anti-3-hydroxy-2-(1-methylethyl)-3-phenylpropanenitrile

• 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: anti-3-hydroxy-2-(1-methylethyl)-3-phenylpropanenitrile
• 英文别名: (2R)-2-[(R)-hydroxy(phenyl)methyl]-3-methylbutanenitrile
• 化学式: C₁₂H₁₅NO
• 分子量: 189.257
• InChiKey: ZVICCGXBGYJYAH-RYUDHWBXSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.1
• 重原子数：
  14
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.42
• 拓扑面积：
  44
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  anti-3-hydroxy-2-(1-methylethyl)-3-phenylpropanenitrile 在 sodium hydroxide 、 双氧水 作用下， 生成 threo-3-Hydroxy-2-isopropyl-3-phenyl-propionsaeure-amid
  参考文献：
  名称：

  Canceill,J.; Jacques,J., Comptes Rendus des Seances de l'Academie des Sciences, Serie C: Sciences Chimiques, 1969, vol. 269, p. 239 - 240

  摘要：

  DOI：
• 作为产物：
  描述：

  2-bromo-3-methylbutyronitrile 在 钾硼氢 作用下， 以 甲醇 为溶剂， 生成 anti-3-hydroxy-2-(1-methylethyl)-3-phenylpropanenitrile
  参考文献：
  名称：

  Canceill,J.; Jacques,J., Bulletin de la Societe Chimique de France, 1970, p. 2180 - 2187

  摘要：

  DOI：

文献信息

• Asymmetric Transfer Hydrogenation of α-Substituted-β-Keto Carbonitriles via Dynamic Kinetic Resolution
  作者：Fangyuan Wang、Tilong Yang、Ting Wu、Long-Sheng Zheng、Congcong Yin、Yongjie Shi、Xiang-Yu Ye、Gen-Qiang Chen、Xumu Zhang

  DOI：10.1021/jacs.0c13273

  日期：2021.2.17

  A catalytic protocol for the enantio- and diastereoselective reduction of α-substituted-β-keto carbonitriles is described. The reaction involves a DKR-ATH process with the simultaneous construction of β-hydroxy carbonitrile scaffolds with two contiguous stereogenic centers. A wide range of α-substituted-β-keto carbonitriles were obtained in high yields (94%–98%) and excellent enantio- and diastereoselectivities

  描述了用于α-取代的-β-酮腈的对映体和非对映体选择性还原的催化方案。该反应涉及DKR-ATH方法，该方法同时构建具有两个连续的立体异构中心的β-羟基甲腈支架。以高产率（94％–98％）和出色的对映和非对映选择性（高达> 99％ee，高达> 99：1 dr）获得了多种α-取代-β-酮腈。非对映选择性的起源也通过DFT计算得到了合理化。此外，这种方法可以快速获得异戊ox酮和他喷他多的药物中间体。
• Stereospecific Oxycyanation of Alkenes with Sulfonyl Cyanide
  作者：Kensuke Kiyokawa、Miu Ishizuka、Satoshi Minakata

  DOI：10.1002/anie.202218743

  日期：2023.3.13

  Intermolecular oxycyanation of alkenes using p-toluenesulfonyl cyanide (TsCN) in the presence of tris(pentafluorophenyl)borane (B(C6F5)3) as a catalyst was shown to be feasible. The developed method offers a simple, scalable, and straightforward approach to access synthetically useful β-hydroxy nitrile derivatives.

  在三（五氟苯基）硼烷（B（C 6 F 5）3 ）作为催化剂存在下，使用对甲苯磺酰氰（TsCN）进行烯烃的分子间氧氰化被证明是可行的。开发的方法提供了一种简单、可扩展且直接的方法来获取合成有用的β-羟基腈衍生物。
• Canceill,J.; Jacques,J., Comptes Rendus des Seances de l'Academie des Sciences, Serie C: Sciences Chimiques, 1969, vol. 269, p. 239 - 240
  作者：Canceill,J.、Jacques,J.

  DOI：——

  日期：——
• Synthetic Optimization and Structural Limitations of the Nitrile Aldol Reaction
  作者：Paul R. Carlier、Kam Moon Lo、Michael M.-C. Lo、Priscilla C.-K. Lo、Cedric W.-S. Lo

  DOI：10.1021/jo9702148

  日期：1997.9.1

  In an effort to further optimize and to define the structural limitations of the nitrile aldol reaction, several studies were undertaken. Lithiated phenylacetonitrile 1 was demonstrated to exhibit diastereoselectivity for addition to benzaldehyde higher than that of other metalated phenylacetonitriles. With a view toward practical lab-scale synthesis of aldols derived from lithiated arylacetonitriles, the effects of reaction concentration and quenching method on isolated yields of the anti-aldols were readdressed. Secondary aldehydes give reasonable recrystallized yields of anti-aldols at reaction concentrations as high as 0.1 M; pivalaldehyde gives good results at concentrations up to 0.3 M. Thirdly, the aldol reaction of lithiated 1 with para-substituted benzaldehydes 6b-g was then studied; increasing electron-withdrawing power of the para substituent was found to cause a marked decrease in diastereaselectivity. Finally, the aldol reactions of two aliphatic nitriles (isovaleronitrile 4 and tert-butylacetonitrile 5, were studied. Suprisingly, aldol diastereoselectivity of aliphatic nitriles is not uniformly anti-selective, and selectivities overall are lower than those afforded by arylacetonitriles.
• An Efficient Diastereoselective Reduction of α-Alkyl-β-keto Carbonitriles with TiCl4/BH3 or LiBH4/CeCl3 to syn- or anti-α-Alkyl-β-hydroxy Carbonitriles
  作者：Renato Dalpozzo、Giuseppe Bartoli、Marcella Bosco、Antonio De Nino、Antonio Procopio、Letizia Sambri、Antonio Tagarelli

  DOI：10.1002/1099-0690(200108)2001:15<2971::aid-ejoc2971>3.0.co;2-k

  日期：2001.8

  alpha -Alkyl-beta -keto carbonitriles can be reduced stereoselectively to syn- and anti-alpha -alkyl-beta -hydroxy carbonitriles. The stereoselectivity can be explained in terms of properties of the Lewis acid employed. TiCl4 in noncoordinating solvents such as dichloromethane, followed by reduction with the borane/pyridine complex, predominantly led to the syrz-alpha -alkyl-beta -hydroxy carbonitriles, according to a chelate transition state, whereas CeCl3 in coordinating solvents such as THF, followed by reduction with LiBH4, predominantly led to the anti-isomers, in agreement with an open-chain transition state. The reduction to syn-alpha -alkyl-beta -hydroxy carbonitriles is the first general preparation of these compounds.