title: Structural Characterization of N-Alkylated Twisted Amides: Consequences for Amide Bond Resonance and N-C Cleavage.
abstract: Herein, we describe the first structural characterization of N-alkylated twisted amides prepared directly by N-alkylation of the corresponding non-planar lactams. This study provides the first experimental evidence that N-alkylation results in a dramatic increase of non-planarity around the amide N-C(O) bond. Moreover, we report a rare example of a molecular wire supported by the same amide C=O-Ag bonds. Reactivity studies demonstrate rapid nucleophilic addition to the N-C(O) moiety of N-alkylated amides, indicating the lack of n(N) to π*(C=O) conjugation. Most crucially, we demonstrate that N-alkylation activates the otherwise unreactive amide bond towards σ N-C cleavage by switchable coordination.
authors.affiliation: Department of Chemistry, Rutgers University, 73 Warren Street, Newark, NJ, 07102, USA.
authors.forename: Feng
authors.initials: F
authors.lastname: Hu
authors.affiliation: Department of Chemistry, Rutgers University, 73 Warren Street, Newark, NJ, 07102, USA.
authors.forename: Roger
authors.initials: R
authors.lastname: Lalancette
authors.affiliation: Department of Chemistry, Rutgers University, 73 Warren Street, Newark, NJ, 07102, USA. michal.szostak@rutgers.edu.
authors.forename: Michal
authors.identifier: http://orcid.org/0000-0002-9650-9690
authors.initials: M
authors.lastname: Szostak
keywords: N-coordination; N−C activation; N−C cleavage; amide bonds; twisted amides