title: Formal Total Synthesis of (±)-Strictamine by [2,3]-Sigmatropic Stevens Rearrangements.
abstract: To date, more than 100 congeners of the akuammiline alkaloid family have been isolated. Their signature structural element is a methanoquinolizidine moiety, a cage-like scaffold structurally related to adamantane. The structural variations of the family members originate from oxidative processes that mostly trigger rearrangements of the methanoquinolizidine motif. The family of the akuammiline alkaloids is best represented by strictamine. It bears the least functionalized carbon skeleton of all family members without lacking the signature structural motifs. Herein, we report the formal synthesis of strictamine through a Stevens [2,3]-sigmatropic rearrangement as a key step and the synthetic pitfalls related with its synthesis.
authors.affiliation: Faculty of Chemistry, University of Konstanz, Universitätsstr. 10, 78457, Konstanz, Germany.|Current address: Department of Medicinal Chemistry, University of Minnesota, 2231 Sixth Street SE, Minneapolis, Minnesota, 55455, USA.
authors.forename: Ruben
authors.initials: R
authors.lastname: Eckermann
authors.affiliation: Faculty of Chemistry, University of Konstanz, Universitätsstr. 10, 78457, Konstanz, Germany.
authors.forename: Michael
authors.initials: M
authors.lastname: Breunig
authors.affiliation: Faculty of Chemistry, University of Konstanz, Universitätsstr. 10, 78457, Konstanz, Germany.
authors.forename: Tanja
authors.initials: T
authors.lastname: Gaich
mesh_terms: D000470:Alkaloids / Q000138:chemical synthesis* / Q000737:chemistry; D000893:Anti-Inflammatory Agents / Q000138:chemical synthesis* / Q000737:chemistry; D029062:Apocynaceae / Q000737:chemistry; D053961:Azabicyclo Compounds / Q000138:chemical synthesis / Q000737:chemistry; D001391:Azo Compounds / Q000138:chemical synthesis / Q000737:chemistry; D061565:Cycloaddition Reaction; D008958:Models, Molecular; D010084:Oxidation-Reduction; D011759:Pyrrolidines / Q000138:chemical synthesis / Q000737:chemistry; D013237:Stereoisomerism; D013882:Thiosemicarbazones / Q000138:chemical synthesis / Q000737:chemistry
chemical_list: D000470:Alkaloids; D000893:Anti-Inflammatory Agents; D053961:Azabicyclo Compounds; D001391:Azo Compounds; D011759:Pyrrolidines; D013882:Thiosemicarbazones; C512188:azomethine; C022062:strictamine; C032519:pyrrolidine
keywords: Stevens rearrangement; [2,3]-sigmatropic rearrangement; alkaloids; diazo compounds; total synthesis