(7R,7aR,Z)-6-ethylidene-7-methyltetrahydropyrrolo[1,2-c]oxazol-3(1H)-one | 1197285-69-0

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 唑烷类
• 英文名称: (7R,7aR,Z)-6-ethylidene-7-methyltetrahydropyrrolo[1,2-c]oxazol-3(1H)-one
• 英文别名: (6Z,7R,7aR)-6-ethylidene-7-methyl-1,5,7,7a-tetrahydropyrrolo[1,2-c][1,3]oxazol-3-one
• CAS: 1197285-69-0
• 化学式: C₉H₁₃NO₂
• 分子量: 167.208
• InChiKey: BRRQKIMNDGINSA-RVLUYLEASA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.8
• 重原子数：
  12
• 可旋转键数：
  0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.67
• 拓扑面积：
  29.5
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  (7R,7aR,Z)-6-ethylidene-7-methyltetrahydropyrrolo[1,2-c]oxazol-3(1H)-one 在 戴斯-马丁氧化剂 、 三乙胺 、 sodium hydroxide 作用下， 以 乙醇 、 二氯甲烷 、 水 为溶剂， 反应 8.0h， 生成 tert-butyl (2R,3R,Z)-4-ethylidene-2-formyl-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
• 作为产物：
  描述：

  (R)-4-vinyloxazolidin-2-one 在 bis(1,5-cyclooctadiene)rhodium(I) tetrafluoroborate 、 氢气 、 sodium hydride 、 (R)-2,2'-bis(diphenylphosphanyl)-1,1'-binaphthyl 作用下， 以 四氢呋喃 、 1,2-二氯乙烷 、 mineral oil 为溶剂， 反应 5.5h， 生成 (7R,7aR,Z)-6-ethylidene-7-methyltetrahydropyrrolo[1,2-c]oxazol-3(1H)-one
  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。
• Stereoselective total synthesis of the E-isomer of putative lucentamycin A
  作者：Khalid B. Selim、Baeck Kyoung Lee、Taebo Sim

  DOI：10.1016/j.tetlet.2012.08.092

  日期：2012.10

  A synthesis of the E-isomer of the proposed structure of the novel tripeptide, lucentamycin A, was performed in an attempt to define the correct stereochemistry of this natural product. The synthetic route developed employs a stereoselective Rh-catalyzed reductive cyclization process to generate the key pyrrolidine residue in the target and a stereospecific inversion of the Z-olefin geometry to form

  为了确定这种天然产物的正确的立体化学，进行了新颖的三肽提议的结构，荧光素霉素A的E-异构体的合成。开发的合成路线采用立体选择性Rh-催化的还原环化过程以在靶中产生关键的吡咯烷残基，以及Z-烯烃几何结构的立体有择的转化以形成所需的E-异构体。随后的酰胺偶联反应提供了所需的假定的路他霉素A的E-异构体。合成的E - 1a NMR数据与天然存在的路他霉素A的NMR数据比较表明，它们不是相同的物质，并且E与天然荧光素A相比，发现-1a对结肠癌细胞系HCT-116没有抗增殖活性。
• 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.