2018-02-022018-02-022016-10-071477-0520http://hdl.handle.net/2133/10491The Duff reaction is one of the most employed methods for the ortho-formylation of phenols; however, not much is truly known about its mechanism. Using DFT calculations, we disclose the first theoretical study regarding the selectivity-determining step of the reaction. We have found that this stage is governed by a hydrogen bond, that gives rise to a cyclohexa-2,4-dienone intermediate and establishes the position where the formylation will take place. These findings were evaluated by analysis of the reaction outcome of several non-symmetrically substituted phenols.application/pdf10496-10501engopenAccessDuff ReactionOrtho-formylation of PhenolsDFT CalculationsHydrogen BondNon-symmetrically Substituted PhenolsarticleGrimblat, NicolásSarotti, Ariel MarceloKaufman, Teodoro SaúlSimonetti, Sebastián OsvaldoRoyal Society of ChemistryUniversidad Nacional de Rosario