Lignin is the second most abundant natural polymer. Its use and targeted functionalisation within biomass refinery processes, however, still needs to be further explored and developed. The oxidative functionalisation, and thus valorisation of lignin, is a very promising way to go, since it holds the possibilities to yield highly functionalised, monomeric or oligomeric products that can serve as starting materials for other valorisation processes in the chemical and pharmaceutical industries. Gaining a profound knowledge about the structure of lignin, being able to analyse structural features, and understanding the mechanisms that guide the reactions leading to the oxidative derivatisation, depolymerisation and functionalisation of lignin samples from different renewable sources are key requirements for developing successful valorisation protocols for lignin. In this review, we wish to revisit, and set into context, some important achievements in the field of oxidatively upgrading lignin. We will focus on organometal catalyses (MTO, salen complexes, POMs), biomimetic catalyses (porphyrins), and enzymatic catalyses (laccase, peroxidase) for upgrading lignin and lignin model compounds. Details of mechanistic implications and means of potential manipulations of reaction outcomes are discussed. © 2013 Elsevier B.V. All rights reserved.
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