Iron-catalyzed hydrobenzylation: stereoselective synthesis of (–)-eugenial C

Metal-hydride hydrogen atom transfer (MHAT) has emerged as a useful tool to form quaternary carbons from alkenes via hydrofunctionalization. Methods to date that cross-couple alkenes with sp3 partners rely on heterobimetallic catalysis to merge the two cycles. Here we report a monometallic cross-coupling via putative MHAT/SH2 steps that solves a key stereochemical problem in the synthesis of meroterpenoid eugenial C and obviates the need for nickel in these hydrobenzylations generally. The concise synthesis benefits from a conformationally-locked o,o'-disubstituted benzyl bromide and a locally-sourced chiral pool terpene coupling partner.