A theoretical study of the Duff reaction : insights into its selectivity

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 stag...

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Autores principales: Grimblat, Nicolás, Sarotti, Ariel Marcelo, Kaufman, Teodoro Saúl, Simonetti, Sebastián Osvaldo
Formato: article artículo publishedVersion
Lenguaje:Inglés
Publicado: Royal Society of Chemistry 2018
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Acceso en línea:http://hdl.handle.net/2133/10491
http://hdl.handle.net/2133/10491
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Sumario: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.