N-(R)-phenylglycyl-(S)-1-phenylethylamine | 60656-55-5

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 英文名称: N-(R)-phenylglycyl-(S)-1-phenylethylamine
• 英文别名: (S)-1-phenylethyl-(R)-phenylglycinamide；(2R)-2-amino-2-phenyl-N-[(1S)-1-phenylethyl]acetamide
• CAS: 60656-55-5
• 化学式: C₁₆H₁₈N₂O
• 分子量: 254.332
• InChiKey: KOTUCVMGXNNUJL-SWLSCSKDSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.2
• 重原子数：
  19
• 可旋转键数：
  4
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.19
• 拓扑面积：
  55.1
• 氢给体数：
  2
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  N-(R)-phenylglycyl-(S)-1-phenylethylamine 在 palladium on activated charcoal 甲酸 、 氢气 、 溶剂黄146 作用下， 以 甲醇 为溶剂， 反应 5.5h， 生成 N--(S)-α-methylbenzylamine
  参考文献：
  名称：

  Asymmetric Hydrogenation Catalyzed by the (Achiral Base)bis(dimethylglyoximato)cobalt(II)–Chiral Cocatalyst System. The Preparation of a New Type of Chiral Cocatalyst and Its Application to the Asymmetric Hydrogenation of MethylN-(Acetylamino)acrylate and Benzil

  摘要：

  在非手性基团配位的双(二甲基乙二肟)钴(II)–手性共催化剂体系中，作为一种新型的手性共催化剂，制备了在α-或β-碳上含有酰胺基的三级胺，并使用它们进行了不对称氢化反应的研究。通过使用N-[(2S,3S)-2-乙酰氧基-3-二甲基氨基-3-苯基丙酰基]-(R)-α-甲基苯乙胺，光学产率达到了34.5%的ee值；这是迄今为止在该体系下对甲基N-(乙酰氨基)丙烯酸酯进行不对称氢化反应中获得的最高值。当N-[N,N-二甲基-(S)-苯丙氨酰]-α-甲基苯乙胺的α-甲基苯乙胺部分发生构型改变时，甲基N-(乙酰氨基)丙烯酸酯的氢化反应中的立体选择性发生了反转，而通过构型改变对苯偶酰的氢化反应中的立体选择性没有发生反转。从这些事实可以推断，手性氨基酸酰胺与甲基N-(乙酰氨基)丙烯酸酯之间的酰胺基氢键可能作为一种吸引力，增强不对称氢化反应的立体选择性。

  DOI：

  10.1246/bcsj.54.2136
• 作为产物：
  描述：

  左旋苯甘氨酸 在 盐酸 、 三乙胺 作用下， 以 1,4-二氧六环 、 乙醚 、 氯仿 、 水 为溶剂， 反应 2.0h， 生成 N-(R)-phenylglycyl-(S)-1-phenylethylamine
  参考文献：
  名称：

  An ‘easy-on, easy-off’ protecting group for the enzymatic resolution of (±)-1-phenylethylamine in an aqueous medium

  摘要：

  A new approach has been developed for the biocatalytic resolution of (+/-)-1-phenylethylamine in 100% aqueous medium based on two integrated enzymatic steps: protection and deprotection of the reactive amine enantiomer catalyzed by the same enzyme-penicillin acylase from Alcaligenes faecalis. An 'easy-on, easy-off' protecting group has been introduced using (R)-phenyl-glycine amide as the acyl donor. (R)-Phenylglycyl-substituted (R)-1-phenylethylamine was poorly soluble and precipitated at enzymatic acylation in an alkaline medium (pH 10-11), driving the synthesis towards high yields. Conversely at pH <7.5, its solubility was continuously increasing, which rendered the subsequent deacylation by the same enzyme highly efficient. In contrast to the resolutions, which employ one biocatalytic step, the new approach made it possible to exploit two sequential enantioselective enzymatic reactions implementing a double enantioselectivity control. Effective enzymatic resolution of (+/-)-1-phenylethylamine in an aqueous medium was performed with (R)-phenyl-glycine amide as an acyl donor using the suggested approach. (C) 2004 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetasy.2004.06.051

文献信息

• An ‘easy-on, easy-off’ protecting group for the enzymatic resolution of (±)-1-phenylethylamine in an aqueous medium
  作者：Dorel T. Guranda、Andrey I. Khimiuk、Luuk M. van Langen、Fred van Rantwijk、Roger A. Sheldon、Vytas K. Švedas

  DOI：10.1016/j.tetasy.2004.06.051

  日期：2004.9

  A new approach has been developed for the biocatalytic resolution of (+/-)-1-phenylethylamine in 100% aqueous medium based on two integrated enzymatic steps: protection and deprotection of the reactive amine enantiomer catalyzed by the same enzyme-penicillin acylase from Alcaligenes faecalis. An 'easy-on, easy-off' protecting group has been introduced using (R)-phenyl-glycine amide as the acyl donor. (R)-Phenylglycyl-substituted (R)-1-phenylethylamine was poorly soluble and precipitated at enzymatic acylation in an alkaline medium (pH 10-11), driving the synthesis towards high yields. Conversely at pH <7.5, its solubility was continuously increasing, which rendered the subsequent deacylation by the same enzyme highly efficient. In contrast to the resolutions, which employ one biocatalytic step, the new approach made it possible to exploit two sequential enantioselective enzymatic reactions implementing a double enantioselectivity control. Effective enzymatic resolution of (+/-)-1-phenylethylamine in an aqueous medium was performed with (R)-phenyl-glycine amide as an acyl donor using the suggested approach. (C) 2004 Elsevier Ltd. All rights reserved.
• Asymmetric Hydrogenation Catalyzed by the (Achiral Base)bis(dimethylglyoximato)cobalt(II)–Chiral Cocatalyst System. The Preparation of a New Type of Chiral Cocatalyst and Its Application to the Asymmetric Hydrogenation of Methyl<i>N</i>-(Acetylamino)acrylate and Benzil
  作者：Seiji Takeuchi、Yoshiaki Ohgo

  DOI：10.1246/bcsj.54.2136

  日期：1981.7

  As a new type of chiral cocatalyst in the achiral base-coordinated bis(dimethylglyoximato)cobalt(II)–chiral cocatalyst system, tertiary amines with an amide group at α- or β-carbon were prepared, and asymmetric hydrogenation was examined by using them. The optical yield reached 34.5% enantiomeric excess(ee) by using N-[(2S,3S)-2-acetoxy-3-dimetnylamino-3-phenylpropionyl]-(R)-α-methylbenzylamine; this is the highest value attained so far in the asymmetric hydrogenation of methyl N-(acetylamino)acrylate with this system. The enantioselectivity in the hydrogenation of methyl N-(acetylamino)acrylate was reversed with a configurational alteration of the α-methylbenzylamine moiety of N-[N,N-dimethyl-(S)-phenylalanyl]-α-methylbenzylamine, while it was not reversed in the hydrogenation of benzil by the configurational alteration. From these facts, it is deduced that the hydrogen bond between amide groups of the chiral amino carboxamides and methyl N-(acetylamino)acrylate may act as an attractive force to enhance the enantioselectivity of the asymmetric hydrogenation.

  在非手性基团配位的双(二甲基乙二肟)钴(II)–手性共催化剂体系中，作为一种新型的手性共催化剂，制备了在α-或β-碳上含有酰胺基的三级胺，并使用它们进行了不对称氢化反应的研究。通过使用N-[(2S,3S)-2-乙酰氧基-3-二甲基氨基-3-苯基丙酰基]-(R)-α-甲基苯乙胺，光学产率达到了34.5%的ee值；这是迄今为止在该体系下对甲基N-(乙酰氨基)丙烯酸酯进行不对称氢化反应中获得的最高值。当N-[N,N-二甲基-(S)-苯丙氨酰]-α-甲基苯乙胺的α-甲基苯乙胺部分发生构型改变时，甲基N-(乙酰氨基)丙烯酸酯的氢化反应中的立体选择性发生了反转，而通过构型改变对苯偶酰的氢化反应中的立体选择性没有发生反转。从这些事实可以推断，手性氨基酸酰胺与甲基N-(乙酰氨基)丙烯酸酯之间的酰胺基氢键可能作为一种吸引力，增强不对称氢化反应的立体选择性。