title: A theoretical study of the Duff reaction: insights into its selectivity.
abstract: The 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.
authors.affiliation: Instituto de Química Rosario (IQUIR, CONICET-UNR), Facultad de Ciencias Bioquímicas y Farmacéuticas, Universidad Nacional de Rosario, Suipacha 531, Rosario (2000), Argentina. grimblat@iquir-conicet.gov.ar simonetti@iquir-conicet.gov.ar.
authors.forename: Nicolás
authors.initials: N
authors.lastname: Grimblat
authors.affiliation: Instituto de Química Rosario (IQUIR, CONICET-UNR), Facultad de Ciencias Bioquímicas y Farmacéuticas, Universidad Nacional de Rosario, Suipacha 531, Rosario (2000), Argentina. grimblat@iquir-conicet.gov.ar simonetti@iquir-conicet.gov.ar.
authors.forename: Ariel M
authors.initials: AM
authors.lastname: Sarotti
authors.affiliation: Instituto de Química Rosario (IQUIR, CONICET-UNR), Facultad de Ciencias Bioquímicas y Farmacéuticas, Universidad Nacional de Rosario, Suipacha 531, Rosario (2000), Argentina. grimblat@iquir-conicet.gov.ar simonetti@iquir-conicet.gov.ar.
authors.forename: Teodoro S
authors.initials: TS
authors.lastname: Kaufman
authors.affiliation: Instituto de Química Rosario (IQUIR, CONICET-UNR), Facultad de Ciencias Bioquímicas y Farmacéuticas, Universidad Nacional de Rosario, Suipacha 531, Rosario (2000), Argentina. grimblat@iquir-conicet.gov.ar simonetti@iquir-conicet.gov.ar.
authors.forename: Sebastian O
authors.initials: SO
authors.lastname: Simonetti