Reactivity of cyclopropanic δ-oxo-α,β-unsaturated esters towards SmI 2: 3- exo- trig cyclisation versus cyclopropane ring opening

Abstract

trans-(2′,2′-Diphenyl-bicyclopropyl-2-yl)-4,4-dimethyl-5-oxo-pent-2-enoic acid methyl ester 9, undergoes 3- exo- trig cyclisation in the presence of SmI 2 without competitive ring opening of Newcomb's bicyclopropylic probe next to the carbonyl group. From this result, it may be concluded that the absence of ring opening observed earlier in the case of 5-cyclopropyl-4,4-dimethyl-5-oxo-pent-2-enoate 7 is not due to the potentially reversible character of this process. Meanwhile, as deduced from kinetic considerations based on data of the literature, the absence of ring opening does not necessarily mean that formation of ketyl radicals is not involved in the 3- exo- trig cyclisations of δ-oxo-α,β-unsaturated esters. Compounds 7 and 9 cyclise with total syn selectivity, leading ultimately to lactones. This syn selectivity contrasts with that of other alkylic δ-oxo-α,β-unsaturated esters.