(R)-1-(2-chlorophenyl)-1-(trichlorosilyl)ethane | 154377-49-8

• 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: (R)-1-(2-chlorophenyl)-1-(trichlorosilyl)ethane
• 英文别名: 1-(2-chlorophenyl)-1-(trichlorosilyl)ethane；trichloro-[(1R)-1-(2-chlorophenyl)ethyl]silane
• CAS: 154377-49-8
• 化学式: C₈H₈Cl₄Si
• 分子量: 274.049
• InChiKey: GSBAJXTTZFUBES-ZCFIWIBFSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.64
• 重原子数：
  13
• 可旋转键数：
  1
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.25
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  0

反应信息

• 作为反应物：
  描述：

  (R)-1-(2-chlorophenyl)-1-(trichlorosilyl)ethane 在 potassium fluoride 、 双氧水 、 potassium hydrogencarbonate 作用下， 以 四氢呋喃 、 甲醇 为溶剂， 反应 16.0h， 以86%的产率得到(R)-1-(2-氯苯基)乙醇
  参考文献：
  名称：

  芳烃的高度对映选择性氢化硅烷化

  摘要：

  目前，将烯烃转化为旋光醇的最有效和最经济的方法是两步序列：氢化硅烷化/氧化。许多工作致力于阐明该过程的有效催化剂，但迄今为止只有一种有效且高度立体选择性的过程可用。在此，我们提出了一种用于芳族烯烃不对称氢化硅烷化的新型催化体系，该体系以高产率和对该反应观察到的最高对映选择性（高达 99% ee）得到产物。该反应对各种取代的芳族烯烃有效，在 Tamao 氧化后可以高产率获得几乎光学纯的苄醇。

  DOI：

  10.1021/ja025617q
• 作为产物：
  描述：

  2-氯苯乙烯 在 bis(η3-allyl-μ-chloropalladium(II)) 、 (S_A,R_C,R_C)-BINOL=P-N-(1-ethylphenyl)2 三氯硅烷 作用下， 反应 40.33h， 以89%的产率得到(R)-1-(2-chlorophenyl)-1-(trichlorosilyl)ethane
  参考文献：
  名称：

  芳烃的高度对映选择性氢化硅烷化

  摘要：

  目前，将烯烃转化为旋光醇的最有效和最经济的方法是两步序列：氢化硅烷化/氧化。许多工作致力于阐明该过程的有效催化剂，但迄今为止只有一种有效且高度立体选择性的过程可用。在此，我们提出了一种用于芳族烯烃不对称氢化硅烷化的新型催化体系，该体系以高产率和对该反应观察到的最高对映选择性（高达 99% ee）得到产物。该反应对各种取代的芳族烯烃有效，在 Tamao 氧化后可以高产率获得几乎光学纯的苄醇。

  DOI：

  10.1021/ja025617q

文献信息

• Highly Enantioselective Hydrosilylation of Aromatic Alkenes
  作者：Jakob F. Jensen、Bo Y. Svendsen、Thomas V. la Cour、Henriette L. Pedersen、Mogens Johannsen

  DOI：10.1021/ja025617q

  日期：2002.5.1

  Currently, the most effective and economic way to convert an alkene into an optically active alcohol is the two-step sequence: hydrosilylation/oxidation. Much work has been devoted to elucidating effective catalysts for this process, but hitherto only one effective and highly stereoselective process has been available. Herein we present a novel catalytic system for the asymmetric hydrosilylation of

  目前，将烯烃转化为旋光醇的最有效和最经济的方法是两步序列：氢化硅烷化/氧化。许多工作致力于阐明该过程的有效催化剂，但迄今为止只有一种有效且高度立体选择性的过程可用。在此，我们提出了一种用于芳族烯烃不对称氢化硅烷化的新型催化体系，该体系以高产率和对该反应观察到的最高对映选择性（高达 99% ee）得到产物。该反应对各种取代的芳族烯烃有效，在 Tamao 氧化后可以高产率获得几乎光学纯的苄醇。
• Asymmetric Hydrosilylation of Styrenes by Use of New Chiral ­Phosphoramidites
  作者：Xinsheng Li、Jianan Song、Dongcheng Xu、Lichun Kong

  DOI：10.1055/s-2008-1032199

  日期：2008.3

  New chiral phosphoramidites were synthesized from chiral unsymmetrical amines and BINOL in good yields. Enantioselective hydrosilylation of styrenes with trichlorosilane in the presence of palladium complexes of these ligands provided chiral silanes in medium to high yields. Oxidation of these chiral silanes with hydrogen peroxide gave the corresponding chiral secondary alcohols in up to 97% ee.

  由手性不对称胺和 BINOL 合成了新的手性亚磷酰胺，收率良好。在这些配体的钯配合物存在下，苯乙烯与三氯硅烷的对映选择性氢化硅烷化以中等至高产率提供手性硅烷。用过氧化氢氧化这些手性硅烷得到相应的手性仲醇，最高可达 97% ee。
• Asymmetric Hydrosilylation of Styrenes Catalyzed by Palladium−MOP Complexes:  Ligand Modification and Mechanistic Studies
  作者：Tamio Hayashi、Seiji Hirate、Kenji Kitayama、Hayato Tsuji、Akira Torii、Yasuhiro Uozumi

  DOI：10.1021/jo001614p

  日期：2001.2.1

  In the palladium-catalyzed asymmetric hydrosilylation of styrene (3a) with trichlorosilane, several chiral monophosphine ligands, (R)-2-diarylphosphino-1,1'-binaphthyls(2a-g), were examined for their enantioselectivity. The highest enantioselectivity was observed in the reaction with (R)-2-bis [3,5-bis(trifluoromethyl)phenyl] phosphino-l,1'-binaphthyl (2g), which gave (S)-1-phenylethanol (5a) of 98% ee after oxidation of the hydrosilylation product, 1-phenyl-1-(trichlorosilyl)ethane (4a). The palladium complex of 2g also efficiently catalyzed the asymmetric hydrosilylation of substituted styrenes on the phenyl ring or at the beta position to give the corresponding chiral benzylic alcohols of over 96% ee. Deuterium-labeling studies on the hydrosilylation of regiospecifically deuterated styrene revealed that P-hydrogen elimination from l-phenylethyl(silyl)palladium intermediate is very fast compared with reductive elimination giving hydrosilylation product when ligand 2g is used. The reaction of o-allylstyrene (9) with trichlorosilane catalyzed by (R)-2g/Pd gave (1S,2R)-1-methyl-2-(trichlorosilylmethyl)indan (10) (91% ee) and (S)-1-(2-(propenyl)phenyl)-1-trichlorosilylethanes (11a and 11b) (95% ee). On the basis of their opposite configurations at the benzylic position, a rationale for the high enantioselectivity of ligand 2g is proposed.
• Regio- and enantioselective hydrosilylation of 1-arylalkenes by use of palladium-MOP catalyst
  作者：Yasuhiro Uozumi、Kenji Kitayama、Tamio Hayashi

  DOI：10.1016/s0957-4166(00)82214-4

  日期：1993.1

  Hydrosilylation of styrenes bearing beta-substituents with trichlorosilane was catalyzed by a palladium complex (0.1 mol %) coordinated with (R)-2-methoxy-2'-diphenylphosphino-1,1'-binaphthyl ((R)-MeO-MOP) to give high yields of optically active 1-aryl-1-silylalkanes (80 similar to 85% ee) as single regioisomers. The resulting silanes were readily converted into the corresponding optically active alcohols (80 similar to 99% yield).
• Asymmetric palladium-catalyzed hydrosilylation of styrenes using efficient chiral spiro phosphoramidite ligands
  作者：Xun-Xiang Guo、Jian-Hua Xie、Guo-Hua Hou、Wen-Jian Shi、Li-Xin Wang、Qi-Lin Zhou

  DOI：10.1016/j.tetasy.2004.05.038

  日期：2004.7

  Asymmetric hydrosilylation of styrene derivatives with trichlorosilane in the presence of palladium complexes of chiral spiro phosphoramidites provided 1-aryl-1-silylalkanes as single regioisomers in high yields, which have been oxidized with hydrogen peroxide to give the corresponding chiral alcohols in up to 99.1% ee. (C) 2004 Elsevier Ltd. All rights reserved.