Autoxidation of salvinorin A under basic conditions.
[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.
Munro
Thomas A
TA
School of Chemistry, Bio21 Molecular Science and Biotechnology Institute, The University of Melbourne, Victoria, 3010, Australia.
Goetchius
Glenn W
GW
Roth
Bryan L
BL
Vortherms
Timothy A
TA
Rizzacasa
Mark A
MA
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
D004224:Diterpenes; D045785:Diterpenes, Clerodane; D006878:Hydroxides; D017680:Potassium Compounds; C090499:salvinorin A; C029943:potassium hydroxide; D000432:Methanol