Research into the oxidation of abietic acid–derived enone with atmospheric oxygen. Issue 4 (3rd February 2020)

• Record Type: Journal Article
• Authors: Masnyk, Marek; Kuśmirek, Damian; Trzybiński, Damian; Frelek, Jadwiga
• Is Part Of: Chirality. Volume 32:Issue 4(2020)
• Page Start: 437
• Page End: 445
• Publication Date: 2020-02-03
• Subjects: abietic acid -- aerobic oxidation -- autooxidation -- enones -- hydroperoxides; Chirality -- Periodicals; Pharmaceutical chemistry -- Periodicals; 541.22
• DOI: 10.1002/chir.23176
• Languages: English
• ISSNs: 0899-0042

Abstract

Abstract: This work presents results of methyl 7‐oxoabiet‐13(14)‐en‐18‐oate (3 ) self‐oxidation with air‐oxygen in the presence of various bases such as triethylamine or sodium t ‐butoxide. While under aerobic conditions, the use of sodium t ‐butoxide as a base results in the formation of four isomeric alcohols, an addition of triethylamine into reaction medium directs the enone 3 oxidation to hydroperoxides. To clarify this base dependence and to obtain more in‐depth information about this reaction additional studies with cyclohexenone as a reference enone have been undertaken. Their results demonstrated the predisposition of abietane hydroperoxides to oxidize α, β‐unsaturated ketones to epoxides in the presence of t ‐butoxide while reducing the hydroperoxide group to hydroxyl. This ability of hydroperoxides to epoxidize conjugated double bonds and confirmed by the present study intermolecular course allowed proposing a plausible mechanism for this reaction. Abstract :