Asymmetric synthesis of all eight seven-carbon dipropionate stereotetrads.
Enantiopure cycloheptadienyl sulfones 6 and 7 are diastereoselectively epoxidized to yield epoxyvinyl sulfones 8, 9, 14, and 16 in high yields and diastereomeric ratios. Syn and anti methylation of epoxides 8, 9, 14, and 16 enables access to all eight possible diastereomeric stereotetrads, seven of which are commonly found in polypropionate natural products. Anti methylations of the above epoxides are possible by either the reaction of methyl organometallics promoted by copper(I), or via reaction with trimethylaluminum to yield stereotetrads 11, 12, 22, and 24. Syn methylations are achieved via Lawton SN2' reaction in the case of stereotetrads 10, 15, and 38, while stereotetrad 13 is accessed by an oxidation/reduction alcohol inversion sequence from stereotetrad 11. All stereotetrads were obtained in high diastereomeric ratios and yields, and their relative stereochemistry was confirmed by X-ray crystallography. Oxidative cleavage of the cyclic stereotetrads yields termini-differentiated acyclic heptanyl stereotetrads ready for use in building larger fragments in the course of target syntheses.
El-Awa
Ahmad
A
Department of Chemistry, Purdue University, West Lafayette, Indiana 47907, USA.
du Jourdin
Xavier Mollat
XM
Fuchs
Philip L
PL
D002384:Catalysis; D004852:Epoxy Compounds / Q000138:chemical synthesis; D007202:Indicators and Reagents; D008745:Methylation; D010084:Oxidation-Reduction; D011422:Propionates / Q000138:chemical synthesis / Q000737:chemistry; D013237:Stereoisomerism; D013256:Steroids / Q000138:chemical synthesis / Q000737:chemistry*; D013450:Sulfones / Q000737:chemistry
D004852:Epoxy Compounds; D007202:Indicators and Reagents; D011422:Propionates; D013256:Steroids; D013450:Sulfones