Synthesis and chemistry of 2,3-dioxabicyclo[2.2.2]octane-5,6-diols.
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.
Valente
Peter
P
Department of Chemistry, The University of Adelaide, South Australia 5005, Australia.
Avery
Thomas D
TD
Taylor
Dennis K
DK
Tiekink
Edward R T
ER
D019086:Bridged Bicyclo Compounds, Heterocyclic / Q000138:chemical synthesis* / Q000737:chemistry*; D015394:Molecular Structure; D000442:Octanols / Q000138:chemical synthesis* / Q000737:chemistry*; D013237:Stereoisomerism
D019086:Bridged Bicyclo Compounds, Heterocyclic; D000442:Octanols