Abstract Treatment of different types of alcohols with tetrahydrofuran (THF) in the presence of VCl 3 and CCl 4 smoothly afforded the corresponding THF-based acetals in excellent yields. The reaction is fast at room temperature, and several functional groups are tolerated, with no racemization being observed. A radical mechanism, based on Cl 3 C. as the active species, is proposed for this novel kind of transformation, which complements the classical ...