(R)-N-Crotonoyl-2-phenylglycinol | 141542-64-5

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 脂肪酰基
• 英文名称: (R)-N-Crotonoyl-2-phenylglycinol
• 英文别名: (2R)-N-crotonyl-2-amino-2-phenylethanol；(E)-N-[(1R)-2-hydroxy-1-phenylethyl]but-2-enamide
• CAS: 141542-64-5
• 化学式: C₁₂H₁₅NO₂
• 分子量: 205.257
• InChiKey: GMYOPCGTCFICQZ-GSQGTZRGSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.2
• 重原子数：
  15
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.25
• 拓扑面积：
  49.3
• 氢给体数：
  2
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  (R)-N-Crotonoyl-2-phenylglycinol 在 copper(l) iodide 、 三甲基氯硅烷 、 三氟化硼乙醚 作用下， 以 甲苯 为溶剂， 反应 43.25h， 生成 (R)-2,2-Dimethyl-3-(3-methylbutanoyl)-4-phenyloxazolidine
  参考文献：
  名称：

  Effective Enantiocontrol in Conjugate Additions of Organocuprates. Highly Selective 1,5-Chiral Induction in the Conjugate Additions of Cuprates to .alpha.,.beta.-Unsaturated Amide Derivatives of 2,2-Dimethyloxazolidine Chiral Auxiliaries

  摘要：

  alpha,beta-Unsaturated amide derivatives of 2,2-dimethyloxazolidines, developed as new chirality-controlling auxiliaries based on the restricted rotation of the amide linkage, have been applied to the enantiocontrol of conjugate additions of lithium and magnesium cuprates. High selectivities of 1,5-chiral inductions are attained, indicating their promising synthetic potential in asymmetric synthesis. The diastereofacial selectivities depend upon the efficiency of steric shielding by the 4-substituent of the chiral auxiliary, and the reaction of (S)-4-benzyl-3-[(E)-2-butenoyl]-2,2,5,5-tetramethyloxazolidine with Ph(2)CuMgBr.MgBrI is exclusively lk-1,5-inductive. Use of organolithium and organomagnesium show opposite low selectivities. It is concluded that the stereochemistry of cuprate conjugate addition is determined at the step of formation of the d,pi* type charge transfer complexes.

  DOI：

  10.1021/jo00102a018
• 作为产物：
  描述：

  2-丁烯酰氯 、 D-苯甘氨醇 在 三乙胺 作用下， 以 二氯甲烷 为溶剂， 反应 5.0h， 以75%的产率得到(R)-N-Crotonoyl-2-phenylglycinol
  参考文献：
  名称：

  Effective Enantiocontrol in Conjugate Additions of Organocuprates. Highly Selective 1,5-Chiral Induction in the Conjugate Additions of Cuprates to .alpha.,.beta.-Unsaturated Amide Derivatives of 2,2-Dimethyloxazolidine Chiral Auxiliaries

  摘要：

  alpha,beta-Unsaturated amide derivatives of 2,2-dimethyloxazolidines, developed as new chirality-controlling auxiliaries based on the restricted rotation of the amide linkage, have been applied to the enantiocontrol of conjugate additions of lithium and magnesium cuprates. High selectivities of 1,5-chiral inductions are attained, indicating their promising synthetic potential in asymmetric synthesis. The diastereofacial selectivities depend upon the efficiency of steric shielding by the 4-substituent of the chiral auxiliary, and the reaction of (S)-4-benzyl-3-[(E)-2-butenoyl]-2,2,5,5-tetramethyloxazolidine with Ph(2)CuMgBr.MgBrI is exclusively lk-1,5-inductive. Use of organolithium and organomagnesium show opposite low selectivities. It is concluded that the stereochemistry of cuprate conjugate addition is determined at the step of formation of the d,pi* type charge transfer complexes.

  DOI：

  10.1021/jo00102a018

文献信息

• Diastereoselective Synthesis of Chiral Amidophosphonates by 1,5-Asymmetric Induction
  作者：Géraldine Castelot-Deliencourt、Elisabeth Roger、Xavier Pannecoucke、Jean-Charles Quirion

  DOI：10.1002/1099-0690(200108)2001:16<3031::aid-ejoc3031>3.0.co;2-5

  日期：2001.8

  We have investigated two simple diastereoselective syntheses of substituted β-amidophosphonates. The first one involved a Michael addition to α,β-unsaturated amides 6 and 8a−d, derived from chiral amino alcohols, and permitted the preparation of alkyl-substituted derivatives 7 and 9a−d with high diastereoselectivities (up to 95%) with the aid of a 1,5-asymmetric induction. The second one, involving

  我们研究了取代 β-酰胺基膦酸酯的两种简单的非对映选择性合成。第一个涉及对衍生自手性氨基醇的 α,β-不饱和酰胺 6 和 8a-d 进行迈克尔加成，并允许制备具有高非对映选择性（高达 95%）的烷基取代衍生物 7 和 9a-d 1,5-不对称感应的帮助。第二个涉及手性 β-酰胺基膦酸酯 14a-c 的 1,5-诱导烷基化，在产率方面很有希望，但非对映选择性令人失望（高达 50%）。最后，手性助剂的去除提供了膦酰基羧酸，能够提供对合成生物活性产品非常感兴趣的广泛化合物的途径。
• Asymmetric michael reactions : enantioselective synthesis of δ-oxo-acids
  作者：François Michelon、Annie Pouilhès、Nguyen Van Bac、Nicole Langlois

  DOI：10.1016/s0040-4039(00)91721-0

  日期：1992.3

  Beta-substituted and alpha,beta-disubstituted delta-oxo acids are synthetized with high enantiomeric excess from chiral 2-propenyl oxazolines 8 and 11, whilst 2-vinyl oxazolines 7 and 10 are less efficient asymmetric inductors.
• Dahuron, Nathalie; Langlois, Nicole; Chiaroni, Angele, Heterocycles, 1996, vol. 42, # 2, p. 635 - 643
  作者：Dahuron, Nathalie、Langlois, Nicole、Chiaroni, Angele、Riche, Claude

  DOI：——

  日期：——
• Alternative synthesis of α-substituted β-amidophosphines by [1,4]-addition. A new route to chiral ligands
  作者：Matthieu Léautey、Géraldine Castelot-Deliencourt、Philippe Jubault、Xavier Pannecoucke、Jean-Charles Quirion

  DOI：10.1016/s0040-4039(02)02250-5

  日期：2002.12

  Phosphine-borane can be diastereoselectively added to chiral alpha,beta-unsaturated amides 3, using amino-alcohols as chiral inducers, leading to alpha-substituted beta-amidophosphine boranes 4 with up to 74% diastereomeric excess. Selective deprotection afforded optically pure carboxylic derivatives 5 which are key intermediates for the synthesis of various potential chiral ligands for asymmetric catalysis. (C) 2002 Published by Elsevier Science Ltd.