Ti-Mediated Efficient Reductive Dehalogenation of Carbon-Halogen Bonds

A mild and efficient methodology for the reductive dehalogenation of carbon–halogen bonds in both activated (allylic or benzylic) and non‐activated halides with excess TiIII is thoroughly described. A detailed computational and experimental study corroborates that the reaction occurs via the allyl(benzyl) radical and allyl(benzyl)‐Ti, which is protonated by a Brønsted acid, and proceeds regioselectively in the case of allylic derivatives. This synthetic method is compatible with a wide range of functional groups and reaction conditions, and thus presents a mild process for reductive dehalogenation in the field of organic synthesis. Alternative to dehalogenation: A mild and efficient methodology for the reductive dehalogenation of carbon–halogen bonds with excess TiIII is described. Detailed computational and experimental studies corroborate the reaction mechanism. This approach is an interesting alternative to dehalogenation reactions mainly for its high compatibility with several functional groups and chemoselectivity.