(S)-methyl 3-methyl-2-(p-tolylamino)butanoate | 67679-47-4

• 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)-methyl 3-methyl-2-(p-tolylamino)butanoate
• 英文别名: methyl (S)-3-methyl-2-(p-tolylamino)butanoate；N-(4-methylphenyl)-L-valine methyl ester；methyl (2S)-3-methyl-2-(4-methylanilino)butanoate
• CAS: 67679-47-4
• 化学式: C₁₃H₁₉NO₂
• 分子量: 221.299
• InChiKey: VGTXSZFAUFPYSU-LBPRGKRZSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.6
• 重原子数：
  16
• 可旋转键数：
  5
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.46
• 拓扑面积：
  38.3
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  (S)-methyl 3-methyl-2-(p-tolylamino)butanoate 在 三乙基硼 、 氧气 、 三正丁基氢锡 、 N,N,N-trimethylbenzenemethanaminium dichloroiodate 、 N,N-二异丙基乙胺 、 calcium carbonate 作用下， 以 甲醇 、 二氯甲烷 为溶剂， 反应 12.0h， 生成 (R)-1-(2-oxo-1-methylindoline)-1-S-isopropyl-acetic acid methyl ester
  参考文献：
  名称：

  Relaying Asymmetry of Transient Atropisomers of o-Iodoanilides by Radical Cyclizations

  摘要：

  Atropisomers of N-2 degrees -alkyl-N-acryloyl-2-iodoanlides have been resolved by chromatography and crystallization-induced asymmetric transformation. These molecules have atropisomerization barriers of 23-24 kcal/mol and return to equilibrium ratios over several hours at ambient temperature in solution. The transient chirality can be locked in by radical cyclizations, which provide N-2 degrees -alkyl-3-methyl-1,3-dihydroindol-2-ones with high levels of chirality transfer. The mechanistic model features a stereoselective aryl radical cyclization that is more rapid than the rotation of the N-aryl bond of the anilide.

  DOI：

  10.1021/ja055666d
• 作为产物：
  描述：

  4-甲苯硼酸 、 L-缬氨酸甲酯盐酸盐 在 copper diacetate 、 4 A molecular sieve 、 三乙胺 作用下， 以 二氯甲烷 为溶剂， 以67%的产率得到(S)-methyl 3-methyl-2-(p-tolylamino)butanoate
  参考文献：
  名称：

  N-Arylation of α-aminoesters with p-tolylboronic acid promoted by copper(II) acetate

  摘要：

  Copper-promoted N-arylation of alpha-amino esters with p-tolylboronic acid at room temperature was accomplished with little or no racemization. (C) 2003 Published by Elsevier Science Ltd.

  DOI：

  10.1016/s0040-4039(02)02882-4

文献信息

• Direct Aryl C−H Amination with Primary Amines Using Organic Photoredox Catalysis
  作者：Kaila A. Margrey、Alison Levens、David A. Nicewicz

  DOI：10.1002/anie.201709523

  日期：2017.12.4

  photoredox catalyst under an aerobic atmosphere. A wide variety of primary amines, including amino acids and more complex amines are competent coupling partners. Various electron‐rich aromatics and heteroaromatics are useful scaffolds in this reaction, as are complex, biologically active arenes. We also describe the ability to functionalize arenes that are not oxidized by an acridinium catalyst, such as

  芳烃的直接催化CH胺化是一种强大的合成策略，在制药，农用化学品和材料化学中具有有用的应用。尽管在催化CHH功能化方面取得了进步，但脂肪胺偶联剂的使用仍然受到限制。本文描述的是在需氧气氛下使用using啶光氧化还原催化剂通过直接C H官能化，使用伯胺构建C N键。各种各样的伯胺，包括氨基酸和更复杂的胺都是有效的偶联伙伴。各种富电子芳族化合物和杂芳族化合物以及复杂的具有生物活性的芳烃在该反应中都是有用的支架。我们还描述了功能化未被not啶催化剂（如苯和甲苯）氧化的芳烃的功能，
• Synthesis of 1,5-Benzothiazepine Dipeptide Mimetics via Two CuI-Catalyzed Cross Coupling Reactions
  作者：Jiangang Gan、Dawei Ma

  DOI：10.1021/ol900943b

  日期：2009.7.2

  amino acids gives N-aryl amino acids, which are converted into linear dipeptides via iodination and condensation with l-cysteine derived acyl chloride. Cyclization is achieved via a CuI/N,N-dimethylglycine catalyzed intramolecular coupling of aryl iodides with the liberated thiol to afford 1,5-benzothiazepine dipeptide mimetics.

  CuI催化的4-甲基苯基溴化物与氨基酸的偶合生成N-芳基氨基酸，其通过碘化和与1-半胱氨酸衍生的酰氯缩合而转化为线性二肽。通过CuI / N，N，N-二甲基甘氨酸催化的芳基碘化物与释放的硫醇的分子内偶联来实现环化，从而提供1，5-苯并噻氮杂二肽模拟物。
• N-Arylation of α-aminoesters with p-tolylboronic acid promoted by copper(II) acetate
  作者：Patrick Y.S Lam、Damien Bonne、Guillaume Vincent、Charles G Clark、Andrew P Combs

  DOI：10.1016/s0040-4039(02)02882-4

  日期：2003.2

  Copper-promoted N-arylation of alpha-amino esters with p-tolylboronic acid at room temperature was accomplished with little or no racemization. (C) 2003 Published by Elsevier Science Ltd.
• Relaying Asymmetry of Transient Atropisomers of <i>o</i>-Iodoanilides by Radical Cyclizations
  作者：Marc Petit、Andre J. B. Lapierre、Dennis P. Curran

  DOI：10.1021/ja055666d

  日期：2005.11.1

  Atropisomers of N-2 degrees -alkyl-N-acryloyl-2-iodoanlides have been resolved by chromatography and crystallization-induced asymmetric transformation. These molecules have atropisomerization barriers of 23-24 kcal/mol and return to equilibrium ratios over several hours at ambient temperature in solution. The transient chirality can be locked in by radical cyclizations, which provide N-2 degrees -alkyl-3-methyl-1,3-dihydroindol-2-ones with high levels of chirality transfer. The mechanistic model features a stereoselective aryl radical cyclization that is more rapid than the rotation of the N-aryl bond of the anilide.