3-(5-cyclohexylpenta-2E,4E-dienamido)-4,4-dimethoxy-5,6-epoxycyclohex-2-en-1-one

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 3-(5-cyclohexylpenta-2E,4E-dienamido)-4,4-dimethoxy-5,6-epoxycyclohex-2-en-1-one
• 英文别名: (2E,4E)-5-cyclohexyl-N-[(1R,6S)-2,2-dimethoxy-5-oxo-7-oxabicyclo[4.1.0]hept-3-en-3-yl]penta-2,4-dienamide
• 化学式: C₁₉H₂₅NO₅
• 分子量: 347.411
• InChiKey: PVMYXHUGMZSUNW-JMRJQHPDSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.1
• 重原子数：
  25
• 可旋转键数：
  6
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.58
• 拓扑面积：
  77.2
• 氢给体数：
  1
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  3-(5-cyclohexylpenta-2E,4E-dienamido)-4,4-dimethoxy-5,6-epoxycyclohex-2-en-1-one 在 正丁基锂 、 4-甲基苯磺酸吡啶 作用下， 以 四氢呋喃 、 正己烷 、 水 、 丙酮 为溶剂， 反应 6.17h， 生成 3-(2-cyclohexylpenta-2E,4E-dienamido)-4-(2"E-bromoethenyl)-4-hydroxy-5,6-epoxycyclohex-2-en-1-one
  参考文献：
  名称：

  Total Synthesis of (±)-Nisamycin

  摘要：

  We have developed a highly convergent synthesis of the manumycin-type m-C7N-antibiotic nisamycin that is applicable to other members of this family of antibiotics. The synthesis features a three-step sequence to the epoxyquinol core that serves as a scaffold for the attachment of the polyene side chains. The eastern polyene side chain was constructed via a novel organozirconocene-mediated synthesis. Zirconocene methodology was also applied to the synthesis of the polyene side chains of asukamycin. The southern side chain of nisamycin was introduced via a Stille reaction that employed a vinyl bromo ketone, derived from an acid-sensitive bromo ketal. Pd-mediated coupling of the vinyl bromide with a stannyl TIPS ester gave TIPS-protected nisamycin that was readily converted to the natural product.

  DOI：

  10.1021/jo990413m
• 作为产物：
  描述：

  tri(propan-2-yl)silyl (E)-5-cyclohexyl-5-hydroxypent-3-enoate 在 吡啶 、 4-二甲氨基吡啶 、 草酰氯 、 N,N-二异丙基乙胺 作用下， 以 四氢呋喃 、 N,N-二甲基甲酰胺 为溶剂， 反应 7.5h， 生成 3-(5-cyclohexylpenta-2E,4E-dienamido)-4,4-dimethoxy-5,6-epoxycyclohex-2-en-1-one
  参考文献：
  名称：

  Total Synthesis of (±)-Nisamycin

  摘要：

  We have developed a highly convergent synthesis of the manumycin-type m-C7N-antibiotic nisamycin that is applicable to other members of this family of antibiotics. The synthesis features a three-step sequence to the epoxyquinol core that serves as a scaffold for the attachment of the polyene side chains. The eastern polyene side chain was constructed via a novel organozirconocene-mediated synthesis. Zirconocene methodology was also applied to the synthesis of the polyene side chains of asukamycin. The southern side chain of nisamycin was introduced via a Stille reaction that employed a vinyl bromo ketone, derived from an acid-sensitive bromo ketal. Pd-mediated coupling of the vinyl bromide with a stannyl TIPS ester gave TIPS-protected nisamycin that was readily converted to the natural product.

  DOI：

  10.1021/jo990413m

文献信息

• Asymmetric synthesis of the mC7N core of the manumycin family: Preparation of (+)-MT 35214 and a formal total synthesis of (−)-alisamycin
  作者：Gregor Macdonald、Lilian Alcaraz、Norman J Lewis、Richard J.K Taylor

  DOI：10.1016/s0040-4039(98)01047-8

  日期：1998.7

  An asymmetric approach to the mC(7)N epoxyquinone central unit of the manumycin antibiotics is described based on the enantioselective (89% ee) chiral phase transfer epoxidation of a substituted cyclohexenone. The chiral epoxide is employed in the first syntheses of the tide compounds in enantiomerically pure form. (C) 1998 Elsevier Science Ltd. All rights reserved.
• Total Synthesis of (±)-Nisamycin
  作者：Peter Wipf、Philip D. G. Coish

  DOI：10.1021/jo990413m

  日期：1999.7.1

  We have developed a highly convergent synthesis of the manumycin-type m-C7N-antibiotic nisamycin that is applicable to other members of this family of antibiotics. The synthesis features a three-step sequence to the epoxyquinol core that serves as a scaffold for the attachment of the polyene side chains. The eastern polyene side chain was constructed via a novel organozirconocene-mediated synthesis. Zirconocene methodology was also applied to the synthesis of the polyene side chains of asukamycin. The southern side chain of nisamycin was introduced via a Stille reaction that employed a vinyl bromo ketone, derived from an acid-sensitive bromo ketal. Pd-mediated coupling of the vinyl bromide with a stannyl TIPS ester gave TIPS-protected nisamycin that was readily converted to the natural product.