The paper by Vladimir Grushin et al. deals with a highly efficient process for Azidocarbonylation of iodoarenes with CO and NaN3, a novel Heck-type carbonylation reaction. The reaction, catalyzed by Xantphos-Pd, occurs in an organic solvent–H2O biphasic system to furnish aroyl azides under vey mild conditions (room temperature, 1 atm) and exhibits high functional group tolerance. The catalyst loading has been lowered to 0.2% without any losses in selectivity at nearly 100% conversion to synthesize a series of aroyl azides in 80–90% isolated yield on a gram scale. Furthermore, the ArCON3 product can be used without isolation for further transformations in situ. The reaction mechanism has also been studied in detail.
The Challenge of Palladium-Catalyzed Aromatic Azidocarbonylation: From Mechanistic and Catalyst Deactivation Studies to a Highly Efficient Process
Fedor M. Miloserdov, Claire L. McMullin, Marta Marti´nez Belmonte, Jordi Benet-Buchholz, Vladimir I. Bakhmutov, Stuart A. Macgregor, and Vladimir V. Grushin
2014, 33 (3), pp 736–752
This paper is one of the articles on the most read articles list in Organometallics.