Issue 10, 2017

Origins of high catalyst loading in copper(i)-catalysed Ullmann–Goldberg C–N coupling reactions


A mechanistic investigation of Ullmann–Goldberg reactions using soluble and partially soluble bases led to the identification of various pathways for catalyst deactivation through (i) product inhibition with amine products, (ii) by-product inhibition with inorganic halide salts, and (iii) ligand exchange by soluble carboxylate bases. The reactions using partially soluble inorganic bases showed variable induction periods, which are responsible for the reproducibility issues in these reactions. Surprisingly, more finely milled Cs2CO3 resulted in a longer induction period due to the higher concentration of the deprotonated amine/amide, leading to suppressed catalytic activity. These results have significant implications on future ligand development for the Ullmann–Goldberg reaction and on the solid form of the inorganic base as an important variable with mechanistic ramifications in many catalytic reactions.

Graphical abstract: Origins of high catalyst loading in copper(i)-catalysed Ullmann–Goldberg C–N coupling reactions

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Article type
Edge Article
28 Jun 2017
29 Aug 2017
First published
29 Aug 2017
This article is Open Access

All publication charges for this article have been paid for by the Royal Society of Chemistry
Creative Commons BY license

Chem. Sci., 2017,8, 7203-7210

Origins of high catalyst loading in copper(I)-catalysed Ullmann–Goldberg C–N coupling reactions

G. J. Sherborne, S. Adomeit, R. Menzel, J. Rabeah, A. Brückner, M. R. Fielding, C. E. Willans and B. N. Nguyen, Chem. Sci., 2017, 8, 7203 DOI: 10.1039/C7SC02859H

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