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Nickel‐Catalyzed Esterification of Aliphatic Amides
Author(s) -
Hie Liana,
Baker Emma L.,
Anthony Sarah M.,
Desrosiers JeanNicolas,
Senanayake Chris,
Garg Neil K.
Publication year - 2016
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.201607856
Subject(s) - chemistry , amide , steric effects , catalysis , nucleophile , bond cleavage , peptide bond , stereocenter , nickel , heteroatom , combinatorial chemistry , organic chemistry , selectivity , enantioselective synthesis , ring (chemistry) , enzyme
Recent studies have demonstrated that amides can be used in nickel‐catalyzed reactions that lead to cleavage of the amide C−N bond, with formation of a C−C or C−heteroatom bond. However, the general scope of these methodologies has been restricted to amides where the carbonyl is directly attached to an arene or heteroarene. We now report the nickel‐catalyzed esterification of amides derived from aliphatic carboxylic acids. The transformation requires only a slight excess of the alcohol nucleophile and is tolerant of heterocycles, substrates with epimerizable stereocenters, and sterically congested coupling partners. Moreover, a series of amide competition experiments establish selectivity principles that will aid future synthetic design. These studies overcome a critical limitation of current Ni‐catalyzed amide couplings and are expected to further stimulate the use of amides as synthetic building blocks in C−N bond cleavage processes.