title: Autoxidation of salvinorin A under basic conditions.
abstract: [reaction: see text] Treatment of salvinorin A (1a) with KOH in MeOH gave the enedione 3, for which the dienone structure 7 was recently proposed. Also isolated, after methylation, were the secotriesters 4a-c. A mechanism for this unusual series of autoxidations is proposed. Surprisingly, 4a showed weak affinity at the kappa-opioid receptor. Divinatorins A-C (2a-c) showed no affinity at opioid receptors. Attempted reduction of 3 to a novel salvinorin diol (9d) was unsuccessful, but careful deacetylation of salvinorin C (9a) provided a viable route to this compound. A general method for identifying salvinorin 8-epimers by TLC is also presented.
authors.affiliation: School of Chemistry, Bio21 Molecular Science and Biotechnology Institute, The University of Melbourne, Victoria, 3010, Australia.
authors.forename: Thomas A
authors.initials: TA
authors.lastname: Munro
authors.forename: Glenn W
authors.initials: GW
authors.lastname: Goetchius
authors.forename: Bryan L
authors.initials: BL
authors.lastname: Roth
authors.forename: Timothy A
authors.initials: TA
authors.lastname: Vortherms
authors.forename: Mark A
authors.initials: MA
authors.lastname: Rizzacasa
mesh_terms: D004224:Diterpenes / Q000138:chemical synthesis / Q000737:chemistry*; D045785:Diterpenes, Clerodane; D006878:Hydroxides / Q000737:chemistry; D000432:Methanol / Q000737:chemistry; D008968:Molecular Conformation; D010084:Oxidation-Reduction; D017680:Potassium Compounds / Q000737:chemistry; D013237:Stereoisomerism
chemical_list: D004224:Diterpenes; D045785:Diterpenes, Clerodane; D006878:Hydroxides; D017680:Potassium Compounds; C090499:salvinorin A; C029943:potassium hydroxide; D000432:Methanol