pikronolide | 51724-55-1

• 分子结构分类: 有机化合物 - 苯丙烷和聚酮 - 大环内酯类和类似物
• 英文名称: pikronolide
• 英文别名: (3R,5R,6S,7S,9R,11E,13S,14R)-14-ethyl-6,13-dihydroxy-3,5,7,9,13-pentamethyl-1-oxacyclotetradec-11-ene-2,4,10-trione
• CAS: 51724-55-1
• 化学式: C₂₀H₃₂O₆
• 分子量: 368.47
• InChiKey: LGZPXBXIIGFHEV-UHTWHWNNSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.6
• 重原子数：
  26
• 可旋转键数：
  1
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.75
• 拓扑面积：
  101
• 氢给体数：
  2
• 氢受体数：
  6

反应信息

• 作为产物：
  描述：

  (3R,5R,6S,7S,9R,13R,14R)-14-ethyl-13-benzyloxy-6-(4-methoxybenzyloxy)-3,5,7,9,13-pentamethyl-1-oxacyclotetradec-11(E)-ene-2,4,10-trione 在 水 、 2,3-二氯-5,6-二氰基-1,4-苯醌 作用下， 以 二氯甲烷 为溶剂， 反应 19.0h， 以81%的产率得到pikronolide
  参考文献：
  名称：

  Highly stereoselective total synthesis of pikronolide, the aglycon of the first macrolide antibiotic pikromycin. Crucial role of benzyl-type protecting groups removable by 2,4-dichloro-5,6-dicyanobenzoquinone oxidation.

  摘要：

  首次合成了皮克诺利德，皮克霉素的苷元，皮克霉素是第一个被分离的巨环抗生素。两个片段 i (5：C-1-C-10) 和 ii (6：C-11-C-15) 是从 D-葡萄糖高立体选择性合成的，并通过 Yamaguchi 方法结合形成酯(17)，该酯随后通过 Nicolaou 开发的分子内 Wittig-Horner 反应进行大环化，最终分离得到了产率极高的 14 元环烯酮 (18)。去保护基团和 Swern 氧化反应得到皮克诺利德 (2)。在这次合成中，3,4-二甲氧苯基、4-甲氧苯基和苯基保护基团在羟基功能上起到了关键作用。

  DOI：

  10.1248/cpb.35.2228

文献信息

• Total Synthesis of Pikromycin
  作者：Hong-Se Oh、Han-Young Kang

  DOI：10.1021/jo201158q

  日期：2012.1.20

  The total synthesis of pikromycin (6), the first isolated macrolide antibiotic, was achieved. The target macrolide was retrosynthetically divided into two parts, pikronolide (6a) (aglycon) and d-desosamine. The aglycon was synthesized using key reactions such as an asymmetric aldol reaction, Yamaguchi esterification, and ring-closing metathesis. The aglycon was coupled successfully with the trichloroacetimidate

  第一个分离出的大环内酯类抗生素吡咯霉素（6）的总合成得以实现。将目标大环内酯逆合成合成为两部分，吡克洛内酯（6a）（糖苷配基）和d-去糖胺。糖苷配基是使用关键反应合成的，例如不对称的醛醇缩合反应，山口酯化反应和闭环易位反应。在路易斯酸性条件下，将糖苷配基与d-去糖胺的三氯乙亚胺衍生物成功偶联，得到吡咯霉素。Narbomycin（5）也从narbonolide（合成5A）相同的条件下。
• Chiral synthesis of polyketide-derived natural products. 10. Stereoselective synthesis of pikronolide, the aglycon of the 14-membered ring macrolide pikromycin, from D-glucose. Role of MPM and DMPM protection
  作者：Noriyuki. Nakajima、Tatsuo. Hamada、Tatsuyoshi. Tanaka、Yuji. Oikawa、Osamu. Yonemitsu

  DOI：10.1021/ja00275a063

  日期：1986.7
• An Alternative and Facile Synthesis of Pikronolide
  作者：Noriyuki Nakajima、MAkoto Ubukata、Osamu Yonemitsu

  DOI：10.3987/com-97-s38

  日期：——

  An alternative and facile synthesis of pikronolide (2), the aglycon of pikromycin (1), via coupling between the C-11-C-15 fragment (10) and the C-I-C-l0 fragment (12), Homer-Emmons cyclization, regioselective protection of the C-5-hydroxy group, and oxidation of the C-3-hydroxy group, is described. In this synthesis, the conformational analysis by NMR played mt important role.
• NAKAJIMA, NORIYUKI;TANAKA, TATSUYOSHI;HAMADA, TATSUO;OIKAWA, YUJI;YONEMIT+, CHEM. AND PHARM. BULL., 35,(1987) N 6, 2228-2237
  作者：NAKAJIMA, NORIYUKI、TANAKA, TATSUYOSHI、HAMADA, TATSUO、OIKAWA, YUJI、YONEMIT+

  DOI：——

  日期：——
• Highly stereoselective total synthesis of pikronolide, the aglycon of the first macrolide antibiotic pikromycin. Crucial role of benzyl-type protecting groups removable by 2,4-dichloro-5,6-dicyanobenzoquinone oxidation.
  作者：NORIYUKI NAKAJIMA、TATSUYOSHI TANAKA、TATSUO HAMADA、YUJI OIKAWA、OSAMU YONEMITSU

  DOI：10.1248/cpb.35.2228

  日期：——

  The first total synthesis of pikronolide, the aglycon of pikromycin, isolated as the first macrolide antibiotic, is described. Two segments i (5 : C-1-C-10) and ii (6 : C-11-C-15) were synthesized highly stereoselectively from D-glucose and coupled by Yamaguchi's method to give the ester (17), which was subjected to macrocyclization by means of the intramolecular Wittig-Horner reaction developed by Nicolaou, and the 14-membered cyclic enone (18) was isolated in excellent yield. Removal of protecting groups and Swern oxidation gave pikronolide (2). In this synthesis, 3, 4-dimethoxybenzyl, 4-methoxybenzyl, and benzyl protecting group for hydroxy function played a crucial role.

  首次合成了皮克诺利德，皮克霉素的苷元，皮克霉素是第一个被分离的巨环抗生素。两个片段 i (5：C-1-C-10) 和 ii (6：C-11-C-15) 是从 D-葡萄糖高立体选择性合成的，并通过 Yamaguchi 方法结合形成酯(17)，该酯随后通过 Nicolaou 开发的分子内 Wittig-Horner 反应进行大环化，最终分离得到了产率极高的 14 元环烯酮 (18)。去保护基团和 Swern 氧化反应得到皮克诺利德 (2)。在这次合成中，3,4-二甲氧苯基、4-甲氧苯基和苯基保护基团在羟基功能上起到了关键作用。