N-allyl ynamides have been found to undergo a novel Pd-catalyzed N-to-C allyl transfer through a Pd-p-allyl-ketenimine complex to form ketenimines in situ. Alternatively, a thermal 3-aza-Claisen rearrangement can furnish the same ketenimine intermediates, which followed by trapping with N and O-nucleophiles results in the de novo synthesis of a-allyl amidines, vinylogous amidines, and imidates. Without an external nucleophile present, an unexpected 1,3-sulfonyl shift can intercept the ketenimine intermediate, allowing access to quaternary nitriles. Similarly, a tandem aza-Claisen�[3,3]-sigmatrophic rearrangement can be used to generate a,b-unsaturated mixed anhydrides with excellent control of the olefin geometry.

Exploration of novel rearrangements of <i>N</i>-allyl ynamides

242nd National Meeting (2011)

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Exploration of novel rearrangements of N-allyl ynamides