4 years ago

Unexpected Direct Synthesis of N-Vinyl Amides through Vinyl Azide–Enolate [3+2] Cycloaddition

Unexpected Direct Synthesis of N-Vinyl Amides through Vinyl Azide–Enolate [3+2] Cycloaddition
Margaret A. Brimble, Paul A. Hume, Hans Choi, Harry J. Shirley, Daniel P. Furkert
The unexpected synthesis of industrially important N-vinyl amides directly from aldehydes and α,β-unsaturated N-vinyl amides from esters is reported. This reaction probably proceeds through an initial [3+2] azide–enolate cycloaddition involving a vinyl azide generated in situ. A survey of the reaction scope and preliminary mechanistic findings supported by quantum computational analysis are reported, with implications for the future development of atom-efficient amide synthesis. Intriguingly, this study suggests that (cautious) reevaluation of azidoethene as a synthetic reagent may be warranted. Worth another look: Industrially important N-vinyl amides were synthesized directly from aldehydes/esters and 1-azido-2-iodoethane. Quantum-chemical calculations support the proposed mechanism involving [3+2] cycloaddition of the enolate derived from the aldehyde or ester with a vinyl azide generated in situ (see scheme). The results suggest that azidoethene itself may be worth (cautious) reevaluation as an atom-efficient synthetic reagent.

Publisher URL: http://onlinelibrary.wiley.com/resolve/doi

DOI: 10.1002/anie.201702727

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