(3R,4R,5RS)-3,4,5-trimethylpyrrolidin-2-one | 331816-41-2

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡咯烷类
• 英文名称: (3R,4R,5RS)-3,4,5-trimethylpyrrolidin-2-one
• 英文别名: (3R,4R)-3,4,5-trimethylpyrrolidin-2-one
• CAS: 331816-41-2
• 化学式: C₇H₁₃NO
• 分子量: 127.186
• InChiKey: SOPHRCJZGNBNCM-QYRBDRAASA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1
• 重原子数：
  9
• 可旋转键数：
  0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.86
• 拓扑面积：
  29.1
• 氢给体数：
  1
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  (3R,4R,5RS)-3,4,5-trimethylpyrrolidin-2-one 在 10percent Pd/C N-甲基吗啉 、 盐酸 、 4-二甲氨基吡啶 、 sodium hydroxide 、 氢气 、 盐酸-N-乙基-Nˊ-(3-二甲氨基丙基)碳二亚胺 、 N-[(dimethylamino)-3-oxo-1H-1,2,3-triazolo[4,5-b]pyridin-1-yl-methylene]-N-methylmethanaminium hexafluorophosphate 作用下， 以 1,4-二氧六环 、 甲醇 、 二氯甲烷 为溶剂， 20.0 ℃ 、100.0 kPa 条件下， 反应 50.0h， 生成 benzyl (2R,3R,4R)-4-[[(2R,3R,4R)-4-[[(2R,3R,4R)-4-[[(2R,3R,4R)-4-[[(2R,3R,4R)-4-[[(2R,3R,4R)-2,3-dimethyl-4-[(2-methylpropan-2-yl)oxycarbonylamino]pentanoyl]amino]-3-methyl-2-(2-methylpropyl)pentanoyl]amino]-2,3-dimethylpentanoyl]amino]-3-methyl-2-(2-methylpropyl)pentanoyl]amino]-2,3-dimethylpentanoyl]amino]-3-methyl-2-(2-methylpropyl)pentanoate
  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)-4-isopropyl-3-((2R,3R,4RS)-2,3-dimethyl-4-nitropentanoyl)-5,5-diphenyloxazolidin-2-one 在 镍 氢气 作用下， 生成 (3R,4R,5RS)-3,4,5-trimethylpyrrolidin-2-one
  参考文献：
  名称：

  Preparation and determination of X-ray-crystal and NMR-solution structures of γ2,3,4-peptides

  摘要：

  (R,R,R)-δ-氨基酸的侧链位于 2-、3-和 4-位，是通过将酰基噁唑烷酮与硝基烯烃加成并氢化而制备的，已被δ-四肽和δ-六肽偶联，这些δ-四肽和δ-六肽在晶体状态和 MeOH 溶液中形成了 (M)-2.614 螺旋。

  DOI：

  10.1039/b008377l

文献信息

• γ2-,γ3-, andγ2,3,4-Amino Acids, Coupling toγ-Hexapeptides: CD Spectra, NMR Solution and X-ray Crystal Structures ofγ-Peptides
  作者：Dieter Seebach、Meinrad Brenner、Magnus Rueping、Bernhard Jaun

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

  日期：2002.2.1

  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.
• Preparation and determination of X-ray-crystal and NMR-solution structures of γ2,3,4-peptides
  作者：Dieter Seebach、Meinrad Brenner、Magnus Rueping、Bernd Schweizer、Bernhard Jaun

  DOI：10.1039/b008377l

  日期：——

  (R,R,R)-γ-Amino acids with side chains in the 2-, 3-, and 4-positions, prepared by addition of acyloxazolidinones to a nitroolefin and hydrogenation, have been coupled to γ- tetra-, and γ-hexapeptides which are shown to form (M)-2.614 helices in the crystal state and in MeOH solution.

  (R,R,R)-δ-氨基酸的侧链位于 2-、3-和 4-位，是通过将酰基噁唑烷酮与硝基烯烃加成并氢化而制备的，已被δ-四肽和δ-六肽偶联，这些δ-四肽和δ-六肽在晶体状态和 MeOH 溶液中形成了 (M)-2.614 螺旋。