Diastereospecific Gold(I)-Catalyzed Cyclization Cascade for the Controlled Preparation of N- and N,O-Heterocycles.

The reaction of oxime-tethered 1,6-enynes with a cationic gold(I) catalyst demonstrates a great potential for the synthesis of a range of heterocycles in a diastereospecific fashion. The control of the configuration of the oxime and the alkene of the enyne moiety is the key to selectively obtain dihydro-1,2-oxazines, isoxazolines or dihydropyrrole-N-oxides as single diastereoisomers. As supported by DFT calculations, these cascade reactions proceed stepwise, by the intramolecular addition of the O or N atom of the oxime onto cyclopropyl gold(I) carbene intermediates. In this study, a rare [3,3]-sigmatropic rearrangement of nitrones is also observed.