Dalian Institute of Chemical Physics (DICP) of the Chinese Academy of Sciences (CAS) scientists have developed a new strategy for heterogeneous catalytic successive cleavage and functionalization of C–C bonds in alcohols. The study was published in Chem.
The oxidative cleavage and functionalization of C–C bonds in alcohols has emerged as a powerful tool for the conversion of alcohols to a variety of value-added chemicals, given that alcohols can be broadly accessible from both fossil resources and naturally renewable biomass.
Some homogeneous catalytic systems have been well established for the cleavage and functionalization of alcohols. Over-reliance on stoichiometric and environmentally unfriendly oxidants and high loading of precious metal catalysts still limit most of these reaction classes.
Scientists developed a novel and efficient protocol that enables the direct synthesis of amides via heterogeneous manganese oxide catalyzed successive cleavage and amidation of C-C bonds in alcohols with oxygen as an environmentally benign oxidant and ammonia as nitrogen source.
They found that a wide range of primary and secondary alcohols, 1,2-diols and even β-O-4 and β-1 lignin model compounds could undergo C–C bond cleavage smoothly to deliver one- or multiple-carbon shorter amides. A slight modification of the reaction conditions allowed for the cleavage and cyanation of alcohols to access sterically hindered nitriles.
This protocol features good functional-group tolerance, facile scalability, cost-effective and recyclable catalyst. It has been applied to the late-stage amidation and cyanation of bioactive alcohols. This offers an efficient way to generate natural product derivatives for drug discovery and chemical biology.