L-脯氨酸,5-乙烯基-1-[(4-甲基苯基)磺酰]-,甲基酯,反- | 138958-13-1

• 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
• 中文名称: L-脯氨酸,5-乙烯基-1-[(4-甲基苯基)磺酰]-,甲基酯,反-
• 英文名称: methyl (2S,5S)-1-tosyl-5-vinylpyrrolidine-2-carboxylate
• 英文别名: (2S,5S)-N-tosyl-5-vinylproline methyl ester
• CAS: 138958-13-1
• 化学式: C₁₅H₁₉NO₄S
• 分子量: 309.386
• InChiKey: VKLRETUBNFQFAH-OCCSQVGLSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.88
• 重原子数：
  21.0
• 可旋转键数：
  4.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.4
• 拓扑面积：
  63.68
• 氢给体数：
  0.0
• 氢受体数：
  4.0

反应信息

• 作为产物：
  描述：

  1-carbomethoxy-5-methoxy-L-proline methyl ester 在 Lindlar's catalyst 吡啶 、 碘代三甲硅烷 、 四丁基氟化铵 、 氢气 、 四氯化钛 作用下， 以 四氢呋喃 、 二氯甲烷 、 乙酸乙酯 为溶剂， 20.0 ℃ 、101.33 kPa 条件下， 反应 38.17h， 生成 L-脯氨酸,5-乙烯基-1-[(4-甲基苯基)磺酰]-,甲基酯,反-
  参考文献：
  名称：

  Syntheses of proline analogs as potential mechanism-based inhibitors of proline dehydrogenase: 4-methylene-L-, (E)- and (Z)-4-(fluoromethylene)-L-, cis- and trans-5-ethynyl-(.+-.)-, and cis- and trans-5-vinyl-L-proline

  摘要：

  Proline dehydrogenase is an enzyme involved in the energetic processes required for flight in certain insects including the tse-tse fly. Proline analogues were designed for the inhibition of this enzyme. For this purpose 4-methylene-L-proline and (E)- and (Z)-4-(fluoromethylene)-L-proline were prepared from trans-4-hydroxyl-L-proline through the following sequence: protection at the nitrogen with a tert-butoxycarbonyl and at the caboxylic acid as methyl ester, oxidation of the hydroxyl group to a ketone, Wittig reaction, and removal of the protecting groups. The cis- and trans-5-ethynyl-(+/-)-proline was prepared from N-(tert-butoxycarbonyl)-3-(trimethylsilyl)-2-propynylamine whose dianion reacted with 1,2-epoxy 4-bromobutane. Cyclization in the presence of trifluoroacetic acid, oxidation of the primary alcohol to acid, and removal of the protecting groups gave cis- and trans-5-ethynyl-(+/-)-proline. Stereoselectivity was observed in the reaction of the dianion of 3-(trimethylsilyl)-2-propynylamine with 1,2-epoxy-4-bromobutane. The cis- and trans-5-vinyl-L-prolines were prepared from N-(methoxycarbonyl)-5-methoxy-L-proline ester by reaction with bis(trimethylsilyl)acetylene in the presence of titanium tetrachloride followed by sequential removal of the protecting groups and by reduction. The cis and trans configuration of the 5-vinyl-L-proline obtained was established by comparison of the NMR spectrum of the trans-N-tosyl-5-vinyl-(+/-)-proline methyl ester with the published spectrum of the trans derivative.

  DOI：

  10.1021/jo00033a029

文献信息

• Intramolecular Nicholas Reaction: Stereoselective Synthesis of 5-Alkynylproline Derivatives
  作者：J. Nicolás Hernández、Miguel A. Ramírez、Matías L. Rodríguez、Víctor S. Martín

  DOI：10.1021/ol800544a

  日期：2008.6.1

  The intramolecular Nicholas reaction of propargylic alcohols derived from N, N-acyl-diprotected omega-semialdehydes obtained from glutamic acid provided stereoselectively 5-alkynylproline derivatives. The suitable choice of the N-protecting group (tosyl or benzoyl derivative) permitted control of the stereochemistry during the ring formation. Semiempirical calculations of the species involved in the

  衍生自谷氨酸的N，N-酰基双保护的ω-半醛的炔丙醇的分子内尼古拉斯反应提供了立体选择性的5-炔基脯氨酸衍生物。的N-保护基团（甲苯磺酰基或苯甲酰基衍生物）的适当选择的环的形成过程中所允许的立体化学的控制。半环化涉及的物种的半经验计算支持观察到的立体化学。