F. Bower、M. Carmen Galan

  DOI：10.1039/c4ob02056a

  日期：——

  Versatile syntheses of C2-linked and C2-symmetric carbohydrate-based imidazol(in)ium salts from functionalised amino-carbohydrate derivatives are reported. The novel NHCs were ligated to [Rh(COD)Cl]2 and evaluated in Rh-catalysed asymmetric hydrosilylation of ketones with good yields and promising enantioselectivities.

  报道了从官能化的氨基碳水化合物衍生物多功能合成C 2连接的和C 2对称的基于碳水化合物的咪唑盐。将新型NHC连接到[Rh（COD）Cl] 2上，并在Rh催化的酮的不对称氢化硅烷化中进行了评估，产率高，对映选择性高。
• Rhodium(I)-catalysed asymmetric hydrosilylation of ketones using new diferrocenyl dichalcogenides (R,S)-{[EC5H3CHMe(NMe2)]Fe(C5H5)}2(E = S, Se, Te), as chiral ligands
  作者：Yoshiaki Nishibayashi、Jai Deo Singh、Kyohei Segawa、Shin-ichi Fukuzawa、Sakae Uemura

  DOI：10.1039/c39940001375

  日期：——

  The new chiral compounds, (R,S)-di[2-(1-dimethylaminoethyl)ferrocenyl] dichalcogenides (R,S)-[EC5H3CHMe(NMe2)]Fe(C5H5)}2(E = S, Se, Te), work effectively as chiral ligands for the rhodium(I)-catalysed asymmetric hydrosilylation of alkyl aryl ketones resulting in high enantiomeric excess and moderate chemical yields.

  新型手性化合物，(R,S)-二[2-(1-二甲氨基乙基)二茂铁基]二硫属化物（R,S）-[EC5H3CHMe(NMe2)]Fe(C5H5)}2(E = S, Se, Te)，作为铑(I)催化下烷基芳基酮不对称氢硅烷化的手性配体效果显著，获得了高对映体过量率和适中的化学产率。
• Chiral Frustrated Lewis Pairs Catalyzed Highly Enantioselective Hydrosilylations of Ketones
  作者：Xiaoqin Liu、Qiaotian Wang、Caifang Han、Xiangqing Feng、Haifeng Du

  DOI：10.1002/cjoc.201900121

  日期：2019.7

  A highly enantioselective Piers‐type hydrosilylation of simple ketones was successfully realized using a chiral frustrated Lewis pair of tri‐tert‐butylphosphine and chiral diene‐derived borane as catalyst. A wide range of optically active secondary alcohols were furnished in 80%—99% yields with 81%—97% ee's under mild reaction conditions.

  简单酮的对映体选择性高墩型氢化硅烷化，使用手性路易斯沮丧对三- ，成功地实现叔丁基膦和手性二烯衍生的硼烷作为催化剂。在温和的反应条件下，提供了多种旋光性仲醇，收率为80％-99％，ee为81％-97％。
• Enantioselective Zinc-Catalyzed Hydrosilylation of Ketones using Pybox or Pybim Ligands
  作者：Kathrin Junge、Konstanze Möller、Bianca Wendt、Shoubhik Das、Dirk Gördes、Kerstin Thurow、Matthias Beller

  DOI：10.1002/asia.201100561

  日期：2012.2.6

  The combination of ZnEt2 and chiral pyridinebisoxazoline (pybox) or pyridinebisimidazoline (pybim) ligands catalyzed the asymmetric hydrosilylation of aryl, alkyl, cyclic, heterocyclic, and aliphatic ketones. Under mild conditions, high yields and good enantioselectivities were achieved. ESI measurements allowed for the characterization of the active catalyst.

  ZnEt 2和手性吡啶双恶唑啉（pybox）或吡啶双咪唑啉（pybim）配体的组合催化了芳基，烷基，环状，杂环和脂肪族酮的不对称氢化硅烷化。在温和的条件下，获得了高收率和良好的对映选择性。ESI测量允许表征活性催化剂。
• Asymmetric Hydrosilylation of Ketones Using<b><i>Trans</i></b>-Chelating Chiral Peralkylbisphosphine Ligands Bearing Primary Alkyl Substituents on Phosphorus Atoms
  作者：Ryoichi Kuwano、Masaya Sawamura、Junya Shirai、Masatoshi Takahashi、Yoshihiko Ito

  DOI：10.1246/bcsj.73.485

  日期：2000.2

  Asymmetric hydrosilylation of simple ketones with diphenylsilane proceeded at -40 °C in the presence of a rhodium complex (0.001—0.01 molar amount) coordinated with a trans-chelating chiral bisphosphine ligand bearing linear alkyl substituents on the phosphorus atoms, (R,R)-(S,S)-Et-, Pr-, or BuTRAP, giving the corresponding optically active (S)-secondary alcohols with up to 97% ee. The asymmetric

  简单酮与二苯基硅烷的不对称氢化硅烷化在 -40 °C 下在铑配合物（0.001-0.01 摩尔量）存在下进行，该配合物与在磷原子上带有线性烷基取代基的反式螯合手性双膦配体（R，R） -(S,S)-Et-、Pr- 或 BuTRAP，得到相应的光学活性 (S)-仲醇，其 ee 高达 97%。使用具有更大 P 取代基的 TRAP 配体的不对称氢化硅烷化导致低得多的对映选择性。EtTRAP-铑催化剂对于具有铑原子配位位点的酮酯的不对称氢化硅烷化也有效（高达 98% ee）。通过使用 2.5 摩尔二苯基硅烷的不对称还原，从相应的二酮中获得了高达 99% ee 的旋光对称二醇。