N-benzoyl-tert-leucine methyl ester | 119768-87-5

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: N-benzoyl-tert-leucine methyl ester
• 英文别名: methyl 2-benzoylamino-3,3-dimethylbutanoate；Methyl 2-benzamido-3,3-dimethylbutanoate
• CAS: 119768-87-5
• 化学式: C₁₄H₁₉NO₃
• 分子量: 249.31
• InChiKey: DVVYZGGPAJZHLS-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.9
• 重原子数：
  18
• 可旋转键数：
  5
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.43
• 拓扑面积：
  55.4
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  N-benzoyl-tert-leucine methyl ester 在 C₂₇H₃₁N₂O₂⁽¹⁺⁾*Cl^(1-) 、 sodium hydroxide 作用下， 以 氯仿 为溶剂， 反应 24.0h， 以6%的产率得到N-benzoyl-L-tert-leucine
  参考文献：
  名称：

  相转移催化碱水解对N-保护的氨基酸酯的动力学动力学拆分

  摘要：

  描述了用合成的小分子催化剂对α-手性酯的不对称碱水解。奎宁衍生的季铵盐用作手性相转移催化剂，可通过动态动力学拆分促进CHCl 3 / NaOH（aq）中N保护的氨基酸六氟异丙基酯的碱水解，以中等至良好的收率提供相应的产物（最高99％）和最高96：4 er。使用DFT计算和伪过渡态（pseudo-TS）构象搜索进行的实验和计算机制研究提供了考虑立体选择性起源的TS模型。该模型表明，π-堆积和H-键相互作用在稳定TS结构中起重要作用。

  DOI：

  10.1021/acscatal.8b00693
• 作为产物：
  描述：

  DL-叔亮氨酸 在 盐酸 、 三乙胺 作用下， 以 二氯甲烷 为溶剂， 生成 N-benzoyl-tert-leucine methyl ester
  参考文献：
  名称：

  Design of Radical-Resistant Amino Acid Residues:  A Combined Theoretical and Experimental Investigation

  摘要：

  Ab initio calculations have been used to design radical-resistant amino acid residues. Optimized structures of free and protected amino acids and their corresponding alpha-carbon-centered radicals were determined with B3-LYP/6-31G(d). Single-point RMP2/6-31G(d) calculations on these structures were then used to obtain radical stabilization energies, to examine the effect of steric repulsion between the side chains and amide carbonyl groups on the stability of alpha-carbon-centered peptide radicals. Relative to glycine, the destabilization for alanine and valine residues was found to be approximately 9 and 18 kJ mol(-1), respectively, which correlates with the reactivity of analogous amino acid residues in peptides toward hydrogen atom abstraction in conventional free radical reactions. To design amino acid residues that would resist radical reactions, strategies by which the steric effects could be magnified were considered. This resulted in the identification of tert-leucine and 3,3,3-trifluoroalanine as suitable molecules. With these amino acid residues, the destabilization of the alpha-carbon-centered radicals relative to that of glycine is increased substantially to approximately 36 and 41 kJ mol(-1), respectively. The theoretical predictions have been supported by experimental observations: a tert-leucine derivative was shown to be very slow to react with N-bromosuccinimide, while the corresponding trifluoroalanine derivative was found to be inert.

  DOI：

  10.1021/ja029674v

文献信息

• New syntheses of α-amino acids based on n-acylimino acetates
  作者：Thomas Bretschneider、Wolfgang Miltz、Peter Münster、Wolfgang Steglich

  DOI：10.1016/s0040-4020(01)86046-4

  日期：1988.1
• BRETSCHNEIDER, THOMAS;MILTZ, WOLFGANG;MUNSTER, PETER;STEGLICH, WOLFGANG, TETRAHEDRON, 44,(1988) N 17, C. 5403-5414
  作者：BRETSCHNEIDER, THOMAS、MILTZ, WOLFGANG、MUNSTER, PETER、STEGLICH, WOLFGANG

  DOI：——

  日期：——
• Dynamic Kinetic Resolution of N-Protected Amino Acid Esters via Phase-Transfer Catalytic Base Hydrolysis
  作者：Eiji Yamamoto、Kodai Wakafuji、Yuho Furutachi、Kaoru Kobayashi、Takashi Kamachi、Makoto Tokunaga

  DOI：10.1021/acscatal.8b00693

  日期：2018.7.6

  Asymmetric base hydrolysis of α-chiral esters with synthetic small-molecule catalysts is described. Quaternary ammonium salts derived from quinine were used as chiral phase-transfer catalysts to promote the base hydrolysis of N-protected amino acid hexafluoroisopropyl esters in a CHCl3/NaOH (aq) via dynamic kinetic resolution, providing the corresponding products in moderate to good yields (up to 99%)

  描述了用合成的小分子催化剂对α-手性酯的不对称碱水解。奎宁衍生的季铵盐用作手性相转移催化剂，可通过动态动力学拆分促进CHCl 3 / NaOH（aq）中N保护的氨基酸六氟异丙基酯的碱水解，以中等至良好的收率提供相应的产物（最高99％）和最高96：4 er。使用DFT计算和伪过渡态（pseudo-TS）构象搜索进行的实验和计算机制研究提供了考虑立体选择性起源的TS模型。该模型表明，π-堆积和H-键相互作用在稳定TS结构中起重要作用。
• Design of Radical-Resistant Amino Acid Residues:  A Combined Theoretical and Experimental Investigation
  作者：Anna K. Croft、Christopher J. Easton、Leo Radom

  DOI：10.1021/ja029674v

  日期：2003.4.1

  Ab initio calculations have been used to design radical-resistant amino acid residues. Optimized structures of free and protected amino acids and their corresponding alpha-carbon-centered radicals were determined with B3-LYP/6-31G(d). Single-point RMP2/6-31G(d) calculations on these structures were then used to obtain radical stabilization energies, to examine the effect of steric repulsion between the side chains and amide carbonyl groups on the stability of alpha-carbon-centered peptide radicals. Relative to glycine, the destabilization for alanine and valine residues was found to be approximately 9 and 18 kJ mol(-1), respectively, which correlates with the reactivity of analogous amino acid residues in peptides toward hydrogen atom abstraction in conventional free radical reactions. To design amino acid residues that would resist radical reactions, strategies by which the steric effects could be magnified were considered. This resulted in the identification of tert-leucine and 3,3,3-trifluoroalanine as suitable molecules. With these amino acid residues, the destabilization of the alpha-carbon-centered radicals relative to that of glycine is increased substantially to approximately 36 and 41 kJ mol(-1), respectively. The theoretical predictions have been supported by experimental observations: a tert-leucine derivative was shown to be very slow to react with N-bromosuccinimide, while the corresponding trifluoroalanine derivative was found to be inert.