We report the divergent catalytic transformation of alkene-tethered isoxazol-5­(4H)-ones by using rhodium and cobalt catalysts to afford 2H-pyrroles (with Rh catalyst) and azabicyclic cyclopropanes (with Co catalyst). The rhodium-catalyzed 2H-pyrrole formation involving hydrogen shift is supported by deuterium-labeling experiments. The control experiments in the cobalt-catalyzed reaction indicate that the bicyclic aziridines as the primary product undergo a skeletal rearrangement assisted by metal iodide salts.

anti-Selective iodocyanation and dicyanation of various internal alkynes has been developed by means of a simple copper catalyst system. The selectivity of the products was switched by tuning the reaction conditions. Mechanistic studies have revealed all of the stepwise pathways including diiodide formation, selective monocyanation, and second cyanation processes.

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