Multifold Bond Cleavage and Formation between MeOH and Quinoxalines (or Benzothiazoles): Synthesis of Carbaldehyde Dimethyl Acetals

A K(2)S(2)O(8)-mediated direct cross-coupling of quinoxalines (or benzothiazoles) with methanol leading to 2-quinoxalinyl (or 2-benzothiazolyl) carbaldehyde dimethyl acetals has been achieved. 2-Quinoxalinyl carbaldehyde dimethyl acetals were readily converted into 2-quinoxalinyl carbaldehydes in good to excellent yields under acidic conditions. Preliminary mechanistic studies suggest that the reaction proceeds via multifold bond cleavage and formation between methanol and N-heterocycles involving a dioxygen-participated radical process. This method allows for the synthesis of a variety of 2-quinoxalinyl (or 2-benzothiazolyl) carbaldehyde dimethyl acetals directly via cross-coupling of simple N-heterocyclic C-H bond and methanol under aldehyde-, acid-, and transition-metal-free conditions.