An extensive range of functionalized aliphatic ketones with good functional‐group tolerance has been prepared by a NiI‐promoted coupling of either primary or secondary alkyl iodides with NN2 pincer NiII‐acyl complexes. The latter were easily accessed from the corresponding NiII‐alkyl complexes with stoichiometric CO. This Ni‐mediated carbonylative coupling is adaptable to late‐stage carbon isotope labeling, as illustrated by the preparation of isotopically labelled pharmaceuticals. Preliminary investigations suggest the intermediacy of carbon‐centered radicals.

A palladium-catalyzed carbonylative approach for the direct conversion of (hetero)aryl bromides into their α,α-bis(trifluoromethyl)carbinols is described, and it employs only stoichiometric amounts of carbon monoxide and trifluoromethyltrimethylsilane. In addition, aryl fluorosulfates proved highly compatible with these reaction conditions. The method is tolerant of a diverse set of functional groups, and it is adaptable to late-stage carbon-isotope labeling.

An extensive range of functionalized aliphatic ketones with good functional‐group tolerance has been prepared by a NiI‐promoted coupling of either primary or secondary alkyl iodides with NN2 pincer NiII‐acyl complexes. The latter were easily accessed from the corresponding NiII‐alkyl complexes with stoichiometric CO. This Ni‐mediated carbonylative coupling is adaptable to late‐stage carbon isotope labeling, as illustrated by the preparation of isotopically labelled pharmaceuticals. Preliminary investigations suggest the intermediacy of carbon‐centered radicals.

Ap alladium-catalyzed carbonylative approachf or the direct conversion of (hetero)aryl bromides into their a,abis(trifluoromethyl)carbinols is described, and it employs only stoichiometric amounts of carbon monoxide and trifluoromethyltrimethylsilane.I na ddition, aryl fluorosulfates proved highly compatible with these reaction conditions.T he method is tolerant of ad iverse set of functional groups,a nd it is adaptable to late-stage carbon-isotope labeling. Conflict of interestTr oels Skrydstrup is ac o-owner of SyTracks a/s,w hich commercializes COgen and the two-chamber technology.