N-Benzal-l-valine methyl ester

• 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-Benzal-l-valine methyl ester
• 英文别名: (R,S)-2-(Benzylidene-amino)-3-methyl-butyric acid methyl ester；methyl (2S)-2-(benzylideneamino)-3-methylbutanoate
• 化学式: C₁₃H₁₇NO₂
• 分子量: 219.283
• InChiKey: SWJMYFGBQCCKMR-LBPRGKRZSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3
• 重原子数：
  16
• 可旋转键数：
  5
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.38
• 拓扑面积：
  38.7
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  N-Benzal-l-valine methyl ester 在 四氯化钛 氢氧化钾 、 氢化铝 作用下， 以 四氢呋喃 为溶剂， 反应 20.0h， 生成 (S)-1-phenylbut-3-en-1-amine
  参考文献：
  名称：

  新型“ Ti（O）”在TiCl4（催化）/ Al双金属系统中诱导亚胺的烯丙基化。l-缬氨酸的手性转移至高烯丙基胺

  摘要：

  亚胺与烯丙基溴的“ Barbier型”烯丙基化已经成功地通过铝（1当量）和氯化钛（IV）（THF当量）在THF中的作用完成。α-氨基酸酯向均烯丙基胺的手性转移通过N-苯并缬氨酸甲酯的烯丙基化，然后进行碱水解和电解脱羧来证明。

  DOI：

  10.1016/s0040-4039(00)89015-2
• 作为产物：
  描述：

  methyl N-phenylmethylenecarbamate 在 Oxone 、 potassium carbonate 作用下， 以 氯仿 为溶剂， 反应 3.75h， 生成 N-Benzal-l-valine methyl ester
  参考文献：
  名称：

  N-Alkyloxycarbonyl-3-aryloxaziridines: Their Preparation, Structure, and Utilization As Electrophilic Amination Reagents

  摘要：

  AbstractThis paper reports the synthesis of a series of N‐protected oxaziridines (N‐Moc, Boc, Z or Fmoc) and discusses their ability to deliver their N‐alkoxycar‐bonyl fragment to amines, enolates, sulfur, and phosphorus nucleophiles (electrophilic amination). These oxaziridines are prepared by oxidation of the corresponding imines with oxone or anhydrous MCPBA lithium salt as the source of oxygen. They transfer their N‐protected fragment to primary and secondary amines to give protected hydrazines in fair to excellent yield. The nitrogen transfer to free amino acids (in form of their R4N+ salts) is particularly fast, even at low temperature, providing L (or D) N‐protected α‐hydrazino acids. Enolates are C‐aminated to give N‐protected α‐amino ketones, esters, or amides in modest yield, due to a side aldol reaction of the unreacted enolate with the released benzaldehyde. With tertiary amines (Et3N), sulfides (PhSMe), and phosphines (Ph3P), amination and oxidation proceed in a parallel way; the amount of amination product increases when the temperature is lowered (kinetic control). Some of the factors that can orient the oxaziridine reactivity towards amination or oxidation of nucleophiles are considered.

  DOI：

  10.1002/chem.19970031019

文献信息

• Chemoselective Reductive Amination of Aldehydes and Ketones by Dibutylchlorotin Hydride-HMPA Complex
  作者：Toshihiro Suwa、Erika Sugiyama、Ikuya Shibata、Akio Baba

  DOI：10.1055/s-2000-6273

  日期：——

  Reductive amination of various aldehydes and ketones has been performed effectively by pentacoordinate chloro-substituted tin hydride complex, Bu2SnClH-HMPA. The tin reagent worked particularly well for the case using weakly basic aromatic amines as starting substrates. Stoichiometric amounts of a substrate and a reducing agent were adequate for the reaction. The Sn-Cl bond in the complex plays an

  通过五配位氯取代的氢化锡络合物 Bu2SnClH-HMPA 可以有效地进行各种醛和酮的还原胺化。锡试剂在使用弱碱性芳香胺作为起始底物的情况下效果特别好。化学计量量的底物和还原剂足以进行反应。配合物中的 Sn-Cl 键在亚胺形成和随后的还原两个步骤中都起着重要作用。无论起始羰基和胺中的其他官能团如卤素、碳-碳双键和羟基如何，都可以实现羰基的高度化学选择性还原。
• Synthesis of novel glycopeptidomimetics via Nβ-protected-amino alkyl isonitrile based Ugi 4C reaction
  作者：Basavalingappa Vasantha、Girish Prabhu、Hosmani Basavaprabhu、Vommina V. Sureshbabu

  DOI：10.1016/j.tetlet.2013.06.013

  日期：2013.8

  The Ugi-4C reaction employing Nβ-protected-amino alkyl isonitrile, amino acid ester, aldehyde, and glycosyl acid has resulted in novel glycosylated peptidomimetics. The extension of MCR products for the synthesis of N,N′-orthogonally protected glycosylated peptidomimetics has also been demonstrated.

  采用的Ugi-4C反应Ñ β -保护的氨基烷基异腈，氨基酸酯，醛和糖基酸已导致新颖糖基化的肽模拟物。还已经证明了MCR产物用于合成N，N'-正交保护的糖基化肽模拟物的扩展。
• A convenient method for the enantiomeric separation of α-amino acid esters as benzophenone imine Schiff base derivatives
  作者：Hu Huang、Wen Jun Xu、Jing-Yu Jin、Joon Hee Hong、Hyun-Jae Shin、Wonjae Lee

  DOI：10.1007/s12272-012-0609-6

  日期：2012.6

  the separation of α-amino acid esters as benzophenone Schiff base derivatives on coated chiral stationary phases (CSPs) (Chiralcel OD-H, Chiralcel OD, Chiralpak AD-H, Chiralpak AD, and Chiralpak AS) or covalently immobilized CSPs (Chiralpak IA, Chiralpak IB, and Chiralpak IC) derived from polysaccharide derivatives is described. Benzophenone imine derivatives of α-amino acid esters were readily prepared

  一种方便的液相色谱方法，用于在涂层手性固定相 (CSP)（Chiralcel OD-H、Chiralcel OD、Chiralpak AD-H、Chiralpak AD 和 Chiralpak AS）上或共价分离作为二苯甲酮席夫碱衍生物的 α-氨基酸酯描述了源自多糖衍生物的固定化 CSP（Chiralpak IA、Chiralpak IB 和 Chiralpak IC）。通过在 2-丙醇中搅拌二苯甲酮亚胺和 α-氨基酸酯的盐酸盐，很容易制备 α-氨基酸酯的二苯甲酮亚胺衍生物。色谱分离以1.0 mL/min的流速和254 nm的检测波长进行；0.5% 2-丙醇/己烷 (v/v) 用于 CSP。总的来说，Chiralpak IC 的分辨率优于其他 CSP。此外，
• Indium–Silver- and Zinc–Silver-Mediated Barbier–Grignard-Type Alkylation Reactions of Imines by Using Unactivated Alkyl Halides in Aqueous Media
  作者：Zhi-Liang Shen、Hao-Lun Cheong、Teck-Peng Loh

  DOI：10.1002/chem.200701468

  日期：2008.2.18

  efficient and practical method for the Barbier-Grignard-type alkylation reactions of simple imines by using a one-pot condensation of various aldehydes, amines (including the aliphatic and chiral version), and secondary alkyl iodides has been developed. The reaction proceeded more efficiently in water than in organic solvents. Without the use of CuI, it mainly gave the imine self-reductive coupling product

  在In或Zn / AgI / InCl（3）存在的情况下，通过使用一锅缩合的各种醛，胺（包括脂肪族和手性化合物）的简单亚胺进行Barbier-Grignard型烷基化反应的高效实用方法版本），并且已经开发了仲烷基碘。该反应在水中比在有机溶剂中更有效地进行。不使用CuI，它主要得到亚胺自还原偶联产物，它不是烷基化产物。当使用L-缬氨酸甲酯作为底物时，获得了良好的非对映选择性（高达92：8 dr）。
• N-amination using N-methoxycarbonyl-3-phenyloxaziridine. Direct access to chiral N_β-protected α-hydrazinoacids and carbazates
  作者：Joëlle Vidal、Jacques Drouin、André Collet

  DOI：10.1039/c39910000435

  日期：——

  Primary and secondary amines N–H, including α-aminoacids, can be converted under mild conditions to the corresponding carbazates N–NH–CO2Me, on reaction with N-methoxycarbonyl-3-phenyloxaziridine 1.

  初级和次级胺的 N–H，包括 α-氨基酸，可以在温和条件下与 N-甲氧基碳酰基-3-苯基呋喃啶 1 反应，转化为相应的脲体 N–NH–CO2Me。