Nickel-Catalyzed N‑Arylation of Sulfinamides: A Comparative Study versus Analogous Sulfonamide Cross-Couplings

Despite recent progress regarding the metal-catalyzed C–N cross-coupling of (hetero)­aryl (pseudo)­halides with NH substrates, such transformations involving sulfinamide nucleophiles are underdeveloped. Herein we report on Ni-catalyzed C–N cross-couplings of this type, employing primarily tert-butan...

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Bibliographic Details
Published in:Organometallics 2023-07, Vol.42 (14), p.1704-1710
Main Authors: Simon, Connor M., Robertson, Katherine N., DeRoy, Patrick L., Yadav, Arun A., Johnson, Erin R., Stradiotto, Mark
Format: Article
Language:English
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Summary:Despite recent progress regarding the metal-catalyzed C–N cross-coupling of (hetero)­aryl (pseudo)­halides with NH substrates, such transformations involving sulfinamide nucleophiles are underdeveloped. Herein we report on Ni-catalyzed C–N cross-couplings of this type, employing primarily tert-butanesulfinamide (i.e., Ellman’s sulfinamide) as a test nucleophile. Inexpensive and abundant (hetero)­aryl chlorides proved to be suitable reaction partners in such reactions when using (L)­Ni­(o-tol)Cl (L = CyPAd-DalPhos or PhPAd-DalPhos) precatalysts. We also present results of an experimental and computational study focusing on C–N reductive elimination involving newly prepared and isolated sulfinamido (L)­Ni­(o-tol)­(NHS­(O)tBu) complexes, in which deprotonation leading to the formation of the putative anionic nitrene species [(L)­Ni­(o-tol)­(NS­(O)tBu)]− represents the preferred pathway for C–N reductive elimination, in keeping with our past study of related sulfonamido complexes.
ISSN:0276-7333
1520-6041
DOI:10.1021/acs.organomet.2c00545