The napyradiomycins are an intriguing family of halogenated natural products with activity against several tumor cell lines as well as some of the worst bacterial strains known to humanity, including methicillin-resistant Staphylococcus aureas and vancomycin-resistant strains of Enterococcus faecium. This communication delineates the first asymmetric total synthesis of (-)-napyradiomycin A1 by a strategy that features a two-step total synthesis of flaviolin, the first highly asymmetric halogenation of a simple alkene, and a Johnson-Claisen rearrangement that generates a quaternary carbon next to a glucal-like oxygen.

Room-temperature Ni(0)-catalyzed cross-coupling reactions of aryl arenesulfonates with arylboronic acids are described. The Ni(0) catalyst, derived from Ni(COD)2 and PCy3, proved to be a general one for the Suzuki-Miyaura cross-coupling of a variety of aryl arenesulfonates. The mild reaction condition, the readily availability of the catalyst, and excellent coupling yields make aryl arenesulfonates potentially useful substrates in organic synthesis.

A practical and straightforward synthetic route to construct a variety of 3-CF/CF-containing chromones via photoredox catalysis was developed. This novel protocol features a visible-light-induced radical-triggered tandem cyclization.