(3E)-2-<oxy>-4-phenyl-3-butenenitrile | 100573-23-7

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: (3E)-2-<oxy>-4-phenyl-3-butenenitrile
• 英文别名: (E)-2-(tert-butyl-dimethyl-silanyloxy)-2-methyl-4-phenyl-but-3-enenitrile；2-(tert-Butyldimethylsiloxy)-2-methyl-4-phenyl-3-butennitril；(3E)-2-{[dimethyl(1,1-dimethylethyl)silyl]oxy}-4-phenyl-3-butenenitrile；(E)-2-[tert-butyl(dimethyl)silyl]oxy-2-methyl-4-phenylbut-3-enenitrile
• CAS: 100573-23-7
• 化学式: C₁₇H₂₅NOSi
• 分子量: 287.477
• InChiKey: BLXOGZFURSKYAR-OUKQBFOZSA-N

物化性质

• 沸点：
  100 °C(Press: 0.01 Torr)
• 密度：
  0.964±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  5.0
• 重原子数：
  20
• 可旋转键数：
  5
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.47
• 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：

  叔丁基氰基二甲基硅烷 、 苄叉丙酮 在 P(i-PrNCH₂CH₂)N 作用下， 以 四氢呋喃 为溶剂， 反应 1.0h， 以98%的产率得到(3E)-2-<oxy>-4-phenyl-3-butenenitrile
  参考文献：
  名称：

  P(RNCH2CH2)N: efficient catalysts for the cyanosilylation of aldehydes and ketones

  摘要：

  The 1,2-addition of trialkylsilylcyanides to aldehydes and ketones produces the corresponding protected cyanohydrins in good to excellent yields when carried out at 0 degrees C to room temperature in the presence of catalytic amounts of the nonionic strong base P(RNCH2CH2)N (R = Me, i-Pr) in THF. These catalysts are easily removed from the product by hydrolysis or column filtration through silica gel. (c) 2005 Published by Elsevier Ltd.

  DOI：

  10.1016/j.tetlet.2005.09.032

文献信息

• Robust and Efficient, Yet Uncatalyzed, Synthesis of Trialkylsilyl-Protected Cyanohydrins from Ketones
  作者：Fabien L. Cabirol、Angela E. C. Lim、Ulf Hanefeld、Roger A. Sheldon、Ilya M. Lyapkalo

  DOI：10.1021/jo702587e

  日期：2008.3.1

  High-yielding cyanosilylation of ketones with NaCN and various chlorotrialkylsilanes in DMSO proceeds smoothly without catalysis to give silyl-protected ketone cyanohydrins. The unique role of DMSO consists in rendering naked cyanide anions that reversibly add to the CO bond at the rate-determining step followed by fast trapping of the transient tertiary sodium cyanoalcoholates with chlorotrialkylsilanes

  在DMSO中，用NaCN和各种氯三烷基硅烷对酮进行高产率的氰基甲硅烷基化反应可顺利进行，而无需催化，即可得到甲硅烷基保护的酮氰醇。DMSO的独特作用在于提供裸氰化物阴离子，该阴离子在速率确定步骤可逆地添加到C O键中，然后用氯代三烷基硅烷或原位生成的氰基三烷基硅烷快速捕获瞬态叔氰醇钠。制备上，该反应与应用昂贵的Me 3 SiCN的最著名的催化氰基硅烷化反应体系相匹配，并证明了在空间上被三烷基甲硅烷基保护的氰醇的合成中空前的效率。
• Huenig, Siegfried; Reichelt, Helmut, Chemische Berichte, 1986, vol. 119, # 6, p. 1772 - 1800
  作者：Huenig, Siegfried、Reichelt, Helmut

  DOI：——

  日期：——
• 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.
• HUNIG S.; REICHELT H., CHEM. BER., 119,(1986) N 6, 1772-1800
  作者：HUNIG S.、 REICHELT H.

  DOI：——

  日期：——
• P(RNCH2CH2)N: efficient catalysts for the cyanosilylation of aldehydes and ketones
  作者：Brandon M. Fetterly、John G. Verkade

  DOI：10.1016/j.tetlet.2005.09.032

  日期：2005.11

  The 1,2-addition of trialkylsilylcyanides to aldehydes and ketones produces the corresponding protected cyanohydrins in good to excellent yields when carried out at 0 degrees C to room temperature in the presence of catalytic amounts of the nonionic strong base P(RNCH2CH2)N (R = Me, i-Pr) in THF. These catalysts are easily removed from the product by hydrolysis or column filtration through silica gel. (c) 2005 Published by Elsevier Ltd.