Premium
Structural Characterization of N‐Alkylated Twisted Amides: Consequences for Amide Bond Resonance and N−C Cleavage
Author(s) -
Hu Feng,
Lalancette Roger,
Szostak Michal
Publication year - 2016
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.201600919
Subject(s) - alkylation , amide , chemistry , moiety , bond cleavage , cleavage (geology) , planarity testing , stereochemistry , peptide bond , reactivity (psychology) , nucleophile , resonance (particle physics) , crystallography , organic chemistry , catalysis , materials science , medicine , enzyme , alternative medicine , physics , pathology , particle physics , fracture (geology) , composite material
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.