methyl (3aS,3bR,6aR,7aS)-5-methylidene-1-oxo-3a,4,6,6a,7,7a-hexahydro-3H-pentaleno[1,2-c]furan-3b-carboxylate | 203188-69-6

• 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 (3aS,3bR,6aR,7aS)-5-methylidene-1-oxo-3a,4,6,6a,7,7a-hexahydro-3H-pentaleno[1,2-c]furan-3b-carboxylate
• CAS: 203188-69-6
• 化学式: C₁₃H₁₆O₄
• 分子量: 236.268
• InChiKey: AGVIODYECKNLKQ-AVWBDOJWSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.9
• 重原子数：
  17
• 可旋转键数：
  2
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.69
• 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：

  二碘甲烷 、 methyl (3aS,3bR,6aR,7aS)-5-methylidene-1-oxo-3a,4,6,6a,7,7a-hexahydro-3H-pentaleno[1,2-c]furan-3b-carboxylate 在 diethylzinc 作用下， 以 正己烷 、 二氯甲烷 为溶剂， 反应 8.0h， 以84%的产率得到methyl (3'aS-(3'aα,3'bβ,6'aβ,7'aα))-hexahydro-1'-oxospiro[cyclopropane-1,5'-(1'H)-pentaleno[1,2-c]furan]-3'b(4'H)-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,5S,6aR,7aS)-5-hydroxy-1-oxo-5-(trimethylsilylmethyl)-3a,4,6,6a,7,7a-hexahydro-3H-pentaleno[1,2-c]furan-3b-carboxylate 在 氢氟酸 作用下， 以 乙腈 为溶剂， 反应 0.33h， 以99%的产率得到methyl (3aS,3bR,6aR,7aS)-5-methylidene-1-oxo-3a,4,6,6a,7,7a-hexahydro-3H-pentaleno[1,2-c]furan-3b-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

文献信息

• Formal Asymmetric Synthesis of Pentalenolactone E and Pentalenolactone F-1. Retrosynthesis and π-Facial Differentiation in Palladium-Catalyzed and Dipolar [3 + 2]-Cycloaddition Reactions of Bicyclic Alkenes: Evidence for Electrostatic Control of Stereoselectivity
  作者：Bernd Rosenstock、Hans-Joachim Gais、Eva Herrmann、G. Raabe、Paul Binger、Andreas Freund、Petra Wedemann、Carl Krüger、Jörg Lindner

  DOI：10.1002/(sici)1099-0690(199802)1998:2<257::aid-ejoc257>3.0.co;2-z

  日期：1998.2

  in which the hydroxy group occupies the pseudoaxial position, to be the more stable one. According to force-field calculations, the 5E-conformation seems to be stabilized by an intramolecular electrostatic interaction between the hydroxylic oxygen atom and the lactone carbonyl group, corresponding to the initial step of an intermolecular nucleophilic attack at the carbonyl group. The O−C1 distance and

  已成功开发了戊二酸内酯E（2a）和戊二酸内酯F（2b）的不对称合成成功的新策略。此策略涉及的环的组件A 2A和2B通过冰儿型Pd催化[3 + 2] diquinene的-环反应7与二苯基-取代的亚甲基环丙烷18。通过使用猪肝酯酶催化的对映选择性水解作为关键步骤，可从二酯8分8个步骤以对映体纯净状态获得对苯二酚7。1,3-偶极和Pd催化的[3 + 2]-环加成反应以及7的Michael反应的非预期的面部选择性已经观察到。因此，7与CH 2 N 2以98％或更高的立体选择性反应，有利于在凹侧发生反应，并形成了顺式三环烷27。Trost型Pd催化7与11的反应，根据溶剂的极性，比例为1：1.7至1：5.3的全反式三奎烷6和顺式三奎烷12。7与亚甲基环丙烷（13）在甲苯中经Binger型Pd催化的环加成反应，以1：7的比例提供6和12的混合物。在Pd催化的反应中在具有苯基取代的亚甲基环丙烷14a /
• 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.