methyl (1R,5S,6S,8R)-10,10-dimethyl-2-oxo-3-oxatricyclo[6.3.0.01,5]undecane-6-carboxylate | 203188-75-4

• 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 (1R,5S,6S,8R)-10,10-dimethyl-2-oxo-3-oxatricyclo[6.3.0.01,5]undecane-6-carboxylate
• CAS: 203188-75-4
• 化学式: C₁₄H₂₀O₄
• 分子量: 252.31
• InChiKey: AFIQQDQNOUAIOM-MAGOMRGPSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2
• 重原子数：
  18
• 可旋转键数：
  2
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.86
• 拓扑面积：
  52.6
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  methyl (1R,5S,6S,8R)-10,10-dimethyl-2-oxo-3-oxatricyclo[6.3.0.01,5]undecane-6-carboxylate 在 正丁基锂 、 二异丁基氢化铝 作用下， 以 四氢呋喃 、 正己烷 为溶剂， 反应 6.25h， 生成 methyl (1R,2S,5S,6S,8R)-2-hydroxy-10,10-dimethyl-3-oxatricyclo[6.3.0.01,5]undecane-6-carboxylate
  参考文献：
  名称：

  Formal Asymmetric Synthesis of Pentalenolactone E and Pentalenolactone F-2. Construction of the Angular Diquinanoid δ-Lactone

  摘要：

  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.

  DOI：

  10.1002/(sici)1099-0690(199802)1998:2<275::aid-ejoc275>3.0.co;2-z
• 作为产物：
  描述：

  methyl (3aS,3bR,6aR,7aS)-5,5-dimethyl-1-oxo-3a,4,6,6a,7,7a-hexahydro-3H-pentaleno[1,2-c]furan-3b-carboxylate 、 原甲酸三甲酯 在 对甲苯磺酸 作用下， 以 甲醇 为溶剂， 反应 3.0h， 以98%的产率得到methyl (1R,5S,6S,8R)-10,10-dimethyl-2-oxo-3-oxatricyclo[6.3.0.01,5]undecane-6-carboxylate
  参考文献：
  名称：

  Formal Asymmetric Synthesis of Pentalenolactone E and Pentalenolactone F-2. Construction of the Angular Diquinanoid δ-Lactone

  摘要：

  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.

  DOI：

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