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How bulky ligands control the chemoselectivity of Pd-catalyzed N-arylation of ammonia

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Abstract

Steric bulk has been recognized as a central design principle for supporting ligands in the widely utilized Buchwald–Hartwig amination. In a recent example, it was shown that a Pd-catalyst carrying a phosphine ligand can successfully aminate aryl halides using ammonia as the nitrogen source. Interestingly, the chemoselectivity of this reaction was found to depend on the steric demand of the phosphine ligand. Whereas a sterically less demanding phosphine affords diphenylamine as the major product, it was shown that the amination reaction can be stopped after the first amination to give aniline if a sterically more encumbering phosphine ligand is used. Density functional theory calculations were carried out to examine the relationship between the steric demand of the phosphine ligand and the chemoselectivity. It was found that the key feature that leads to the chemoselectivity is the ability of the phosphine ligand to rotate the biaryl moiety of the ligand away from the Pd-center upon amine addition to release some of the steric crowding from the Pd-coordination site.

Graphical abstract: How bulky ligands control the chemoselectivity of Pd-catalyzed N-arylation of ammonia

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Article information


Submitted
22 Jun 2019
Accepted
01 Dec 2019
First published
12 Dec 2019

This article is Open Access
All publication charges for this article have been paid for by the Royal Society of Chemistry

Chem. Sci., 2020, Advance Article
Article type
Edge Article

How bulky ligands control the chemoselectivity of Pd-catalyzed N-arylation of ammonia

S. Kim, S. Kim and M. Baik, Chem. Sci., 2020, Advance Article , DOI: 10.1039/C9SC03095F

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