The synthesis of nitrogenous heterocycles via metalloamination/cyclization of hydrazinoalkenes and o-methoxylaminoalkenes is reported. The metalloamination is observed to be facile even in molecules lacking Thorpe-Ingold conformational activation, and both pyrrolidines and piperidines are formed efficiently with excellent diastereoselectivity. The resulting heterocycles possessing a zinc-carbon bond can be efficiently functionalized in-situ resulting in the synchronous formation of N-C bonds and C-C bonds. Recently, ligands have been investigated that show influence on diastereoselectivity and enantioselectivity. For substituted alkenes, vinylcyclopropanes underogo concurrent cyclization and ring opening. Of particular note, both styrenes and ortho-substituted styrenes are well tolerated for metalloamination/cyclization.

Intramolecular metalloaminations of <i>N,N</i>-dimethylhydrazinoalkenes

249th National Meeting (2015)

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Intramolecular metalloaminations of N,N-dimethylhydrazinoalkenes