Reactions of Fluoroalkanes with Mg−Mg Bonds: Scope, sp³C−F/sp²C−F Coupling and Mechanism

sp³C−F Bonds of fluoroalkanes (7 examples; 1°, 2° and 3°) undergo addition to a low-valent Mg−Mg species generating reactive organomagnesium reagents. Further reactions with a series of electrophiles results in a net C−F to C−B, C−Si, C−Sn or C−C bond transformation (11 examples, diversity). The new reactivity has been exploited in an unprecedented one-pot magnesium-mediated coupling of sp³C−F and sp²C−F bonds. Calculations suggest that the sp³C−F bond activation step occurs by frontside nucleophilic attack of the Mg−Mg reagent on the fluoroalkane.