Highly selective divergent oxidative dearomatization coupling reactions, in which the chemoselectivity is controlled by catalysts and bases, are reported herein. Three different kinds of polycyclic cyclohexadienones are produced from the same reactants (41 examples, 85-99% yield). Our method marks a novel copper- and palladium-catalyzed C-H oxidative dearomatization of phenolic derivatives.

A novel Et3N-catalyzed domino oxa-Michael/1,6-addition reaction of ortho-hydroxyphenylsubstituted p-QMs with barbiturate-based olefins is achieved under mild conditions. Various new spiro-barbituratechromans were obtained in excellent yields and diastereoselectivities (90–99% yield, >99:1 dr). The structure of the new compound 3a was determined by single crystal X-ray analysis.