(S)-benzyl (1-oxo-3-phenyl-1-(phenylamino)propan-2-yl)carbamate | 15366-12-8

• 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: (S)-benzyl (1-oxo-3-phenyl-1-(phenylamino)propan-2-yl)carbamate
• 英文别名: benzyl (S)-N-(2-phenyl-1-phenylcarbamoylethyl)carbamate；N-carbobenzoxy-L-phenylalanine anilide；Z-L-Phe-NH-Ph；Cbz-Phe-anilide；N-benzyloxycarbonyl-L-phenylalanine anilide；N-Benzyloxycarbonyl-L-phenylalanin-anilid；Nalpha-Benzyloxycarbonyl-L-phenylalanine-N-phenylamide；benzyl N-[(2S)-1-anilino-1-oxo-3-phenylpropan-2-yl]carbamate
• CAS: 15366-12-8
• 化学式: C₂₃H₂₂N₂O₃
• 分子量: 374.439
• InChiKey: YWAZVNYQZYAOEY-NRFANRHFSA-N

物化性质

• 熔点：
  173-174 °C
• 沸点：
  633.0±55.0 °C(Predicted)
• 密度：
  1.223±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.3
• 重原子数：
  28
• 可旋转键数：
  8
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.13
• 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：

  (S)-benzyl (1-oxo-3-phenyl-1-(phenylamino)propan-2-yl)carbamate 在 palladium on activated charcoal 氢气 、 三乙胺 作用下， 以 四氢呋喃 、 N,N-二甲基甲酰胺 、 异丙醇 为溶剂， 反应 5.0h， 生成 N-苯甲酰基-L-苯丙氨酸苯胺
  参考文献：
  名称：

  Pd-catalyzed enantioselective synthesis of quaternary α-amino acid derivatives using a phenylalanine-derived P-chirogenic diaminophosphine oxide

  摘要：

  A Pd-catalyzed enantio selective synthesis of quaternary alpha-amino acid derivatives using a phenylalanine-derived P-chirogenic diaminophosphine oxide is described. Asymmetric allylic substitution using acyclic beta-keto esters with a nitrogen functional group at the alpha-carbon as prochiral nucleophiles proceeded in the presence of 5 mol % of Pd catalyst, 10 mol % of chiral diaminophosphine oxide 1j, BSA, and appropriate additives, affording the corresponding quaternary alpha-amino acid derivatives in excellent yield and in up to 92% ee. (c) 2007 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetlet.2007.07.020
• 作为产物：
  描述：

  L-苯丙氨酸 在 sodium hydroxide 、 碳酸氢钠 、 1-(3-二甲基氨基丙基)-3-乙基碳二亚胺 作用下， 以 水 、 N,N-二甲基甲酰胺 为溶剂， 生成 (S)-benzyl (1-oxo-3-phenyl-1-(phenylamino)propan-2-yl)carbamate
  参考文献：
  名称：

  Pd-catalyzed enantioselective synthesis of quaternary α-amino acid derivatives using a phenylalanine-derived P-chirogenic diaminophosphine oxide

  摘要：

  A Pd-catalyzed enantio selective synthesis of quaternary alpha-amino acid derivatives using a phenylalanine-derived P-chirogenic diaminophosphine oxide is described. Asymmetric allylic substitution using acyclic beta-keto esters with a nitrogen functional group at the alpha-carbon as prochiral nucleophiles proceeded in the presence of 5 mol % of Pd catalyst, 10 mol % of chiral diaminophosphine oxide 1j, BSA, and appropriate additives, affording the corresponding quaternary alpha-amino acid derivatives in excellent yield and in up to 92% ee. (c) 2007 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetlet.2007.07.020

文献信息

• A Novel Generation of Coupling Reagents. Enantiodifferentiating Coupling Reagents Prepared in Situ from 2-Chloro-4,6-dimethoxy-1,3,5-triazine (CDMT) and Chiral Tertiary Amines
  作者：Zbigniew J. Kamiński、Beata Kolesińska、Janina E. Kamińska、Józef Góra

  DOI：10.1021/jo0101499

  日期：2001.9.1

  enantiomeric enrichment depend on the structures of the amine and carboxylic acid. Calculated Kagan enantioselectivity parameters (s) are in the range 1.6-195. Chiral triazinylammonium chlorides formed in situ from CDMT and chiral tertiary amines are postulated as reactive intermediates involved in the process of enantioselective activation of N-protected amino acids.

  在手性叔胺（例如士的宁，马钱子碱和斯巴丁胺）存在下，通过2-氯-4,6-二甲氧基-1,3,5-三嗪（CDMT）将外消旋的N-保护的氨基酸与氨基成分偶联对映选择性地得到合适的酰胺或二肽，产率为69-85％。优选的对映异构体和对映异构体富集的构型取决于胺和羧酸的结构。计算的Kagan对映选择性参数在1.6-195的范围内。由CDMT和手性叔胺原位形成的手性三嗪基氯化铵被假定为反应性中间体，参与N保护氨基酸的对映选择性活化过程。
• A Convenient Synthesis of Amino Acid Arylamides Utilizing Methanesulfonyl Chloride and N-Methylimidazole
  作者：Weicheng Zhou、Liguang Mao、Zhenyu Wang、Yongjia Li、Xiqian Han

  DOI：10.1055/s-0030-1259099

  日期：2011.1

  N-Cbz-protected amino acids reacted with various arylamines in the presence of methanesulfonyl chloride and N-methylimidazole in dichloromethane to give the corresponding arylamides in high yields. No obvious racemization was observed under the mild conditions.

  N-Cbz 保护的氨基酸在甲磺酰氯和 N-甲基咪唑的存在下在二氯甲烷中与各种芳胺反应，以高产率得到相应的芳基酰胺。在温和条件下未观察到明显的外消旋化。
• Amide Formation Using In Situ Activation of Carboxylic Acids with [Et₂NSF₂]BF₄
  作者：Olivier Mahé、Justine Desroches、Jean-François Paquin

  DOI：10.1002/ejoc.201300289

  日期：2013.7

  The formation of amides through the in situ activation of carboxylic acids with [Et2NSF2]BF4 is presented. A wide range of carboxylic acids and amines were used to produce the corresponding amides in up to 99 % yield. The reaction of hindered amines was also possible in the presence of 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) under slightly modified conditions. An enantiopure carboxylic acid and amine

  介绍了通过用 [Et2NSF2]BF4 原位活化羧酸形成酰胺。使用多种羧酸和胺来生产相应的酰胺，产率高达 99%。在 1,8-二氮杂双环 [5.4.0] undec-7-ene (DBU) 的存在下，在稍加修改的条件下，受阻胺的反应也是可能的。对映纯的羧酸和胺都显示出反应而没有外消旋化。
• Organocatalysis of asymmetric aldol reaction in water: comparison of catalytic properties of (S)-valine and (S)-proline amides
  作者：A. S. Kucherenko、D. E. Siyutkin、R. R. Dashkin、S. G. Zlotin

  DOI：10.1007/s11172-013-0132-z

  日期：2013.4

  (S)-Valine amides containing (S)- or (R)-α-phenylethyl substituents at N1 atom efficiently catalyze asymmetric aldol reactions between cyclic (heterocyclic) ketones and aromatic aldehydes in water, predominantly giving rise to the aldol anti-diastereomers in high yields (up to 98%) and enantiomeric excess (up to 94%).

  含有在N1原子上带有(S)-或(R)-α-苯乙基取代基的(S)-缬氨酰胺，能高效催化水中环状（杂环）酮与芳香醛的不对称Aldol反应，主要生成高产率（高达98%）和高对映体过量（高达94%）的Aldol反式异构体。
• Synthesis of Novel Bidentate P-Chiral Diaminophosphine Oxide Preligands: Application to Pd-Catalyzed Asymmetric Allylic Substitution Reactions
  作者：Teisuke Harada、Tetsuhiro Nemoto、Long Jin、Yasumasa Hamada

  DOI：10.1248/cpb.59.412

  日期：——

  We developed a novel (S)-L-phenylalanine derived-bidentate chiral diaminophosphine oxide (DIAPHOX) preligand (S,SP)-9b, which was successfully applied to Pd-catalyzed asymmetric allylic alkylation and amination. Using the Pd-(S,SP)-9b catalyst system, asymmetric allylic alkylation and amination proceeded very smoothly, affording the corresponding products in excellent yield with high enantiomeric excess. It is noteworthy that both enantiomers were accessible with high enantiomeric purity using the structurally related DIAPHOX preligands (S,SP)-9b and a monodentate chiral diaminophosphine oxide preligand (S,RP)-10a, both of which can be prepared from a single chiral source, (S)-L-phenylalanine.

  我们开发了一种新型的（S）-L-苯丙氨酸衍生的双齿手性二氨基磷氧化物（DIAPHOX）预配体（S,SP）-9b，并成功应用于钯催化的不对称烯丙基烷基化和胺化反应。使用钯-（S,SP）-9b催化体系，不对称烯丙基烷基化和胺化反应顺利进行，产率极高，对映体过量值也很高。值得注意的是，使用结构相关的DIAPHOX预配体（S,SP）-9b和单齿手性二氨基磷氧化物预配体（S,RP）-10a，均可以从单一的手性源（S）-L-苯丙氨酸制备，两种配体都能获得高对映体纯度的两种对映异构体。