N--(S)-α-methylbenzylamine | 17430-32-9

• 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--(S)-α-methylbenzylamine
• 英文别名: N-[Z-(S)-Phe]-(S)-1-phenylethylamine；Benzyloxycarbonyl-(S)-phenylalanin-(S)-α-phenyl-ethylamid；benzyl N-[(2S)-1-oxo-3-phenyl-1-[[(1S)-1-phenylethyl]amino]propan-2-yl]carbamate
• CAS: 17430-32-9
• 化学式: C₂₅H₂₆N₂O₃
• 分子量: 402.493
• InChiKey: YCUSDCUZUDEBCS-CVDCTZTESA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.7
• 重原子数：
  30
• 可旋转键数：
  9
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.2
• 拓扑面积：
  67.4
• 氢给体数：
  2
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  N--(S)-α-methylbenzylamine 在 palladium on activated charcoal 氢气 、 溶剂黄146 作用下， 以 甲醇 为溶剂， 反应 1.0h， 生成 (S)-2-Amino-3-phenyl-N-((S)-1-phenyl-ethyl)-propionamide
  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：

  N-苄氧羰基-L-苯丙氨酸 在 N,N'-二环己基碳二亚胺 作用下， 以 四氢呋喃 为溶剂， 反应 30.0h， 生成 N--(S)-α-methylbenzylamine
  参考文献：
  名称：

  Nickel complexes from α-amino amides as efficient catalysts for the enantioselective Et2Zn addition to benzaldehyde

  摘要：

  Ni2+ complexes derived from simple alpha-amino amides catalyze very efficiently the addition of Et2Zn to benzaldehyde, giving (S)-1-phenylethanol as the major isomer in most cases (94% yield, 97% ee for R=Bn). The nature of the substituent on the amide nitrogen atom seems to play a key role in determining the asymmetric induction observed. (C) 2003 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/s0040-4039(03)01705-2

文献信息

• Superiority of the carbamoylmethyl ester as an acyl donor for the kinetically controlled amide-bond formation mediated by α-chymotrypsinElectronic supplementary information (ESI) available: elemental analyses and HPLC separation data. See http://www.rsc.org/suppdata/p1/b1/b108735p/
  作者：Toshifumi Miyazawa、Eiichi Ensatsu、Nobuhiro Yabuuchi、Ryoji Yanagihara、Takashi Yamada

  DOI：10.1039/b108735p

  日期：2002.1.23

  The superiority of the carbamoylmethyl ester as an acyl donor for the α-chymotrypsin-catalysed kinetically controlled peptide-bond formation is demonstrated in the couplings of an inherently poor amino acid substrate, Ala, with various amino acid residues as amino components and in the couplings of non-protein amino acids such as halogenophenylalanines as carboxylic components. Furthermore, this approach is applied to the amide-bond formation between an amino acid residue and a chiral amine, which is highly diastereoselective.

  研究表明，羰甲基氨基甲酸酯作为酰基供体在α-糜蛋白酶催化的动力学控制的肽键形成反应中具有优越性，这体现在天然不良氨基酸底物Ala与各种氨基酸残基作为氨基组分的偶联反应中，以及与非蛋白氨基酸如卤代苯丙氨酸作为羧基组分的偶联反应中。此外，这种方法还应用于氨基酸残基与手性胺之间的酰胺键形成反应，具有高度立体选择性。
• 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。
• Kinetic regularities of resolution of amines racemates in the acylation reaction with chiral <i>N</i>‐protected amino acids esters
  作者：Stanislav Bakhtin、Marina Sinelnikova

  DOI：10.1002/kin.21681

  日期：2023.11

  establish the reaction orders with respect to the reagents, as well as the kinetic regularities of the enantioselective acylation. It is shown that different kinetic schemes of the reaction take place in protic and aprotic solvents. Based on the experimental data on the reaction kinetics of both the individual enantiomers and the amine racemate, the enantioselectivity values of the acylation are calculated

  本工作研究了光学活性N 4-硝基苯酯作用下酰化反应中1-苯乙胺外消旋体的动力学拆分的动力学和立体化学规律。研究了 2-丙醇和 1,4-二恶烷中的 β-保护苯丙氨酸。使用紫外光谱法进行动力学测量。对反应系列的研究使得建立有关试剂的反应级以及对映选择性酰化的动力学规律成为可能。结果表明，在质子溶剂和非质子溶剂中发生不同的反应动力学方案。根据单个对映体和胺外消旋体的反应动力学实验数据，计算酰化的对映选择性值。已发现溶剂的性质和试剂比例强烈影响动力学拆分的选择性。
• Herlinger,H. et al., Justus Liebigs Annalen der Chemie, 1967, vol. 706, p. 37 - 46
  作者：Herlinger,H. et al.

  DOI：——

  日期：——
• Nickel complexes from α-amino amides as efficient catalysts for the enantioselective Et2Zn addition to benzaldehyde
  作者：M.Isabel Burguete、Manuel Collado、Jorge Escorihuela、Francisco Galindo、Eduardo Garcı́a-Verdugo、Santiago V Luis、Marı́a J Vicent

  DOI：10.1016/s0040-4039(03)01705-2

  日期：2003.9

  Ni2+ complexes derived from simple alpha-amino amides catalyze very efficiently the addition of Et2Zn to benzaldehyde, giving (S)-1-phenylethanol as the major isomer in most cases (94% yield, 97% ee for R=Bn). The nature of the substituent on the amide nitrogen atom seems to play a key role in determining the asymmetric induction observed. (C) 2003 Elsevier Ltd. All rights reserved.