Open AccessDirect Use of Carboxylic Acids in the Photocatalytic Hydroacylation of Styrenes To Generate Dialkyl Ketones
Author(s) -
Jesus I. Martinez Alvarado,
Alyssa B. Ertel,
Andrea Stegner,
Erin E. Stache,
Abigail G. Doyle
Publication year - 2019
Publication title -
organic letters
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.94
H-Index - 239
eISSN - 1523-7060
pISSN - 1523-7052
DOI - 10.1021/acs.orglett.9b03871
Subject(s) - hydroacylation , chemistry , olefin fiber , catalysis , intermolecular force , phosphine , carboxylic acid , photoredox catalysis , photocatalysis , primary (astronomy) , quenching (fluorescence) , organic chemistry , photochemistry , combinatorial chemistry , molecule , aldehyde , fluorescence , physics , astronomy , quantum mechanics
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.