SmI 2 -Mediated 4- Exo -Trig Cyclization of Trifluoromethyl Alkenyl Aldehydes

A SmI2-promoted 4-exo-trig cyclization of trifluoromethylated alkenyl aldehydes has been developed, providing direct access to trifluoromethylcyclobutanols bearing three contiguous stereocenters in promising yields with excellent regioselectivity and diastereoselectivity. Experiments and DFT calculations demonstrate that the fluorine effect plays a crucial role in directing the addition of a ketyl radical to the sterically encumbered alkene carbon, thereby enabling this unusual 4-exo-trig radical cyclization.