A theoretical study of the Duff reaction: insights into its selectivity. Issue 44 (20th October 2016)

• Record Type: Journal Article
• Authors: Grimblat, Nicolás; Sarotti, Ariel M.; Kaufman, Teodoro S.; Simonetti, Sebastian O.
• Is Part Of: Organic & biomolecular chemistry. Volume 14:Issue 44(2016)
• Page Start: 10496
• Page End: 10501
• Publication Date: 2016-10-20
• Subjects: Chemistry, Organic -- Periodicals; Bioorganic chemistry -- Periodicals; Chemistry, Physical organic -- Periodicals; 547
• DOI: 10.1039/c6ob01887d
• Languages: English
• ISSNs: 1477-0520

Abstract

Abstract : The selectivity-determining step of the Duff ortho -formylation was studied using DFT calculations; a hydrogen bond establishes the position where the formylation will take place. 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.