(S)-tert-butyl 2-((2S,3R,E)-4-ethylidene-3-methylpyrrolidine-2-carboxamido)-4-methylpentanoate | 1403324-66-2

• 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
• 英文名称: (S)-tert-butyl 2-((2S,3R,E)-4-ethylidene-3-methylpyrrolidine-2-carboxamido)-4-methylpentanoate
• 英文别名: tert-butyl (2S)-2-[[(2S,3R,4E)-4-ethylidene-3-methylpyrrolidine-2-carbonyl]amino]-4-methylpentanoate
• CAS: 1403324-66-2
• 化学式: C₁₈H₃₂N₂O₃
• 分子量: 324.464
• InChiKey: GYSSDKUIGUOCGW-VWXYDCKNSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.7
• 重原子数：
  23
• 可旋转键数：
  7
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.78
• 拓扑面积：
  67.4
• 氢给体数：
  2
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  (S)-tert-butyl 2-((2S,3R,E)-4-ethylidene-3-methylpyrrolidine-2-carboxamido)-4-methylpentanoate 在 二乙胺 、 三乙胺 、 3-(二乙氧基邻酰氧基)-1,2,3-苯并三嗪-4-酮 作用下， 以 四氢呋喃 为溶剂， 反应 12.0h， 生成 (S)-tert-butyl 2-((2S,3R,4E)-1-((S)-2-benzamido-6-(2,3-bis-(tert-butoxycarbonyl)guanidino)hexanoyl)-4-ethylidene-3-methylpyrrolidine-2-carboxamido)-4-methylpentanoate
  参考文献：
  名称：

  Total Synthesis and Structural Revision of Lucentamycin A

  摘要：

  Lucentamycin A is a marine-derived peptide natural product harboring a unique 4-ethylidene-3-methylproline (Emp) subunit. The proposed structure of lucentamycin A and the core Emp residue have recently been called into question through synthesis. Here, we report the first total synthesis of lucentamycin A, which confirms that the ethylidene substituent in Emp bears an E geometry, in contrast to the originally assigned Z configuration. Synthesis of the desired (E)-Emp subunit required the implementation of a novel strategy starting from Gamer's aldehyde.

  DOI：

  10.1021/jo301723y
• 作为产物：
  描述：

  (S)-tert-butyl 2-((2S,3R,E)-2-((tert-butoxycarbonyl)amino)-4-(chloromethyl)-3-methylhex-4-enamido)-4-methylpentanoate 在 potassium carbonate 作用下， 以 二氯甲烷 、 丙酮 为溶剂， 反应 26.5h， 生成 (S)-tert-butyl 2-((2S,3R,E)-4-ethylidene-3-methylpyrrolidine-2-carboxamido)-4-methylpentanoate
  参考文献：
  名称：

  Total Synthesis and Structural Revision of Lucentamycin A

  摘要：

  Lucentamycin A is a marine-derived peptide natural product harboring a unique 4-ethylidene-3-methylproline (Emp) subunit. The proposed structure of lucentamycin A and the core Emp residue have recently been called into question through synthesis. Here, we report the first total synthesis of lucentamycin A, which confirms that the ethylidene substituent in Emp bears an E geometry, in contrast to the originally assigned Z configuration. Synthesis of the desired (E)-Emp subunit required the implementation of a novel strategy starting from Gamer's aldehyde.

  DOI：

  10.1021/jo301723y

文献信息

• Bioinspired Palladium‐Catalyzed Intramolecular C(sp ³ )−H Activation for the Collective Synthesis of Proline Natural Products
  作者：Quan‐Zhe Li、Si‐Hua Hou、Jun‐Chen Kang、Peng‐Fei Lian、Yu Hao、Chao Chen、Jia Zhou、Tong‐Mei Ding、Shu‐Yu Zhang

  DOI：10.1002/anie.202207088

  日期：2022.8.15

  Bioinspired palladium(II)-catalyzed intramolecular cyclization of amino acid derivatives containing a vinyl iodide moiety by C−H activation enabled rapid access to a wide range of functionalized proline derivatives with an exocyclic double bond. Such functionalized prolines were used as intermediates for the total synthesis of several natural products: lucentamycin A, barmumycin, oxotomaymycin, and

  仿生钯 (II) 催化的通过 C-H 活化对含有碘乙烯部分的氨基酸衍生物进行分子内环化，可以快速获得具有环外双键的各种功能化脯氨酸衍生物。这种功能化的脯氨酸被用作几种天然产物全合成的中间体：光亮霉素 A、巴木霉素、氧代梅霉素和氧代原霉素。
• The formal synthesis of lucentamycin A: Construction of cis -2,3-disubstituted pyrrolidine core by application of SmI 2 -DMPU system
  作者：Kazunori Takahashi、Kei Fukushima、Masayoshi Tsubuki、Toshio Honda

  DOI：10.1016/j.tetlet.2018.02.076

  日期：2018.4

  The formal synthesis of lucentamycin A (1) was accomplished in 14 steps from D-serine methyl ester as a starting material. All the requisite stereogenic centers on the pyrrolidine core of 1 were controlled by SmI2-mediated cyclization. Construction of the methyl unit at the C9 position of 1 was achieved by decarbonylation of lactol 11 with stoichiometric amount of Rh(PPh3)(3)Cl. (C) 2018 Elsevier Ltd. All rights reserved.