Boronic acid/Bronsted acid co-catalyst systems for the synthesis of 2H-chromenes from phenols and alpha,beta-unsaturated carbonyls

Protocols for the synthesis of substituted 2H-chromenes from [small alpha],[small beta]-unsaturated carbonyls and phenols are described. Optimal combinations of arylboronic acids and Bronsted acids have been identified, such that both can be employed in catalytic quantities to accelerate these condensations. The method has been used to synthesize a variety of substituted 2H-chromenes, as well as photochromic naphthopyrans. The use of pentafluorophenylboronic acid and diphenylphosphinic acid enabled an expansion of the electrophile scope to include [small alpha],[small beta]-unsaturated ketones. Hall's 'phase-switching' of boronic acids has been exploited to achieve the separation of the two co-catalysts from unpurified reaction mixtures by a simple liquid-liquid extraction.