Ethanol → Dimethyldioxirane

Participants

Reaction Steps

Donnelly and co-workers (Donnelly, D. M. X.; Fitzpatrick, B. M.; Ryan, S. M.; Finet, J.-P. J. Chem. Soc., Perkin Trans. I 1994, 1794-1801) synthesized the biflavonoids (46) and (47) via arylation of a 3-phenylsulfanylflavanone (48) with an 8-triacetoxyplumbylflavan derivative (49) (2:1 mixture of cis and trans). The dioxolane ring, of the intermediate (50) was cleaved during acid workup. Desulfurization of the intermediate (50) with nickel boride (NaBH4/H2O, NiCl26H2O/EtOH) yielded a chalcone (51) (in a 1.1:1 ratio of E/Z) that was cyclised with anhydrous sodium acetate in refluxing ethanol to the 3,8-biflavanone (46) in 73% yield (only the 2,3-trans isomer was isolated from a mixture of diastereoisomers with an α/β ratio of 1.4:1). Oxidation of (46) with dimethyldioxirane in acetone yielded (47) in 47% yield (Scheme 3). The end products are however not optically active and constitute a racemic mixture.

Provenance & Evidence