(R)-3-({(R)-4-[(S)-3-(tert-Butoxycarbonylamino-methyl)-4-methyl-pentanoylamino]-3-methyl-butyrylamino}-methyl)-5-methyl-hexanoic acid methyl ester | 423184-10-5

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 脂肪酰基
• 英文名称: (R)-3-({(R)-4-[(S)-3-(tert-Butoxycarbonylamino-methyl)-4-methyl-pentanoylamino]-3-methyl-butyrylamino}-methyl)-5-methyl-hexanoic acid methyl ester
• 英文别名: methyl (3R)-5-methyl-3-[[[(3R)-3-methyl-4-[[(3S)-4-methyl-3-[[(2-methylpropan-2-yl)oxycarbonylamino]methyl]pentanoyl]amino]butanoyl]amino]methyl]hexanoate
• CAS: 423184-10-5
• 化学式: C₂₆H₄₉N₃O₆
• 分子量: 499.692
• InChiKey: BEIAPTNELVQXSU-NJDAHSKKSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.6
• 重原子数：
  35
• 可旋转键数：
  18
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.85
• 拓扑面积：
  123
• 氢给体数：
  3
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  (R)-3-({(R)-4-[(S)-3-(tert-Butoxycarbonylamino-methyl)-4-methyl-pentanoylamino]-3-methyl-butyrylamino}-methyl)-5-methyl-hexanoic acid methyl ester 在 N-甲基吗啉 、 sodium hydroxide 、 1-羟基苯并三唑 、 盐酸-N-乙基-Nˊ-(3-二甲氨基丙基)碳二亚胺 作用下， 以 四氢呋喃 、 甲醇 、 二氯甲烷 、 2,2,2-三氟乙醇 为溶剂， 反应 19.0h， 生成 (R)-3-[((R)-4-{(S)-3-[((R)-3-{[(R)-4-((S)-3-Aminomethyl-4-methyl-pentanoylamino)-3-methyl-butyrylamino]-methyl}-5-methyl-hexanoylamino)-methyl]-4-methyl-pentanoylamino}-3-methyl-butyrylamino)-methyl]-5-methyl-hexanoic acid; compound with trifluoro-acetic acid
  参考文献：
  名称：

  γ2-,γ3-, andγ2,3,4-Amino Acids, Coupling toγ-Hexapeptides: CD Spectra, NMR Solution and X-ray Crystal Structures ofγ-Peptides

  摘要：

  There are numerous possible gamma-amino acids with different degrees of substitution and with various constitutions and configurations. Of these the gamma(4)-and the like- and unlike-gamma(2.4)-amino acids have been previously used as building blocks in gamma-peptides. The synthesis of gamma(2)-, gamma(3)-, and gamma(2.3.4) peptides is now described. The corresponding amino acids have been prepared by Michael addition of chiral N-acyl-oxazolidinone enolates to nitro-olefins, with subsequent reduction of the NO2 to NH2 groups. Such additions to E-2-methyl-nitropropene provide (2R,3R,4R)-2-alkyl-3-methyl-4amino-pentanoic acid derivatives (9, 10, 11). Stepwise coupling and fragment coupling lead to gamma-di-, tri-, and hexapeptides (12-23), which were fully characterized. The crystal structures of one of the gamma-amino acids (2,3-dimethyl-4-amino-pentanoic acid .HCl, 9 a), of a gamma(2.3.4)-di- and a gamma(2.3.4)-tetrapeptide (20, 22) are described, and the NMR solution structure in MeOH of a gamma(2.3.4)-hexapeptide (3) has been determined (using TOCSY, COSY, HSQC, HMBC and ROESY measurements and a molecular dynamics simulated-annealing protocol). A linear conformation (sheet-like), a novel (M) helix built of nine-membered hydrogen-bonded rings, and (M) 2.6(14) helices have thus been identified. NMR measurements at different temperatures (298-393 K) and H/D-exchange rates obtained for the y(2.3.4)- -hexapeptide are interpreted as evidence for the stability of the 2.6(14) helix (no "melting") and for its non-cooperative folding mechanism. CD Spectra of the gamma-peptides have been measured in MeOH and CH3CN, indicating that only the protected and unprotected y(2.3.4)-hexapeptide is present as the 2.614 helix in solution. The structures of the gamma(2)- and gamma(3)-hexapeptides (1, 2) could not be determined.

  DOI：

  10.1002/1521-3765(20020201)8:3<573::aid-chem573>3.0.co;2-h
• 作为产物：
  描述：

  (S)-3-{[(tert-butoxycarbonyl)amino]methyl}-3-methylpentanoic acid 、 (R)-3-[((R)-4-Amino-3-methyl-butyrylamino)-methyl]-5-methyl-hexanoic acid methyl ester; compound with trifluoro-acetic acid 在 N-甲基吗啉 、 1-羟基苯并三唑 、 盐酸-N-乙基-Nˊ-(3-二甲氨基丙基)碳二亚胺 作用下， 以 四氢呋喃 为溶剂， 以1.61 g的产率得到(R)-3-({(R)-4-[(S)-3-(tert-Butoxycarbonylamino-methyl)-4-methyl-pentanoylamino]-3-methyl-butyrylamino}-methyl)-5-methyl-hexanoic acid methyl ester
  参考文献：
  名称：

  γ2-,γ3-, andγ2,3,4-Amino Acids, Coupling toγ-Hexapeptides: CD Spectra, NMR Solution and X-ray Crystal Structures ofγ-Peptides

  摘要：

  There are numerous possible gamma-amino acids with different degrees of substitution and with various constitutions and configurations. Of these the gamma(4)-and the like- and unlike-gamma(2.4)-amino acids have been previously used as building blocks in gamma-peptides. The synthesis of gamma(2)-, gamma(3)-, and gamma(2.3.4) peptides is now described. The corresponding amino acids have been prepared by Michael addition of chiral N-acyl-oxazolidinone enolates to nitro-olefins, with subsequent reduction of the NO2 to NH2 groups. Such additions to E-2-methyl-nitropropene provide (2R,3R,4R)-2-alkyl-3-methyl-4amino-pentanoic acid derivatives (9, 10, 11). Stepwise coupling and fragment coupling lead to gamma-di-, tri-, and hexapeptides (12-23), which were fully characterized. The crystal structures of one of the gamma-amino acids (2,3-dimethyl-4-amino-pentanoic acid .HCl, 9 a), of a gamma(2.3.4)-di- and a gamma(2.3.4)-tetrapeptide (20, 22) are described, and the NMR solution structure in MeOH of a gamma(2.3.4)-hexapeptide (3) has been determined (using TOCSY, COSY, HSQC, HMBC and ROESY measurements and a molecular dynamics simulated-annealing protocol). A linear conformation (sheet-like), a novel (M) helix built of nine-membered hydrogen-bonded rings, and (M) 2.6(14) helices have thus been identified. NMR measurements at different temperatures (298-393 K) and H/D-exchange rates obtained for the y(2.3.4)- -hexapeptide are interpreted as evidence for the stability of the 2.6(14) helix (no "melting") and for its non-cooperative folding mechanism. CD Spectra of the gamma-peptides have been measured in MeOH and CH3CN, indicating that only the protected and unprotected y(2.3.4)-hexapeptide is present as the 2.614 helix in solution. The structures of the gamma(2)- and gamma(3)-hexapeptides (1, 2) could not be determined.

  DOI：

  10.1002/1521-3765(20020201)8:3<573::aid-chem573>3.0.co;2-h