(S)-1-(3-chlorophenyl)-1-(trichlorosilyl)ethane

• 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: (S)-1-(3-chlorophenyl)-1-(trichlorosilyl)ethane
• 英文别名: trichloro-[(1S)-1-(3-chlorophenyl)ethyl]silane
• 化学式: C₈H₈Cl₄Si
• 分子量: 274.049
• InChiKey: AMLXZBAKOCHFKD-LURJTMIESA-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：

  (S)-1-(3-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， 生成 (1S)-1-(3-氯苯基)乙醇
  参考文献：
  名称：

  使用新型手性亚磷酰胺对苯乙烯进行不对称氢化硅烷化

  摘要：

  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。

  DOI：

  10.1055/s-2008-1032199
• 作为产物：
  描述：

  3-氯苯乙烯 在 bis(η3-allyl-μ-chloropalladium(II)) 、 (S)-2-diphenylphosphino-1,1'-binaphthyl 三氯硅烷 作用下， 反应 36.0h， 生成 (R)-1-(3-chlorophenyl)-1-(trichlorosilyl)ethane 、 (S)-1-(3-chlorophenyl)-1-(trichlorosilyl)ethane
  参考文献：
  名称：

  钯催化的苯乙烯与新的手性单齿膦配体的不对称氢化硅烷化

  摘要：

  在带有新型手性单齿膦配体（S）-2-二苯基膦-1,1'-联萘基[（S）-H]的钯催化剂（0.1 mol％）存在下，苯乙烯（ArCH CHR）与三氯硅烷的不对称氢化硅烷化-MOP]，然后氧化所得的1-芳基-1-甲硅烷基烷烃，得到旋光性苄醇，其对映体过量最多为96％（ee）。

  DOI：

  10.1039/c39950001533

文献信息

• Palladium-catalysed asymmetric hydrosilylation of styrenes with a new chiral monodentate phosphine ligand
  作者：Kenji Kitayama、Yasuhiro Uozumi、Tamio Hayashi

  DOI：10.1039/c39950001533

  日期：——

  hydrosilylation of styrenes (ArCHCHR) with trichlorosilane in the presence of a palladium catalyst (0.1 mol%) bearing a new chiral monodentate phosphine ligand, (S)-2-diphenylphosphino-1,1′-binaphthyl [(S)-H-MOP], followed by oxidation of the resulting 1-aryl-1-silylalkanes, gives optically active benzylic alcohols of up to 96% enantiomeric excess (e.e.).

  在带有新型手性单齿膦配体（S）-2-二苯基膦-1,1'-联萘基[（S）-H]的钯催化剂（0.1 mol％）存在下，苯乙烯（ArCH CHR）与三氯硅烷的不对称氢化硅烷化-MOP]，然后氧化所得的1-芳基-1-甲硅烷基烷烃，得到旋光性苄醇，其对映体过量最多为96％（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.
• 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.
• 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。