tert-butyl (2R,3R,Z)-4-ethylidene-2-(hydroxymethyl)-3-methylpyrrolidine-1-carboxylate | 1197285-74-7

• 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: tert-butyl (2R,3R,Z)-4-ethylidene-2-(hydroxymethyl)-3-methylpyrrolidine-1-carboxylate
• 英文别名: (2R,3R,Z)-tert-butyl 4-ethylidene-2-(hydroxymethyl)-3-methylpyrrolidine-1-carboxylate；tert-butyl (2R,3R,4Z)-4-ethylidene-2-(hydroxymethyl)-3-methylpyrrolidine-1-carboxylate
• CAS: 1197285-74-7
• 化学式: C₁₃H₂₃NO₃
• 分子量: 241.331
• InChiKey: PICZNPZCXCQRCM-SZAMVBNTSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.4
• 重原子数：
  17
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.77
• 拓扑面积：
  49.8
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  tert-butyl (2R,3R,Z)-4-ethylidene-2-(hydroxymethyl)-3-methylpyrrolidine-1-carboxylate 在 盐酸 、 sodium dihydrogenphosphate 、 2-甲基-2-丁烯 、 戴斯-马丁氧化剂 、 N,N-二异丙基乙胺 、 Methanaminium,N-[(dimethylamino)(3H-1,2,3-triazolo[4,5-b]pyridin-3-yloxy)methylene]-N-methyl-, hexafluorophosphate(1-) 作用下， 以 四氢呋喃 、 1,4-二氧六环 、 乙醚 、 二氯甲烷 、 水 、 叔丁醇 为溶剂， 反应 10.5h， 生成 (S)-methyl 2-((2R,3R,Z)-1-((S)-2-benzamido-6-((Z)-2,3-bis(tert-butoxycarbonyl)guanidino)hexanoyl)-4-ethylidene-3-methylpyrrolidine-2-carboxamido)-4-methylpentanoate
  参考文献：
  名称：

  Rhodium-catalyzed reductive cyclization of 1,6-enynes and stereoselective synthesis of the putative structure of lucentamycin A and its stereoisomers

  摘要：

  A Rh-catalyzed diastereoselective reductive cyclization, mediated by hydrogen, of optically active 1,6-enynes using chiral BINAP was successfully applied to the total synthesis of four stereoisomers of the proposed structure of lucentamycin A. In order to synthesize two of these four stereoisomers, we successfully constructed chiral proline derivatives bearing cis-carbon substituents at C2 and C3 positions based on Krische's methodology, which has very rarely been reported. Anti-proliferative activities on HCT-116 cell line and NMR data of these four stereoisomers were compared with those of naturally occurring lucentamycine A. The results show that the proposed structure of lucentamycin A needs revision. (C) 2012 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2011.12.075
• 作为产物：
  描述：

  (7R,7aR,Z)-6-ethylidene-7-methyltetrahydropyrrolo[1,2-c]oxazol-3(1H)-one 在 三乙胺 、 sodium hydroxide 作用下， 以 乙醇 、 二氯甲烷 、 水 为溶剂， 反应 5.0h， 生成 tert-butyl (2R,3R,Z)-4-ethylidene-2-(hydroxymethyl)-3-methylpyrrolidine-1-carboxylate
  参考文献：
  名称：

  Rhodium-catalyzed reductive cyclization of 1,6-enynes and stereoselective synthesis of the putative structure of lucentamycin A and its stereoisomers

  摘要：

  A Rh-catalyzed diastereoselective reductive cyclization, mediated by hydrogen, of optically active 1,6-enynes using chiral BINAP was successfully applied to the total synthesis of four stereoisomers of the proposed structure of lucentamycin A. In order to synthesize two of these four stereoisomers, we successfully constructed chiral proline derivatives bearing cis-carbon substituents at C2 and C3 positions based on Krische's methodology, which has very rarely been reported. Anti-proliferative activities on HCT-116 cell line and NMR data of these four stereoisomers were compared with those of naturally occurring lucentamycine A. The results show that the proposed structure of lucentamycin A needs revision. (C) 2012 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2011.12.075

文献信息

• Progress toward the Total Synthesis of Lucentamycin A: Total Synthesis and Biological Evaluation of 8-<i>epi</i>-Lucentamycin A
  作者：R. Nathan Daniels、Bruce J. Melancon、Emily A. Wang、Brenda C. Crews、Lawrence J. Marnett、Gary A. Sulikowski、Craig W. Lindsley

  DOI：10.1021/jo902115s

  日期：2009.11.20

  Synthetic efforts toward the cytotoxic peptides lucentamycins A−D are described that resulted in the total synthesis and biological evaluation of 8-epi-lucentamycin A in 15 steps with 2.2% overall yield. The key epi-nonproteogenic 3-methyl-4-ethylideneproline was synthesized via a titanium-mediated cycloisomerization reaction.

  描述了对细胞毒性肽 lucentamycins A-D 的合成努力，导致 8- epi- lucentamycin A的全合成和生物学评估分15 个步骤，总产率为 2.2%。关键外延-nonproteogenic 3-甲基-4- ethylideneproline经由钛介导的环异构反应合成。
• Rhodium-catalyzed reductive cyclization of 1,6-enynes and stereoselective synthesis of the putative structure of lucentamycin A and its stereoisomers
  作者：Young Jin Ham、Hana Yu、Nam Doo Kim、Jung-Mi Hah、Khalid B. Selim、Hwan Geun Choi、Taebo Sim

  DOI：10.1016/j.tet.2011.12.075

  日期：2012.2

  A Rh-catalyzed diastereoselective reductive cyclization, mediated by hydrogen, of optically active 1,6-enynes using chiral BINAP was successfully applied to the total synthesis of four stereoisomers of the proposed structure of lucentamycin A. In order to synthesize two of these four stereoisomers, we successfully constructed chiral proline derivatives bearing cis-carbon substituents at C2 and C3 positions based on Krische's methodology, which has very rarely been reported. Anti-proliferative activities on HCT-116 cell line and NMR data of these four stereoisomers were compared with those of naturally occurring lucentamycine A. The results show that the proposed structure of lucentamycin A needs revision. (C) 2012 Elsevier Ltd. All rights reserved.