Radical cascade cyclizations of unsaturated epoxy­nitriles induced by titanocene chloride proceed in good yields and with excellent diastereoselectivities. From three to seven stereocenters were created by the reaction and a single isomeric product was obtained from most of the substrates examined. The relative configuration of the products is consistent with cyclization occurring via a chair-like transition state. The termination of the radical cascade reaction by 4-exo, 5-exo or 6-exo cyclization onto nitrile is remarkable.

The reaction of a series of 2,3‐epoxy alcohols and the corresponding formates, acetates, and benzoates promoted by Cp₂TiCl has been studied. The different outcome of the reaction of epoxy derivatives has been rationalized in terms of mechanistically biased processes. After homolytic oxirane cleavage, four main types of reaction were found: dehydroxylation, decarboxylation, dehydrogenation, and deoxygenation. The reaction products varied according to the substitution pattern. The radical nature of these eliminations is demonstrated.