On the 6-Exo Atom Transfer Radical Cyclization Reactions of 3-Butenyl 2-Iodoalkanoates

Bis(tributyltin)-initiated atom transfer cyclization reactions of 3-butenyl iodoalkanoates in the
presence of BF3·OEt2 as the catalyst afforded the 6-exo cyclization products as a mixture of 3,4-cis-
and trans-substituted tetrahydro-2H-pyran-2-ones in 53−71% yield with the major isomers being
the cis ones. Ab initio calculations at the B3LYP/6-31G* level on the transition states of the radical
cyclization and on the cyclized products revealed that the reactions are kinetically controlled and
the transition states for the 6-exo radical cyclization are in boat conformations. Moreover, the cis-oriented transition states are of lower energy than the corresponding trans-oriented ones, which
are in excellent agreement with experimental results.