HYDROGEN AND ALLYLATION TRANSFER-REACTIONS IN ACYCLIC FREE-RADICALS

Asymmetric induction involving radicals that are flanked by an ester a nd a stereogenic center bearing a heteroatom has been demonstrated in hydrogen-transfer reactions and allylations. The roles of both structu ral and electronic features in controlling the facial selectivity of t hese radical reactions are best rationalized by a transition state mod el, which resembles the ground state conformation of the radical suppo rted by calculations and ESR studies.