Treatment of the acetylene-substituted cyclobutanone oxime ether (13) with (Me3Si)3SiH leads, in one pot, to the 5,6-bicyclic enone oxime (14) in 70% yield. It is suggested that the formation of (14) from (13) proceeds by way of a novel double ring expansion-transannulation process involving aminyl radical intermediates (see Scheme 3, below). By contrast, treatment of the cyclobutanone (3a) with Bu3SnH instead leads only to the product (11) of hydrostannylation of the acetylene unit in (3a). Neither (3a) nor (13) produced any of the expected bicyclo[3.3.0]octane products, viz. (5a) and (15), following treatment with silanes or stannanes. When a solution of the vinyl bromide-substituted cyclobutanone oxime (42) was irradiated with a sunlamp in the presence of (Me3Si)3SiH, the main product isolated was the triquinane (45) (38%) resulting from a cascade radical 6-exo-trig cyclization, aminyl radical fragmentation, 5-exo-trig radical transannulation, 5-exo-trig cyclization sequence.
