Synthesis and Chemistry of 2,3-Dioxabicyclo[2.2.2]octane-5,6-diols
Date
2009
Authors
Valente, P.
Avery, T.
Taylor, D.
Tiekink, E.
Editors
Advisors
Journal Title
Journal ISSN
Volume Title
Type:
Journal article
Citation
Journal of Organic Chemistry, 2009; 74(1):274-282
Statement of Responsibility
Peter Valente, Thomas D. Avery, Dennis K. Taylor and Edward R. T. Tiekink
Conference Name
Abstract
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.