(S)-1-(4-methoxyphenyl)-1-(trichlorosilyl)ethane | 317832-89-6

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯酚醚
• 英文名称: (S)-1-(4-methoxyphenyl)-1-(trichlorosilyl)ethane
• 英文别名: trichloro-[(1S)-1-(4-methoxyphenyl)ethyl]silane
• CAS: 317832-89-6
• 化学式: C₉H₁₁Cl₃OSi
• 分子量: 269.63
• InChiKey: NXODAHNROMATGZ-ZETCQYMHSA-N

物化性质

• 沸点：
  246.9±23.0 °C(Predicted)
• 密度：
  1.243±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.99
• 重原子数：
  14
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.33
• 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：

  (S)-1-(4-methoxyphenyl)-1-(trichlorosilyl)ethane 生成 (S)-(-)-对甲氧基苯乙醇
  参考文献：
  名称：

  Modification of Chiral Monodentate Phosphine (MOP) Ligands for Palladium-Catalyzed Asymmetric Hydrosilylation of Styrenes

  摘要：

  在钯催化的苯乙烯与三氯硅烷的不对称氢化硅烷化反应中，研究了几种手性单膦配体 (R)-2-二芳基膦基-1,1'-联萘 (2) 的对映选择性。在与 (R)-2-双[3,5-双(三氟甲基)苯基]膦基-1,1'-联萘 (2g) 的反应中观察到最高的对映选择性，得到 98 的 (S)-1-苯基乙醇氢化硅烷化产物氧化后的％ee。

  DOI：

  10.1246/cl.2000.1272
• 作为产物：
  描述：

  4-甲氧基苯乙烯 在 bis(η3-allyl-μ-chloropalladium(II)) 三氯硅烷 作用下， 反应 36.0h， 以93%的产率得到(S)-1-(4-methoxyphenyl)-1-(trichlorosilyl)ethane
  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

文献信息

• The design of second generation MOP-phosphonites: efficient chiral hydrosilylation of functionalised styrenes
  作者：James T. Fleming、Arne Ficks、Paul G. Waddell、Ross W. Harrington、Lee J. Higham

  DOI：10.1039/c5dt04475h

  日期：——

  A series of enantiopure MOP-phosphonite ligands, with tailored steric profiles, have been synthesised and are proven to be very successful in high-yielding, regio- and enantioselective catalytic hydrosilylation reactions of substituted styrenes, affording important chiral secondary alcohols.

  一系列具有定制立体位阻特性的对映纯MOP-膦酸酯配体已经合成，并被证明在取代苯乙烯的高产率、区域选择性和对映选择性催化氢硅烷化反应中非常成功，从而得到重要的手性二级醇。
• 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。
• Modification of Chiral Monodentate Phosphine (MOP) Ligands for Palladium-Catalyzed Asymmetric Hydrosilylation of Styrenes
  作者：Tamio Hayashi、Seiji Hirate、Kenji Kitayama、Hayato Tsuji、Akira Torii、Yasuhiro Uozumi

  DOI：10.1246/cl.2000.1272

  日期：2000.11

  In the palladium-catalyzed asymmetric hydrosilylation of styrene with trichlorosilane, several chiral monophosphine ligands, (R)-2-diarylphosphino-1,1′-binaphthyls (2), were examined for their enantioselectivity. The highest enantioselectivity was observed in the reaction with (R)-2-bis[3,5-bis(trifluoromethyl)phenyl]phosphino-1,1′-binaphthyl (2g), which gave (S)-1-phenylethanol of 98% ee after oxidation of the hydrosilylation product.

  在钯催化的苯乙烯与三氯硅烷的不对称氢化硅烷化反应中，研究了几种手性单膦配体 (R)-2-二芳基膦基-1,1'-联萘 (2) 的对映选择性。在与 (R)-2-双[3,5-双(三氟甲基)苯基]膦基-1,1'-联萘 (2g) 的反应中观察到最高的对映选择性，得到 98 的 (S)-1-苯基乙醇氢化硅烷化产物氧化后的％ee。
• Helical Poly(quinoxaline-2,3-diyl)s Bearing Metal-Binding Sites as Polymer-Based Chiral Ligands for Asymmetric Catalysis
  作者：Takeshi Yamamoto、Michinori Suginome

  DOI：10.1002/anie.200803719

  日期：2009.1.5

  Living it up: Helical polyquinoxalines with single and multiple metal‐binding sites, prepared by living polymerization of o‐diisocyanobenzenes, are used in the asymmetric hydrosilylation of styrenes, resulting in comparable enantioselectivities to those obtained by low‐molecular‐weight catalyst systems (up to 87 % ee, stereochemistry was determined by a chiral initiator) and a turnover number of almost

  增强活性：通过邻二异氰基苯的活性聚合制备的具有单个和多个金属结合位点的螺旋聚喹喔啉可用于苯乙烯的不对称氢化硅烷化反应，其对映选择性可与低分子量催化剂体系获得的对映选择性相当（到87％  ee时，通过手性引发剂测定立体化学），周转数接近1000。
• 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.