(1-(2-trimethylsilyl)phenyl)ethanol | 50882-50-3

• 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: (1-(2-trimethylsilyl)phenyl)ethanol
• 英文别名: 1-(2-Trimethylsilylphenyl)ethylalkohol；1-(2-Trimethylsilylphenyl)ethanol
• CAS: 50882-50-3
• 化学式: C₁₁H₁₈OSi
• 分子量: 194.349
• InChiKey: UXHUENBDPCSURT-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.29
• 重原子数：
  13
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.45
• 拓扑面积：
  20.2
• 氢给体数：
  1
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  cyclopentadienylruthenium(II) trisacetonitrile hexafluorophosphate 、 (1-(2-trimethylsilyl)phenyl)ethanol 以 1,2-二氯乙烷 为溶剂， 生成 (cyclopentadienyl)Ru(1-o-(Si(CH3)3)phenylethanol) hexafluorophosphate 、 (cyclopentadienyl)Ru(1-o-(Si(CH3)3)phenylethanol) hexafluorophosphate
  参考文献：
  名称：

  Planar Chiral (η⁶-Arene) Ruthenium Cp Complexes in Organic Synthesis:  Diastereoselective Complexation of Arene Compounds with Benzylic Alcohol and Its Synthetic Application to Chiral Biaryls

  摘要：

  1-o-Substituted phenylethanols gave diastereoselective ruthenium Cp complexes via coordination of ruthenium with benzylic oxygen. This reaction can be further applied to the diastereoselective ruthenium complexation of delta-lactone-bridged biaryls possessing a chiral benzyl alcohol function at the side chain. Although delta-lactone-bridged biphenyls 10a and 10b exist as an inseparable equilibrated atropisomeric mixture, the corresponding ruthenium complexes 11a and 11b were obtained as a single compound, respectively, with differentiated arene face complexation and fixation of the central bond. Analogous biaryl compound 15 with a naphthalene fragment gave three Cp ruthenium complexes, 16, 17, and 18, in various ratios depending on reaction temperature. Naphthalene ring-coordinated ruthenium complex 16 was isomerized to the complex 17 via axial isomerization and ruthenium fragment migration to the inverted arene face by heating at 50 degreesC in dichloroethane, and the ruthenium complexes 16 and 17 were further transformed to benzene ring-coordinated ruthenium complex 18 by heating at 90degreesC. The diastereoselective ruthenium complexation with fixation (and isomerization) of the axial bond of d-lactone-bridged biaryls 10 and 15 was supported by ab initio calculations. Also, the ab initio calculations of d-lactone-bridged biaryl ruthenium complexes with a naphthalene fragment were well consistent with the experimental results. The obtained ruthenium complexes of d-lactone-bridged biaryls afforded axially chiral biaryls by ring opening of delta-lactone with nonchiral reagents.

  DOI：

  10.1021/om020971i
• 作为产物：
  描述：

  三甲基氯硅烷 、 1-(2-溴苯基)乙醇 在 正丁基锂 作用下， 以 四氢呋喃 为溶剂， 以62%的产率得到(1-(2-trimethylsilyl)phenyl)ethanol
  参考文献：
  名称：

  Application of a promiscuous Arthrobacter sp. from Antarctic in aerobic (R)-selective deracemization and anaerobic (S)-selective reduction

  摘要：

  Inspired by enzyme-catalyzed reactions with microorganisms found in harsh marine environments, in which the amount of oxygen is restrict, we have shown that Arthrobacter sp. can perform different chemical transformations by switching from anaerobic to aerobic reaction conditions. Depending on the presence or absence of oxygen, either alcohol deracemization or ketone reduction with enantiocomplementary selectivities can be performed by the same microorganism. For example, reactions performed in the presence of oxygen favored the deracemization process, in which a racemic mixture of 1-(4-methylphenyl) ethanol was enriched to the (R)-alcohol in high conversion (94%) and high enantiomeric excess (94%). On the other hand, reaction in the absence of oxygen favored the reduction process, in which 4-methyl-acetophenone was converted to the (S)-alcohol in good conversion (58%) and excellent enantiomeric excess (> 99%). These concepts were applied for both deracemization and enantio selective reduction of heteroatom-containing (silicon, phosphorus, tin and boron) molecules. Moreover, preparative scale reactions were also performed for both chemical processes. (C) 2014 Elsevier B.V. All rights reserved.

  DOI：

  10.1016/j.molcatb.2014.09.016

文献信息

• Application of a promiscuous Arthrobacter sp. from Antarctic in aerobic (R)-selective deracemization and anaerobic (S)-selective reduction
  作者：Dayvson J. Palmeira、Lidiane S. Araújo、Juliana C. Abreu、Leandro H. Andrade

  DOI：10.1016/j.molcatb.2014.09.016

  日期：2014.12

  Inspired by enzyme-catalyzed reactions with microorganisms found in harsh marine environments, in which the amount of oxygen is restrict, we have shown that Arthrobacter sp. can perform different chemical transformations by switching from anaerobic to aerobic reaction conditions. Depending on the presence or absence of oxygen, either alcohol deracemization or ketone reduction with enantiocomplementary selectivities can be performed by the same microorganism. For example, reactions performed in the presence of oxygen favored the deracemization process, in which a racemic mixture of 1-(4-methylphenyl) ethanol was enriched to the (R)-alcohol in high conversion (94%) and high enantiomeric excess (94%). On the other hand, reaction in the absence of oxygen favored the reduction process, in which 4-methyl-acetophenone was converted to the (S)-alcohol in good conversion (58%) and excellent enantiomeric excess (> 99%). These concepts were applied for both deracemization and enantio selective reduction of heteroatom-containing (silicon, phosphorus, tin and boron) molecules. Moreover, preparative scale reactions were also performed for both chemical processes. (C) 2014 Elsevier B.V. All rights reserved.
• Planar Chiral (η⁶-Arene) Ruthenium Cp Complexes in Organic Synthesis:  Diastereoselective Complexation of Arene Compounds with Benzylic Alcohol and Its Synthetic Application to Chiral Biaryls
  作者：Ken Kamikawa、Kei Norimura、Masaru Furusyo、Takahiro Uno、Yasuko Sato、Atutoshi Konoo、Gerhard Bringmann、Motokazu Uemura

  DOI：10.1021/om020971i

  日期：2003.3.1

  1-o-Substituted phenylethanols gave diastereoselective ruthenium Cp complexes via coordination of ruthenium with benzylic oxygen. This reaction can be further applied to the diastereoselective ruthenium complexation of delta-lactone-bridged biaryls possessing a chiral benzyl alcohol function at the side chain. Although delta-lactone-bridged biphenyls 10a and 10b exist as an inseparable equilibrated atropisomeric mixture, the corresponding ruthenium complexes 11a and 11b were obtained as a single compound, respectively, with differentiated arene face complexation and fixation of the central bond. Analogous biaryl compound 15 with a naphthalene fragment gave three Cp ruthenium complexes, 16, 17, and 18, in various ratios depending on reaction temperature. Naphthalene ring-coordinated ruthenium complex 16 was isomerized to the complex 17 via axial isomerization and ruthenium fragment migration to the inverted arene face by heating at 50 degreesC in dichloroethane, and the ruthenium complexes 16 and 17 were further transformed to benzene ring-coordinated ruthenium complex 18 by heating at 90degreesC. The diastereoselective ruthenium complexation with fixation (and isomerization) of the axial bond of d-lactone-bridged biaryls 10 and 15 was supported by ab initio calculations. Also, the ab initio calculations of d-lactone-bridged biaryl ruthenium complexes with a naphthalene fragment were well consistent with the experimental results. The obtained ruthenium complexes of d-lactone-bridged biaryls afforded axially chiral biaryls by ring opening of delta-lactone with nonchiral reagents.