Structural Characterization of N‐Alkylated Twisted Amides: Consequences for Amide Bond Resonance and N−C Cleavage |
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| Authors: | Dr Feng Hu Prof?Dr Roger Lalancette Prof?Dr Michal Szostak |
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| Affiliation: | Department of Chemistry, Rutgers University, Newark, NJ, USA |
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| 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 nN 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. |
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| Keywords: | amide bonds N− C activation N− C cleavage N-coordination twisted amides |
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