Azocine derivatives were successfully synthesized from O-propargylic oximes by means of a Rh-catalyzed 2,3-rearrangement/heterocyclization cascade reaction. Moreover, the chirality of the substrate was maintained throughout the cascade process to afford the corresponding optically active azocines.

We show that N-alkynylnitrones are efficiently converted to nitrogenous heterobicyclic compounds with a nitrogen atom at the bridgehead position by using a Rh -catalyst. Our mechanistic studies suggest that the reaction proceeds via an allene intermediate, which is generated in situ through Rh -catalyzed isomerization of the alkyne group.

A series of azocine‐1‐oxides (II) is prepared by a Rh‐catalyzed 2,3‐rearrangement/heterocyclization reaction sequence of corresponding O‐propargylic oximes (I).

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