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Nickel-Catalyzed Esterification of Aliphatic Amides.

ABSTRACT: 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.

SUBMITTER: Hie L

PROVIDER: S-EPMC5161497 | biostudies-literature | 2016 Nov

REPOSITORIES: biostudies-literature

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Nickel-Catalyzed Esterification of Aliphatic Amides.

Hie Liana L Baker Emma L EL Anthony Sarah M SM Desrosiers Jean-Nicolas JN Senanayake Chris C Garg Neil K NK

Angewandte Chemie (International ed. in English) 20161104 48

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 nucleophi ...[more]

PMID: 27813308

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