Asymmetric Conjugate Addition of Phosphine Sulfides to α-Substituted β-Nitroacrylates Using Cinchona Alkaloid Amide Catalysts.

Chiral phosphine-containing amino acids are useful motifs in pharmaceutical compounds. In this study, we developed the asymmetric conjugate addition of phosphine sulfides with α-substituted β-nitroacrylates to synthesize phosphine-containing amino acid precursors with chiral tetrasubstituted carbon centers. This method showed a wide substrate scope, and the obtained products were converted into various chiral compounds.

Photoredox-Catalyzed 1,4-Peroxidation-Sulfonylation of Enynones: A Three-Component Radical Coupling Approach for the Synthesis of Highly Functionalized Allenes.

An Eosin Y-catalyzed visible light-promoted 1,4-peroxidation-sulfonylation of enynones was achieved to give tetrasubstituted allenes. The photoredox catalysis of Eosin Y allowed the concomitant formation of peroxy and sulfonyl radicals, where the preferential peroxy radical addition to the alkene moiety of enynones resulted in the subsequent α-keto radical-sulfonyl radical cross couplings. The developed photoredox catalysis of Eosin Y demonstrates a regioselective 1,4-diradical addition strategy, opening up a new possibility of diradical functionalization of conjugate systems.