rac-acetyl(t-butyl)methylphenylsilane | 129340-98-3

• 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-acetyl(t-butyl)methylphenylsilane
• 英文别名: acetyl(t-butyl)methylphenylsilan；Acetyl(t-butyl)methyl(phenyl)silane；1-(tert-butyl-methyl-phenylsilyl)ethanone
• CAS: 129340-98-3
• 化学式: C₁₃H₂₀OSi
• 分子量: 220.387
• InChiKey: FIKLHTYWOBNOLJ-UHFFFAOYSA-N

物化性质

• 沸点：
  70-71 °C(Press: 0.2 Torr)
• 密度：
  0.92±0.1 g/cm3(Temp: 20 °C; Press: 760 Torr)(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.9
• 重原子数：
  15
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.46
• 拓扑面积：
  17.1
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  rac-acetyl(t-butyl)methylphenylsilane 在 4-二甲氨基吡啶 、 lithium aluminium tetrahydride 、 N,N'-二环己基碳二亚胺 作用下， 以 乙醚 、 二氯甲烷 为溶剂， 反应 50.0h， 生成 rac-(SiR,CS/SiS,CR)-t-butylmethyl-<1-(3,5-dinitrobenzoyloxy)ethyl>phenylsilane
  参考文献：
  名称：

  Stereoselective microbial reduction of racemic acetyl(t-butyl)methylphenylsilane by Trigonopsis variabilis (DSM 70714) and Cornebacterium dioxydans (ATCC 2176)

  摘要：

  (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.

  DOI：

  10.1016/0022-328x(91)83084-h
• 作为产物：
  描述：

  甲基苯基二氯硅烷 在 无水碳酸镉 、 mercury dichloride 作用下， 以 四氢呋喃 为溶剂， 生成 rac-acetyl(t-butyl)methylphenylsilane
  参考文献：
  名称：

  1,2-diastereoselection induced by chiral silicon in the addition of Grignard reagents to acylsilanes

  摘要：

  The reaction of acylsilanes 1 with Grignard reagents gives the diastereomeric alpha-hydroxysilanes 3. The level of asymmetric induction depends on the nature of R1 and R2. Good results were obtained for R1 = t-Bu, R2 = Me and R1 = alpha-Napht, R2 = Ph. Subsequent desilylation occurs with predominant inversion of configuration at carbon.

  DOI：

  10.1016/s0040-4039(00)93607-4

文献信息

• Synthese von racemischem Acetyl(t-butyl)methylphenylsilan und Acetylmethylphenyl[(trimethylsilyl)methyl]silan: Substrate für stereoselektive mikrobielle Reduktionen
  作者：Reinhold Tacke、Kirsten Fritsche、Andrea Tafel、Frank Wuttke

  DOI：10.1016/0022-328x(90)85345-y

  日期：1990.5
• TACKE, REINHOLD;BRAKMANN, SUSANNE;WUTTKE, FRANK;FOOLADI, JAMSHID;SYLDATK,+, J. ORGANOMET. CHEM., 403,(1991) N-2, C. 29-41
  作者：TACKE, REINHOLD、BRAKMANN, SUSANNE、WUTTKE, FRANK、FOOLADI, JAMSHID、SYLDATK,+

  DOI：——

  日期：——
• 1,2-diastereoselection induced by chiral silicon in the addition of Grignard reagents to acylsilanes
  作者：Bianca F Bonini、Stefano Masiero、Germana Mazzanti、Paolo Zani

  DOI：10.1016/s0040-4039(00)93607-4

  日期：1991.11

  The reaction of acylsilanes 1 with Grignard reagents gives the diastereomeric alpha-hydroxysilanes 3. The level of asymmetric induction depends on the nature of R1 and R2. Good results were obtained for R1 = t-Bu, R2 = Me and R1 = alpha-Napht, R2 = Ph. Subsequent desilylation occurs with predominant inversion of configuration at carbon.
• 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.