叔丁基苯氰基硅烷 | 145545-43-3

• 物质功能分类: 化学试剂 - 硅烷试剂
• 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
• 中文名称: 叔丁基苯氰基硅烷
• 英文名称: tert-butyldiphenylsilyl cyanide
• 英文别名: (1,1-dimethylethyl)diphenylsilyl cyanide；[tert-butyl(diphenyl)silyl]formonitrile
• CAS: 145545-43-3
• 化学式: C₁₇H₁₉NSi
• 分子量: 265.43
• InChiKey: ZJHNDMZEXWDAHA-UHFFFAOYSA-N

物化性质

• 沸点：
  136 °C0.7 mm Hg(lit.)
• 密度：
  1.017 g/mL at 25 °C(lit.)
• 闪点：
  >110°C

计算性质

• 辛醇/水分配系数(LogP)：
  3.11
• 重原子数：
  19
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.24
• 拓扑面积：
  23.8
• 氢给体数：
  0
• 氢受体数：
  1

安全信息

• TSCA：
  No
• 危险品标志：
  T
• 安全说明：
  S36/37/39,S45
• 危险类别码：
  R23/24/25
• WGK Germany：
  3
• 危险品运输编号：
  UN 3382 6.1/PG 1

反应信息

• 作为反应物：
  描述：

  樟脑 、 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 108.0h， 以57%的产率得到2-<<(1,1-dimethylethyl)diphenylsilyl>oxy>-1,7,7-trimethylbicyclo<2.2.1>heptane-2-carbonitrile
  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
• 作为产物：
  描述：

  三甲基氰硅烷 、 叔丁基二苯基氯硅烷 在 potassium fluoride 作用下， 以88%的产率得到叔丁基苯氰基硅烷
  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

• An enantioselective approach to ring a of taxol using the wieland-miescher ketone
  作者：Miroslaw Golinski、Sundar Vasudevan、Rey Floresca、Carolyn P. Brock、David S. Watt

  DOI：10.1016/s0040-4039(00)60056-4

  日期：1993.1

  The selective protection of the S-(+)-enantiomer of the Wieland Miescher ketone (2) as the tertbutyldimethylsilyl-protected cyanohydrin 7 and the oxidative cleavage of an alpha-ketol 8 that was derived from 7 provided a model 10 for the A ring of the taxol (1) possessing the correct C-1 stereochemistry of taxol and functionality suitable for further elaboration.