Direct Use of Carboxylic Acids in the Photocatalytic Hydroacylation of Styrenes To Generate Dialkyl Ketones

A general protocol for the hydroacylation of styrenes from aliphatic carboxylic acids is reported. These reactions proceed via β-scission of a phosphoranyl radical that is accessed by photoredox catalysis, followed by addition of the resulting acyl radical to the styrenyl olefin. We show that phosphine tunability is critical for efficient intermolecular coupling due to competitive quenching of the photocatalyst by the olefin. Primary, secondary, and structurally rigid tertiary carboxylic acids all generate valuable unsymmetrical dialkyl ketones

Complementary Stereochemical Outcomes in Proline-Based Self-Regenerations of Stereocenters

Stereoselective alkylations of proline-based amino amides are described, where high levels of either a <i>cis</i> or <i>trans</i> configuration can be attained simply by the choice of the aminal group. Isobutryaldehyde-derived aminals provide the <i>cis</i> configuration, while 1-naphthaldehyde-derived aminals engender the complementary <i>trans</i> configuration

Complementary Stereochemical Outcomes in Proline-Based Self-Regenerations of Stereocenters

Stereoselective alkylations of proline-based amino amides are described, where high levels of either a <i>cis</i> or <i>trans</i> configuration can be attained simply by the choice of the aminal group. Isobutryaldehyde-derived aminals provide the <i>cis</i> configuration, while 1-naphthaldehyde-derived aminals engender the complementary <i>trans</i> configuration