methyl 1,2,4,6,6a,7,8,9-octahydro-8,8-dimethyl-2-oxopentaleno<1,6a-c>pyran-5-carboxylate | 83588-27-6

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 内酯类
• 英文名称: methyl 1,2,4,6,6a,7,8,9-octahydro-8,8-dimethyl-2-oxopentaleno<1,6a-c>pyran-5-carboxylate
• 英文别名: methyl (6aS,9aR)-8,8-dimethyl-2-oxo-1,4,6,6a,7,9-hexahydropentaleno[1,6a-c]pyran-5-carboxylate
• CAS: 83588-27-6
• 化学式: C₁₅H₂₀O₄
• 分子量: 264.321
• InChiKey: IIAADXQBBOINKR-PSLIRLAXSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2
• 重原子数：
  19
• 可旋转键数：
  2
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.73
• 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：

  (2R,6aS,9aS)-1,2,4,6,6a,7,8,9-octahydro-5-iodo-2-methoxy-8,8-dimethylpentaleno<1,6a-c>pyran 在 jones reagent 、 nickel carbonyl 、 硫酸 、 sodium methylate 作用下， 反应 74.0h， 生成 methyl 1,2,4,6,6a,7,8,9-octahydro-8,8-dimethyl-2-oxopentaleno<1,6a-c>pyran-5-carboxylate
  参考文献：
  名称：

  An effective approach to stereocontrolled lactone annulation. Application to the total synthesis of pentalenolactone E methyl ester and a partial elaboration of quadrone

  摘要：

  DOI：

  10.1021/ja00388a029

文献信息

• Formal Asymmetric Synthesis of Pentalenolactone E and Pentalenolactone F-2. Construction of the Angular Diquinanoid δ-Lactone
  作者：Eva Herrmann、Hans-Joachim Gais、Bernd Rosenstock、Gerhard Raabe、Hans Jörg Lindner

  DOI：10.1002/(sici)1099-0690(199802)1998:2<275::aid-ejoc275>3.0.co;2-z

  日期：1998.2

  A formal asymmetric synthesis of pentalenolactone E (1b) and pentalenolactone F (1a) has been accomplished. Ozonolysis of the diphenyl-substituted triquinane 3 and Kauffmann methylenation of ketone 5 with WOCl3/2 MeLi yielded the unsubstituted triquinane 9. The crucial rearrangement of the linear triquinanoid lactone 11 to the angular triquinanoid lactone 14a was accomplished using orthoformate and acid in methanol. Subjecting triquinanes 14a/b to the selenoxide method gave triquinene 15. Homologation of gamma-lactone 15 to the angular diquinanoid delta-lactone 2 via a Horner-Wadsworth-Emmons or Peterson reaction of hemiacetals 16a/b was, however, not successful. Chemoselective reduction of 14a afforded hemiacetals 21a/b, reaction of which with the phosphonate salt 17a ultimately led to the ketene dithioacetal 22. The angular intermediates 25a/b were obtained from 22 by reduction to give the linear hemiacetals 24a/b, which rearranged to the dithio ortholactones 25a/b in the presence of acid. Introduction of the double bond and deprotection were accomplished via selenation of 25a/b with N,N-diethylbenzeneselenylamide and treatment of selenides 30a/b with silver nitrate. The unsaturated aldehydes 28 and 29 thus obtained were converted to 2 and 31, respectively, by oxidation with manganese dioxide in the presence of sodium cyanide, methanol and acetic acid. Alkene 2 was isolated by crystallization.
• An effective approach to stereocontrolled lactone annulation. Application to the total synthesis of pentalenolactone E methyl ester and a partial elaboration of quadrone
  作者：Leo A. Paquette、Gary D. Annis、Heinrich Schostarez

  DOI：10.1021/ja00388a029

  日期：1982.12