Transition Metal-Catalyzed Cross-Couplings of Benzylic Sulfone Derivatives

In recent years, the use of organosulfones as a new class of cross-coupling partner in transition-metal catalyzed reactions has undergone significant advancement. In this personal account, our recent investigations into desulfonylative cross-coupling reactions of benzylic sulfone derivatives catalyzed by Pd, Ni, and Cu catalysis is described. Combined with the facile alpha-functionalizations of sulfones, our methods can be used to form valuable multiply-arylated structures such as di-, tri-, and, tetraarylmethanes from readily available substrates. The reactivity of sulfones can be increased by introducing electron-withdrawing substituents such as 3,5-bis(trifluoromethyl)phenyl and trifluoromethyl groups, which enable more challenging cross-coupling reactions. Reactive intermediates including Cu-carbene complexes were identified as key intermediates in sulfone activation, representing new types of C-SO2 bond activation processes. These results indicate sulfones are powerful functional groups, enabling new catalytic desulfonylative transformations.