methyl 1,2,4,4a,6a,7,8,9-octahydro-8,8-dimethyl-2-oxopentaleno<1,6a-c>pyran-5-carboxylate | 83648-43-5

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 异戊烯醇脂质
• 英文名称: methyl 1,2,4,4a,6a,7,8,9-octahydro-8,8-dimethyl-2-oxopentaleno<1,6a-c>pyran-5-carboxylate
• 英文别名: methyl 1,2,4,4a,6a,7,8,9-octahydro-8,8-dimethyl-2-oxopentaleno[1,6a-c]pyran-5-carboxylate；methyl (4aR,6aS,9aR)-8,8-dimethyl-2-oxo-1,4,4a,6a,7,9-hexahydropentaleno[1,6a-c]pyran-5-carboxylate
• CAS: 83648-43-5
• 化学式: C₁₅H₂₀O₄
• 分子量: 264.321
• InChiKey: AVAFUEPRXLHQPO-VPJDZLOFSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.3
• 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

• 作为反应物：
  描述：

  聚合甲醛 、 methyl 1,2,4,4a,6a,7,8,9-octahydro-8,8-dimethyl-2-oxopentaleno<1,6a-c>pyran-5-carboxylate 生成 pentalenolactone E methyl ester
  参考文献：
  名称：

  （-）-戊烯内酯E甲酯的合成与绝对构型

  摘要：

  从（+）-2-乙氧基羰基-7,7-乙撑二氧双环[3.3.0] octan-3-one 3出发，合成戊二酸内酯E的天然对映体，作为其左旋Me酯1，其通过处理（±）获得- 3与面包酵母。戊烯戊内酯E Me酯的绝对构型如图1所示。

  DOI：

  10.1016/s0040-4020(88)90019-1
• 作为产物：
  描述：

  4,4-二甲基环己酮 在 dirhodium tetraacetate copper(I) chloride 、 chromium(VI) oxide 、 氢氧化钾 、 lithium hydroxide 、 sodium tetrahydroborate 、 对甲苯磺酰叠氮 、 草酰氯 、 2,4,6-三异丙基苯磺酰叠氮化物 、 sodium hydride 、 三乙胺 、 N,N'-二环己基碳二亚胺 作用下， 以 四氢呋喃 、 甲醇 、 二氯甲烷 、 溶剂黄146 为溶剂， 生成 methyl 1,2,4,4a,6a,7,8,9-octahydro-8,8-dimethyl-2-oxopentaleno<1,6a-c>pyran-5-carboxylate
  参考文献：
  名称：

  Intramolecular carbon-hydrogen insertion: synthesis of (.+-.)-pentalenolactone E methyl ester

  摘要：

  DOI：

  10.1021/ja00304a052

文献信息

• Symmetry in retrosynthetic analysis:(±)-pentalenolactone e methyl ester
  作者：Douglass F. Taber、Jonathan L. Schuchardt

  DOI：10.1016/s0040-4020(01)87746-2

  日期：1987.1

  spiroannulation of 4,4-dimethyl cyclohexanone with -(2-iodoethyl)ether, followed by diazo transfer and Wolff rearrangement, gives acid 6. Homologation to the corresponding β-ketoester, followed by diazo transfer and Rh-mediated intramolecular C-H insertion, then gives ester 8. Reduction of 8 followed by dehydration leads to the α,β unsaturated ester, which on exposure to CrO3 in acetic acid is oxidized

  建立了倍半萜类抗生素戊烯戊内酯3的简单途径。因此，将4，4-二甲基环己酮与-（2-碘乙基）醚螺环化，然后进行重氮转移和Wolff重排，得到酸6。同源化为相应的β-酮酸酯，然后进行重氮转移和Rh介导的分子内CH插入，然后得到酯8。还原8，然后脱水，得到α，β不饱和酯，该酯在乙酸中接触CrO 3时，在受阻较小的亚甲基中优先被氧化。然后，α-亚甲基化完成1的合成。
• A total synthesis of pentalenolactone E methyl ester via a [3 + 2] annulation strategy
  作者：Joseph P. Marino、Claudio Silveira、Joao Comasseto、Nicola Petragnani

  DOI：10.1021/jo00227a042

  日期：1987.9
• 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
• Total synthesis of (.+-.)-pentalenolactone E methyl ester
  作者：Leo A. Paquette、Heinrich Schostarez、Gary D. Annis

  DOI：10.1021/ja00411a056

  日期：1981.10