rac-methyl 5-[(E,E)-hexa-1,3-dienyl]-2,5-dimethyl-4-oxo-4,5-dihydrofuran-3-carboxylate

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 二氢呋喃
• 英文名称: rac-methyl 5-[(E,E)-hexa-1,3-dienyl]-2,5-dimethyl-4-oxo-4,5-dihydrofuran-3-carboxylate
• 英文别名: methyl 5-[(1E,3E)-hexa-1,3-dienyl]-2,5-dimethyl-4-oxofuran-3-carboxylate
• 化学式: C₁₄H₁₈O₄
• 分子量: 250.295
• InChiKey: BNZPIQOOHVBONM-BLHCBFLLSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.8
• 重原子数：
  18
• 可旋转键数：
  5
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.43
• 拓扑面积：
  52.6
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为产物：
  描述：

  benzyl rel-(2R,3S)-2-hydroxy-2-methyl-3-[(methylsulfonyl)oxy]butanoate 在 iron(III) chloride 、 sodium tetrahydroborate 、 草酰氯 、 AgOTf 、 palladium 10% on activated carbon 、 双氧水 、 silver(I) acetate 、 palladium diacetate 、 乙酸酐 、 碳酸氢钠 、 溶剂黄146 作用下， 以 四氢呋喃 、 甲醇 、 二氯甲烷 、 水 、 乙酸酐 、 N,N-二甲基甲酰胺 、 乙腈 为溶剂， 反应 148.33h， 生成 rac-methyl 5-[(E,E)-hexa-1,3-dienyl]-2,5-dimethyl-4-oxo-4,5-dihydrofuran-3-carboxylate
  参考文献：
  名称：

  Total Syntheses of the Dihydrofuranonecarboxylate Natural Products Gregatin B and E: Gram-Scale Synthesis of (+)-Gregatin B and Unambiguous Assignment of the Stereostructure of (+)-Gregatin E

  摘要：

  We synthesized the dextrorotatory enantiomers of gregatin B (1.3 g scale) and E, establishing their diene side chains in the last step by Heck coupling with variable iodoolefins. Their counterpart was synthesized in 30% overall yield and with high enantiopurity (97% ee) from benzyl tiglate, beginning with an asymmetric dihydroxylation. The stereostructure of gregatin E followed from HPLC comparisons between the four synthetic stereoisomers of this compound and natural gregatin E, which we isolated from Cadophora gregata.

  DOI：

  10.1021/ol5032602

文献信息

• Total Synthesis of (+)-Gregatin B and E
  作者：Taichi Kusakabe、Yasuko Kawai、Keisuke Kato

  DOI：10.1021/ol402472q

  日期：2013.10.4

  The first total synthesis of (+)-gregatin E and a new total synthesis of (+)-gregatin B are described. Key features of our synthetic approach involve a palladium-catalyzed cyclization–methoxycarbonylation of optically active propargylic acetate and a Suzuki–Miyaura coupling or CuTC-mediated coupling reaction. The absolute configuration of (+)-gregatin E (5R,5′S) is proposed.

  描述了（+）-凝集素E的第一个全合成和（+）-凝集素B的新的全合成。我们的合成方法的关键特征包括光学活性的乙酸炔丙酯的钯催化环化-甲氧基羰基化和Suzuki-Miyaura偶联或CuTC介导的偶联反应。提出了（+）-聚集蛋白E（5 R，5 'S）的绝对构型。
• Total Syntheses of the Dihydrofuranonecarboxylate Natural Products Gregatin B and E: Gram-Scale Synthesis of (+)-Gregatin B and Unambiguous Assignment of the Stereostructure of (+)-Gregatin E
  作者：Fabian Weber、Reinhard Brückner

  DOI：10.1021/ol5032602

  日期：2014.12.19

  We synthesized the dextrorotatory enantiomers of gregatin B (1.3 g scale) and E, establishing their diene side chains in the last step by Heck coupling with variable iodoolefins. Their counterpart was synthesized in 30% overall yield and with high enantiopurity (97% ee) from benzyl tiglate, beginning with an asymmetric dihydroxylation. The stereostructure of gregatin E followed from HPLC comparisons between the four synthetic stereoisomers of this compound and natural gregatin E, which we isolated from Cadophora gregata.