(2Z,4R,5S)-5-hydroxy-2--4-phenyl-2-heptenenitrile | 147471-37-2

• 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: (2Z,4R,5S)-5-hydroxy-2--4-phenyl-2-heptenenitrile
• 英文别名: (Z,4R,5S)-5-hydroxy-2-[[(1R,2S)-1-hydroxy-1-phenylpropan-2-yl]-methylamino]-4-phenylhept-2-enenitrile
• CAS: 147471-37-2
• 化学式: C₂₃H₂₈N₂O₂
• 分子量: 364.488
• InChiKey: FIINTGGOQONETH-DKSRMJLWSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4
• 重原子数：
  27
• 可旋转键数：
  8
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.35
• 拓扑面积：
  67.5
• 氢给体数：
  2
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  (2Z,4R,5S)-5-hydroxy-2--4-phenyl-2-heptenenitrile 在 lithium aluminium tetrahydride 、 dimethyl sulfide borane 、 水 、 草酸 、 三乙胺 、 甘油 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 反应 39.25h， 生成 (S)-3-phenylhexane
  参考文献：
  名称：

  Regio-, stereo-, and enantioselectivity in the electrophilic reactions of 2-amino-4-phenyl-3-butenenitriles

  摘要：

  The allylic anion generated from 2-(N-methylanilino)-4-phenyl-3-butenenitrile (1) reacted with iodomethane and 3-bromo-1-chloropropane in THF/HMPA to give the gamma-substitution products exclusively, predominantly in the 2Z-configuration. Substitution of the N-methylanilino group with the methyl ether of L-(-)-ephedrine resulted in the generation of chiral aminonitrile 2. Lithiated 2 reacted sluggishly in THF with allyl bromide and benzyl chloride in the absence of HMPA to give the gamma-substitution products predominantly in the 2Z-configuration, with little diastereoselectivity. The aminonitrile 3 prepared from cinnamaldehyde, L-(-)-ephedrine, and KCN was lithiated with 2 equiv of LDA resulting in high facial selectivity (76-100% diastereomeric excess) in alkylations in the presence of HMPA and LiI. Lithiated 3 reacted with propionaldehyde, benzaldehyde, and p-bromobenzaldehyde at-78-degrees-C to give the gamma-addition products, predominantly in the 4R-configuration (64-78% de). The stereochemistry of the isomers of each product was determined by chemical correlation and spectral methods including analyses of the CD spectra and X-ray diffraction. A bicyclic transition state C wherein lithium is chelated by both amino and alkoxy groups is proposed to interpret the observed stereoselectivity.

  DOI：

  10.1021/jo00059a027
• 作为产物：
  描述：

  丙醛 、 2--4-phenyl-3-butenenitrile 在 lithium diisopropyl amide 作用下， 生成 (2Z,4S,5R)-5-hydroxy-2--4-phenyl-2-heptenenitrile 、 (2Z,4R,5R)-5-hydroxy-2--4-phenyl-2-heptenenitrile 、 (2Z,4R,5S)-5-hydroxy-2--4-phenyl-2-heptenenitrile
  参考文献：
  名称：

  Regio-, stereo-, and enantioselectivity in the electrophilic reactions of 2-amino-4-phenyl-3-butenenitriles

  摘要：

  The allylic anion generated from 2-(N-methylanilino)-4-phenyl-3-butenenitrile (1) reacted with iodomethane and 3-bromo-1-chloropropane in THF/HMPA to give the gamma-substitution products exclusively, predominantly in the 2Z-configuration. Substitution of the N-methylanilino group with the methyl ether of L-(-)-ephedrine resulted in the generation of chiral aminonitrile 2. Lithiated 2 reacted sluggishly in THF with allyl bromide and benzyl chloride in the absence of HMPA to give the gamma-substitution products predominantly in the 2Z-configuration, with little diastereoselectivity. The aminonitrile 3 prepared from cinnamaldehyde, L-(-)-ephedrine, and KCN was lithiated with 2 equiv of LDA resulting in high facial selectivity (76-100% diastereomeric excess) in alkylations in the presence of HMPA and LiI. Lithiated 3 reacted with propionaldehyde, benzaldehyde, and p-bromobenzaldehyde at-78-degrees-C to give the gamma-addition products, predominantly in the 4R-configuration (64-78% de). The stereochemistry of the isomers of each product was determined by chemical correlation and spectral methods including analyses of the CD spectra and X-ray diffraction. A bicyclic transition state C wherein lithium is chelated by both amino and alkoxy groups is proposed to interpret the observed stereoselectivity.

  DOI：

  10.1021/jo00059a027

文献信息

• Regio-, stereo-, and enantioselectivity in the electrophilic reactions of 2-amino-4-phenyl-3-butenenitriles
  作者：Chih Jung Chang、Jim Min Fang、Li Fan Liao

  DOI：10.1021/jo00059a027

  日期：1993.3

  The allylic anion generated from 2-(N-methylanilino)-4-phenyl-3-butenenitrile (1) reacted with iodomethane and 3-bromo-1-chloropropane in THF/HMPA to give the gamma-substitution products exclusively, predominantly in the 2Z-configuration. Substitution of the N-methylanilino group with the methyl ether of L-(-)-ephedrine resulted in the generation of chiral aminonitrile 2. Lithiated 2 reacted sluggishly in THF with allyl bromide and benzyl chloride in the absence of HMPA to give the gamma-substitution products predominantly in the 2Z-configuration, with little diastereoselectivity. The aminonitrile 3 prepared from cinnamaldehyde, L-(-)-ephedrine, and KCN was lithiated with 2 equiv of LDA resulting in high facial selectivity (76-100% diastereomeric excess) in alkylations in the presence of HMPA and LiI. Lithiated 3 reacted with propionaldehyde, benzaldehyde, and p-bromobenzaldehyde at-78-degrees-C to give the gamma-addition products, predominantly in the 4R-configuration (64-78% de). The stereochemistry of the isomers of each product was determined by chemical correlation and spectral methods including analyses of the CD spectra and X-ray diffraction. A bicyclic transition state C wherein lithium is chelated by both amino and alkoxy groups is proposed to interpret the observed stereoselectivity.