Gallou, Fabrice and Plummer, Scott (2024) Buchwald-Hartwig Aminations of Aryl Halides Using Nitroaromatics as Coupling Partners: Overcoming Hydrodehalogenation Pathway in Water. ACS Catalysis, 14 (6). pp. 4099-4107.

Abstract

An aqueous micellar strategy is developed for the C–N cross-coupling of nitroarenes with aryl halides. The reaction pathway in-cludes the domino aminations of in-situ generated amines from nitroaromatics with aryl halides achieved by overcoming unwanted hydrodehalogenation. A bimetallic palladium (Pd)-copper (Cu) nanocatalyst design achieves the desired reactivity by promoting the amination pathway assisted by Cu-hydride formation and suppressing Pd-hydride-mediated hydrodehalogenation. The nano-catalyst was characterized by 31P and 1H nuclear magnetic resonance and X-ray absorption spectroscopies to understand metal-ligand and metal-metal interactions, respectively. High-resolution transmission electron microscopy was performed to obtain the particle size, shape, distribution, and morphology. X-ray photoelectron spectroscopic studies confirmed the oxidation states of Cu and Pd. Control experiments revealed the significance of amphiphile PS-750-M and each component of the nanocatalyst on the desired coupling. This aqueous strategy applies to many substrates and exhibits excellent functional and protecting group tolerance. The scalability of this methodology is demonstrated on a gram-scale reaction. This approach represents greener and step-economic ways to access arylamines.

Item Type:	Article
Date Deposited:	28 May 2024 00:46
Last Modified:	28 May 2024 00:46
URI:	https://oak.novartis.com/id/eprint/51648