A computationally guided development of the first efficient protocol to trifluoromethylthiolate aryl and vinyl Csp2–O bonds is presented, showcasing important reactivity requirements for the introduction of potentially reactive functional groups under homogeneous Ni-catalysis.

A novel combination of Fe(TAML)Li and (diacetoxyiodo)benzene for the oxidation of primary and secondary alcohols at 25 °C in acetone is reported. In view of the interesting ability of this system to selectively cleave specific types of C–C bonds of elaborated alcohols, the application of this novel combination to the oxidative cleavage of lignin model molecules was investigated. Considering the numerous supported versions of the oxidant as well as the mild conditions employed, the developed methodology appears to be a promising lignin depolymerization strategy.