Browse by author
Lookup NU author(s): Aaron Campbell, Dr Paul Waddell, Dr Corinne Wills, Dr Roly ArmstrongORCiD
This work is licensed under a Creative Commons Attribution 4.0 International License (CC BY 4.0).
Tertiary N-sulfonyl anilides in which the aromatic ring bears a bulky ortho-substituent typically display robust atropisomerism as a result of slow C–N bond rotation. There is intense interest in such molecules, but methods for their catalytic enantioselective synthesis remain underdeveloped. In this work, we report that N-sulfonyl ynamides, in which the nitrogen atom bears an alkynyl substituent, undergo rapid racemization on the time scale of seconds making them an ideal class of starting materials for dynamic kinetic resolution reactions to access C–N atropisomeric targets. We have shown that these ynamides can be straightforwardly prepared and undergo a wide range of different transformations, including hydration, rearrangement, oxidation, (hetero)annulation, and addition processes. All of these reactions lead to a remarkable enhancement in configurational stability, with the products racemizing 5–12 orders of magnitude more slowly than the corresponding ynamide precursors. This is an ideal scenario to achieve dynamic kinetic resolution, a concept which has been validated by the development of a catalytic asymmetric sulfa-Michael addition reaction of pro-atropisomeric ynamides, which delivers highly enantioenriched C–N atropisomeric enamides in up to 97% yield and 97:3 e.r. Detailed experimental and computational studies were performed to explore the origins of asymmetry in this process, and the utility of the novel products was established through a series of derivatization reactions.
Author(s): Campbell ADG, Waddell PG, Wills C, Ermanis K, Armstrong RJ
Publication type: Article
Publication status: Published
Journal: Journal of the American Chemical Society
Year: 2026
Pages: epub ahead of print
Online publication date: 18/08/2026
Acceptance date: 29/07/2026
Date deposited: 19/08/2026
ISSN (print): 0002-7863
ISSN (electronic): 1520-5126
Publisher: American Chemical Society
URL: https://doi.org/10.1021/jacs.6c11216
DOI: 10.1021/jacs.6c11216
Data Access Statement: Deposition Numbers 2558739–2558749 and 2571509 contain the supplementary crystallographic data for this paper. These data can be obtained free of charge via the joint Cambridge Crystallographic Data Centre (CCDC) and Fachinformationszentrum Karlsruhe Access Structures service.
Altmetrics provided by Altmetric
