Photocatalytic Generation of π‐Allyltitanium Complexes via Radical Intermediates

The addition of π-allylmetal complexes to carbonyls is the most important route to homoallylic alcohols. This study reports the first photocatalytic generation of π-allyltitanium complexes by a radical strategy. This novel strategy enables the three-component allylation of carbonyls with 1,3-butadiene, providing rapid access to valuable homoallylic alcohols (over 60 examples). The exceptional regio- and diastereoselectivity provided by dual photoredox/Ti catalysis is comparable to that of the Cr-catalyzed Nozaki-Hiyama-Kishi allylation reaction.