title: Deproto-metallation of N-arylated pyrroles and indoles using a mixed lithium-zinc base and regioselectivity-computed CH acidity relationship.
abstract: The synthesis of N-arylated pyrroles and indoles is documented, as well as their functionalization by deprotonative metallation using the base in situ prepared from LiTMP and ZnCl2·TMEDA (1/3 equiv). With N-phenylpyrrole and -indole, the reactions were carried out in hexane containing TMEDA which regioselectively afforded the 2-iodo derivatives after subsequent iodolysis. With pyrroles and indoles bearing N-substituents such as 2-thienyl, 3-pyridyl, 4-methoxyphenyl and 4-bromophenyl, the reactions all took place on the substituent, at the position either adjacent to the heteroatom (S, N) or ortho to the heteroatom-containing substituent (OMe, Br). The CH acidities of the substrates were determined in THF solution using the DFT B3LYP method in order to rationalize the experimental results.
authors.affiliation: Equipe Chimie et Photonique Moléculaires, Institut des Sciences Chimiques de Rennes, UMR 6226, CNRS-Université de Rennes 1, Bâtiment 10A, Case 1003, Campus de Beaulieu, 35042 Rennes, France ; Laboratoire de Synthèse Organique Appliquée, Faculté des Sciences, Université d'Oran 1 Ahmed Ben Bella, BP 1524 El M'Naouer, 31000 Oran, Algeria.
authors.forename: Mohamed Yacine Ameur
authors.initials: MY
authors.lastname: Messaoud
authors.affiliation: Laboratoire de Synthèse Organique Appliquée, Faculté des Sciences, Université d'Oran 1 Ahmed Ben Bella, BP 1524 El M'Naouer, 31000 Oran, Algeria.
authors.forename: Ghenia
authors.initials: G
authors.lastname: Bentabed-Ababsa
authors.affiliation: Equipe Chimie et Photonique Moléculaires, Institut des Sciences Chimiques de Rennes, UMR 6226, CNRS-Université de Rennes 1, Bâtiment 10A, Case 1003, Campus de Beaulieu, 35042 Rennes, France ; Laboratoire de Synthèse Organique Appliquée, Faculté des Sciences, Université d'Oran 1 Ahmed Ben Bella, BP 1524 El M'Naouer, 31000 Oran, Algeria.
authors.forename: Madani
authors.initials: M
authors.lastname: Hedidi
authors.affiliation: Laboratoire de Synthèse Organique Appliquée, Faculté des Sciences, Université d'Oran 1 Ahmed Ben Bella, BP 1524 El M'Naouer, 31000 Oran, Algeria.
authors.forename: Aïcha
authors.initials: A
authors.lastname: Derdour
authors.affiliation: Equipe Chimie et Photonique Moléculaires, Institut des Sciences Chimiques de Rennes, UMR 6226, CNRS-Université de Rennes 1, Bâtiment 10A, Case 1003, Campus de Beaulieu, 35042 Rennes, France.
authors.forename: Floris
authors.initials: F
authors.lastname: Chevallier
authors.affiliation: UNESCO Chair of Belarusian State University, 14 Leningradskaya Str., Minsk, 220030, Belarus.
authors.forename: Yury S
authors.initials: YS
authors.lastname: Halauko
authors.affiliation: UNESCO Chair of Belarusian State University, 14 Leningradskaya Str., Minsk, 220030, Belarus.
authors.forename: Oleg A
authors.initials: OA
authors.lastname: Ivashkevich
authors.affiliation: Research Institute for Physico-Chemical Problems of Belarusian State University, 14 Leningradskaya Str., Minsk, 220030, Belarus.
authors.forename: Vadim E
authors.initials: VE
authors.lastname: Matulis
authors.affiliation: Laboratoire Littoral Environnement et Sociétés, UMRi CNRS 7266, Université de La Rochelle, 17042 La Rochelle, France.
authors.forename: Laurent
authors.initials: L
authors.lastname: Picot
authors.affiliation: Laboratoire Littoral Environnement et Sociétés, UMRi CNRS 7266, Université de La Rochelle, 17042 La Rochelle, France.
authors.forename: Valérie
authors.initials: V
authors.lastname: Thiéry
authors.affiliation: Centre de Diffractométrie X, Institut des Sciences Chimiques de Rennes, UMR 6226, CNRS-Université de Rennes 1, Bâtiment 10B, Campus de Beaulieu, 35042 Rennes, France.
authors.forename: Thierry
authors.initials: T
authors.lastname: Roisnel
authors.affiliation: Centre de Diffractométrie X, Institut des Sciences Chimiques de Rennes, UMR 6226, CNRS-Université de Rennes 1, Bâtiment 10B, Campus de Beaulieu, 35042 Rennes, France.
authors.forename: Vincent
authors.initials: V
authors.lastname: Dorcet
authors.affiliation: Equipe Chimie et Photonique Moléculaires, Institut des Sciences Chimiques de Rennes, UMR 6226, CNRS-Université de Rennes 1, Bâtiment 10A, Case 1003, Campus de Beaulieu, 35042 Rennes, France.
authors.forename: Florence
authors.initials: F
authors.lastname: Mongin
keywords: CH acidity; indoles; iodolysis; mixed lithium–zinc bases; pyrroles