rac-(SiR,CR/SiS,CS)-t-butyl(1-hydroxyethyl)methylphenylsilan | 614719-66-3

• 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: rac-(SiR,CR/SiS,CS)-t-butyl(1-hydroxyethyl)methylphenylsilan
• 英文别名: t-Butyl(1-hydroxyethyl)methylphenylsilane；1-(tert-butyl-methyl-phenylsilyl)ethanol
• CAS: 614719-66-3
• 化学式: C₁₃H₂₂OSi
• 分子量: 222.403
• InChiKey: DKFMBCUMZSZJPO-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.69
• 重原子数：
  15
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.54
• 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：

  rac-(SiR,CR/SiS,CS)-t-butyl(1-hydroxyethyl)methylphenylsilan 、 3,5-二硝基苯甲酸 以93%的产率得到
  参考文献：
  名称：

  TACKE, REINHOLD;BRAKMANN, SUSANNE;WUTTKE, FRANK;FOOLADI, JAMSHID;SYLDATK,+, J. ORGANOMET. CHEM., 403,(1991) N-2, C. 29-41

  摘要：

  DOI：
• 作为产物：
  描述：

  rac-acetyl(t-butyl)methylphenylsilane 、 氢化铝锂 以93%的产率得到
  参考文献：
  名称：

  TACKE, REINHOLD;BRAKMANN, SUSANNE;WUTTKE, FRANK;FOOLADI, JAMSHID;SYLDATK,+, J. ORGANOMET. CHEM., 403,(1991) N-2, C. 29-41

  摘要：

  DOI：

文献信息

• Zur Stereochemie der mikrobiellen reduktion von rac-acetyl(t-butyl)methylphenylsilan mit Trigonopsis variabilis (DSM 70714) und Corynebacterium dioxydans (ATCC 21766): Aufklärung der absoluten konfiguration der biotransformationsprodukte (SiR,CR)- und (SiS,CR)-t-butyl(l-hydroxyethyl)methylphenylsilan
  作者：Reinhold Tacke、Frank Wuttke、Henning Henke

  DOI：10.1016/0022-328x(92)80002-f

  日期：1992.2

  The stereochemistry of the microbial reduction of rac-acety](t-butyl)methylphenylsilane (rac-1) with cells of Trigonopsis variabilis (DSM 70714) and Corynebacterium dioxydans (ATCC 21766) has been studied. The absolute configuration of the diastereomeric biotransformation products (SiR,CR)- and (SiS,CR)-t-butyl(1-hydroxyethyl)methylphenylsilane ((SiR,CR)-2 and (SiS,CR)-3) has been determined on the basis of a single-crystal X-ray diffraction study of (SiS,CS,C'R)-t-butylmethyl1-[N-(1-(1-naphthyl)ethyl) carbamoyloxy]ethyl}phenylsilane ((SiS,CS,C'R)-5).
• Stereoselective microbial reduction of racemic acetyl(t-butyl)methylphenylsilane by Trigonopsis variabilis (DSM 70714) and Cornebacterium dioxydans (ATCC 2176)
  作者：Reinhold Tacke、Susanne Brakmann、Frank Wuttke、Jamshid Fooladi、Christoph Syldatk、Dietmar Schomburg

  DOI：10.1016/0022-328x(91)83084-h

  日期：1991.2

  (SiR, CR)- and (SiS, CR)-t-butyl(1-hydroxyethyl)methylphenylsilane [(SiR,CR)-2 and (SiS,Cr)-3] have been prepared by (R)-selective microbial reduction of racemic acetyl(t-butyl)methylphenylsilane (rac-1) using resting free cells of the yeast Trigonopsis (DSM 70714) or the bacterium Corynebacterium dioxydans (ATCC 21766). The biotransformations were carried out on a 10 g scale. After separation by column chromatography on silica gel, the optically active diastereomers (SiR, CR)-2 and (SiS,CR)-3 produced by T. variabilis were obtained in good yields [74% ((SiR, CR)-2, 78% ((SiS, CR)}3)T. The products obtained from the reduction with C. dixydants were isolated in significantly lower yields [20% ((SiR, CR)-), 20% ((SiS,CR)-3)]; reaction conditions not optimized). Both bioconversions gave products with high enantiomeric purities [T. variabilis: 97% ee ((SiR, CR)-2), 96% ee ((SiS, CR)-3); C. dioxydans: greater-than-or-equal-to 99% ee ((SiR, CR)-2), greater-than-or-equal-to 99% ee ((SiS, CR)-3)].To throw light on the stereochemical aspects of these biotransformations, an X-ray diffraction study was carried out on the 3,5-dinitrobenzoate of rac-(SiR,CS/SiS,CR)-3. In addition, H-1 NMR spectroscopic stereochemical correlation studies were performed with the (S)-MTPA esters derived from (SiR,CR)-2, (SiS,CR)-3, rac-(SiR,CR/SiS,CS)-2 and rac-(SiR,CS/SiS,CR)-3 [rac-(SiR,CR/SiS,CS)-2 and rac-(SiR,CS/SiS,CR)-3 were obtained by reduction of rac-1 with LiA1H4 in diethyl ether, followed by chromatographic separation of the diastereomers on silica gel]. These stereochemical studies allowed assignment of the absolute configurations and enantiomeric purities of the biotransformation products.