# Mechanistic Study of Photochemical Aminocarbonylation of Alkyl Iodides Catalyzed by a Palladium Catalyst Using Experimental and Computational Methods

## TL;DR

This paper investigates how a palladium catalyst works in a chemical reaction under visible light, revealing a new mechanism and improving reaction efficiency.

## Contribution

The study reveals a novel mechanism involving T1 excited-state ligand dissociation and atom transfer radical addition in aminocarbonylation reactions.

## Key findings

- A T1 excited-state promoted ligand dissociation and atom transfer radical addition is likely the first step in the reaction mechanism.
- Using bidentate ligands improved reaction yields by promoting a cationic carbonylation pathway identified through computational analysis.

## Abstract

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.