title: Total synthesis of (+/-)-stemodinone via an efficient ring-exchange strategy.
abstract: A total synthesis of (+/-)-stemodinone, a tetracyclic stemodane diterpene, from the known tricyclic methyl olefin 11 is described. The key steps involve an efficient ring-exchange reaction and palladium(0)-catalyzed lactone migration. The ring-exchange strategy for controlling the stereochemistry was based on an initial Diels-Alder reaction to form a new ring followed by cleavage of the original ring. Cleavage of the original ring of the Diels-Alder adduct 9 was achieved by an initial regio- and chemoselective Baeyer-Villiger oxidation followed by the Pd(0)-catalyzed lactone-migration reaction reported by us.
authors.affiliation: Graduate School of Pharmaceutical Sciences, Osaka University, 1-6 Yamadaoka, Suita, Osaka 565-0871, Japan. t-tanaka@phs.osaka-u.ac.jp
authors.forename: T
authors.initials: T
authors.lastname: Tanaka
authors.forename: K
authors.initials: K
authors.lastname: Murakami
authors.forename: A
authors.initials: A
authors.lastname: Kanda
authors.forename: D
authors.initials: D
authors.lastname: Patra
authors.forename: S
authors.initials: S
authors.lastname: Yamamoto
authors.forename: N
authors.initials: N
authors.lastname: Satoh
authors.forename: S W
authors.initials: SW
authors.lastname: Kim
authors.forename: S M
authors.initials: SM
authors.lastname: Rahman
authors.forename: H
authors.initials: H
authors.lastname: Ohno
authors.forename: C
authors.initials: C
authors.lastname: Iwata
mesh_terms: D000998:Antiviral Agents / Q000138:chemical synthesis* / Q000737:chemistry; D016590:Aphidicolin / Q000737:chemistry; D004224:Diterpenes / Q000138:chemical synthesis* / Q000737:chemistry; D010946:Plants, Medicinal / Q000737:chemistry*; D013237:Stereoisomerism
chemical_list: D000998:Antiviral Agents; D004224:Diterpenes; D016590:Aphidicolin; C074341:stemodin; C450163:stemodinone