2008/11/26 by Peter Valente, Thomas D. Avery, Dennis K. Taylor +1 · 1 citation
Biochemistry, Genetics and Molecular Biology · Chemistry · #Plant biochemistry and biosynthesis #Synthetic Organic Chemistry Methods #Traditional and Medicinal Uses of Annonaceae
paper · doi:10.1021/jo8020506
openalex publication_date 2008/11/26 · openalex created_date 2025/10/10 · openalex updated_date 2026/06/25
1,4-Disubstituted 2,3-dioxabicyclo[2.2.2]oct-5-enes were dihydroxylated with osmium tetroxide to yield diols anti to the peroxide linkage in a highly selective manner. Reduction of the peroxide bond furnished cyclohexane-1,2,3,4-tetraols with toxocarol relative stereochemistry in excellent yield. This new methodology was employed to synthesize the natural product (1S,2R,3S,4R,5R)-2-methyl-5-(propan-2-yl)cyclohexane-1,2,3,4-tetrol (1) in a short sequence from (R)-alpha-phellandrene. Moreover, during the study of the chemistry of 2,3-dioxabicyclo[2.2.2]octane-5,6-diols a hitherto unknown rearrangement was discovered which has wide applicability for the synthesis of 1,4-dicarbonyls, including optically enriched synthons. A broad range of mechanistic investigations applicable to this rearrangement are also reported.