Per-Ola Norrby (@peonor.bsky.social)

Did you know that simple Pd-phosphines can be photocatalysts? Here, it enables a carbonylative coupling with little excess of CO, perfect for isotope labelling. Great mechanistic study and reaction development by Erik Sundén! doi.org/10.1021/acs....

loading . . .

Mechanistic Study of Photochemical Aminocarbonylation of Alkyl Iodides Catalyzed by a Palladium Catalyst Using Experimental and Computational Methods Aminocarbonylations are versatile reactions amenable to applications in convergent synthesis and isotope labeling. Herein, a mechanistic study of a previously reported visible-light-promoted aminocarbonylation of unactivated alkyl iodides is presented. This study combines in situ spectroscopy, computational chemistry, and organic chemistry techniques. A T1 excited-state promoted ligand dissociation in concert with an atom transfer radical addition was uncovered as a likely first step in the mechanism, instead of the usual three-center oxidative addition. Improvement in the reaction yield was achieved by optimizing the reaction based on mechanistic insights. This took the form of promoting a computationally uncovered cationic carbonylation pathway with the use of bidentate ligands. https://doi.org/10.1021/acs.joc.4c02240