trans-1-<<(1,1-dimethylethyl)diphenylsilyl>oxy>-2-methylcyclohexanecarbonitrile

• 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: trans-1-<<(1,1-dimethylethyl)diphenylsilyl>oxy>-2-methylcyclohexanecarbonitrile
• 英文别名: (1R,2R)-1-[tert-butyl(diphenyl)silyl]oxy-2-methylcyclohexane-1-carbonitrile
• 化学式: C₂₄H₃₁NOSi
• 分子量: 377.602
• InChiKey: GSXRQMCCVZTCMK-YKSBVNFPSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.04
• 重原子数：
  27
• 可旋转键数：
  5
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.46
• 拓扑面积：
  33
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为产物：
  描述：

  2-甲基环己酮 、 叔丁基苯氰基硅烷 在 zinc(II) iodide 作用下， 以 二氯甲烷 为溶剂， 反应 8.0h， 生成 trans-1-<<(1,1-dimethylethyl)diphenylsilyl>oxy>-2-methylcyclohexanecarbonitrile 、 cis-1-<<(1,1-dimethylethyl)diphenylsilyl>oxy>-2-methylcyclohexanecarbonitrile
  参考文献：
  名称：

  Addition of tert-butyldimethyl- or tert-butyldiphenylsilyl cyanide to hindered ketones

  摘要：

  The addition of trimethylsilyl cyanide (TMSCN), tert-butyldimethylsilyl cyanide (TBDMSCN) or tert-butyldiphenylsilyl cyanide (TBDPSCN) to sterically hindered ketones proceeded in good yield under catalysis by Lewis acids (ZnI2, CH2Cl2, 25-degrees-C) or bases (KCN, 18-crown-6, CH2Cl2, 25-degrees-C). For example, the ZnI2-catalyzed addition of TBDMSCN to 2,2-dimethylcyclohexanone (3e), 2,2,6-trimethylcyclohexanone (3f), and 2,2,6,6-tetramethylcyclohexanone (3g) provided the protected cyanohydrins 4e, 4f, and 4g in 94, 83, and 92 % yield, respectively. The C-1 ketone of C-6 dithioketal-protected Wieland-Miescher ketone ((4'aS)-4',4'a,7',8'-tetrahydro-4a'-methylspiro[1,3-dithiolane-2,2'(3'H)-naphthalen]-5'(6'H)-one (+)-(8)) provided (4'aS,5'S)-4',4'a,5',6',7',8'-hexahydro-5'-[(di-methyl(1,1-dimethylethyl)silyl)oxy]-4a'-methylspiro[1,3-dithiolane-2,2'(3'H)-naphthalene]-5'-car-bonitrile (+)-(10b) in 94% yield. An X-ray crystallographic study established that the C-5 center in (+)-10b has the correct absolute stereochemistry needed for a projected synthesis of the C-1 center in the A ring of taxol using (+)-10b as a starting material.

  DOI：

  10.1021/jo00053a030

文献信息

• Addition of tert-butyldimethyl- or tert-butyldiphenylsilyl cyanide to hindered ketones
  作者：Miroslaw Golinski、Carolyn P. Brock、David S. Watt

  DOI：10.1021/jo00053a030

  日期：1993.1

  The addition of trimethylsilyl cyanide (TMSCN), tert-butyldimethylsilyl cyanide (TBDMSCN) or tert-butyldiphenylsilyl cyanide (TBDPSCN) to sterically hindered ketones proceeded in good yield under catalysis by Lewis acids (ZnI2, CH2Cl2, 25-degrees-C) or bases (KCN, 18-crown-6, CH2Cl2, 25-degrees-C). For example, the ZnI2-catalyzed addition of TBDMSCN to 2,2-dimethylcyclohexanone (3e), 2,2,6-trimethylcyclohexanone (3f), and 2,2,6,6-tetramethylcyclohexanone (3g) provided the protected cyanohydrins 4e, 4f, and 4g in 94, 83, and 92 % yield, respectively. The C-1 ketone of C-6 dithioketal-protected Wieland-Miescher ketone ((4'aS)-4',4'a,7',8'-tetrahydro-4a'-methylspiro[1,3-dithiolane-2,2'(3'H)-naphthalen]-5'(6'H)-one (+)-(8)) provided (4'aS,5'S)-4',4'a,5',6',7',8'-hexahydro-5'-[(di-methyl(1,1-dimethylethyl)silyl)oxy]-4a'-methylspiro[1,3-dithiolane-2,2'(3'H)-naphthalene]-5'-car-bonitrile (+)-(10b) in 94% yield. An X-ray crystallographic study established that the C-5 center in (+)-10b has the correct absolute stereochemistry needed for a projected synthesis of the C-1 center in the A ring of taxol using (+)-10b as a starting material.