Alkyl aryl ketones were synthesized by the carbonylative cross-coupling reaction of alkyl iodides and arylboronic acids under combined Pd/light conditions. In this reaction, it is likely that an acylpalladium species would be formed via carbonylation of the alkyl radical, which would then undergo transmetalation of an arylboronic acid to give the corresponding acyl(aryl)palladium species, ready to undergo reductive elimination to yield the alkyl aryl ketone.

A carbonylative Mizoroki-Heck reaction using alkyl iodides was achieved with a Pd/photoirradiation system using DBU as a base. In this reaction, alkyl radicals were formed from alkyl iodides via single-electron transfer (SET) and then underwent a sequential addition to CO and alkenes to give β-keto radicals. It is proposed that DBU would abstract a proton α to carbonyl to form radical anions, giving α,β-unsaturated ketones via SET.

Aromatic β-keto esters were synthesized via a carbonylative cross-coupling reaction of alkyl iodides and arylboronic acids in the presence of a catalytic amount of Pd catalyst. A cooperative radical and Pd-catalyzed mechanism is proposed. † Electronic supplementary information (ESI) available. See

Synthesis of Aromatic -Keto Esters via a Carbonylative Suzuki-Miyaura Coupling Reaction of -Iodo Esters with Arylboronic Acids. -A radical mechanism is proposed. -(SUMINO, S.; UI, T.; RYU*, I.; Org. Chem. Front. 2 (2015) 9, 1085-1087, http://dx.