Deproto-metallation of N-arylated pyrroles and indoles using a mixed lithium–zinc base and regioselectivity-computed CH acidity relationship

Mohamed Yacine Ameur Messaoud 1, 2 Ghenia Bentabed-Ababsa 2 Madani Hedidi 1, 2 Aïcha Derdour 2 Floris Chevallier 1 Yury S. Halauko 3 Oleg A. Ivashkevich 3 Vadim E. Matulis 4 Laurent Picot 5 Valérie Thiéry 5 Thierry Roisnel 1 Vincent Dorcet 1 Florence Mongin 1
1 ISCR - Institut des Sciences Chimiques de Rennes
2 Laboratoire de Synthèse Organique Appliquée
3 UNESCO Chair of Belarusian State University
4 Research Institute for Physico-Chemical Problems
5 LIENSs - LIttoral ENvironnement et Sociétés - UMR 7266
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.
Keywords : iodolysis mixed lithium–zinc bases pyrroles CH acidity indoles
Document type :
Journal articles
Complete list of metadatas

Cited literature [32 references]  Display  Hide  Download
https://hal-univ-rennes1.archives-ouvertes.fr/hal-01248096
Contributor : Florence Mongin <>
Submitted on : Wednesday, December 23, 2015 - 5:32:12 PM
Last modification on : Thursday, December 12, 2019 - 1:51:00 PM

File

bjoc 1860-5397-11-160.pdf
Publisher files allowed on an open archive

Identifiers

Collections

UNIV-RENNES1 | CNRS | SCR-CD | ISCR | ISCR-PRATS | INC-CNRS | UR1-UFR-SPM | ISCR-CORINT | UNIV-ROCHELLE | UNIV-RENNES | INSA-RENNES | INSA-GROUPE

Citation

Mohamed Yacine Ameur Messaoud, Ghenia Bentabed-Ababsa, Madani Hedidi, Aïcha Derdour, Floris Chevallier, et al.. Deproto-metallation of N-arylated pyrroles and indoles using a mixed lithium–zinc base and regioselectivity-computed CH acidity relationship. Beilstein Journal of Organic Chemistry, Beilstein-Institut, 2015, 11, pp.1475-1485. ⟨10.3762/bjoc.11.160⟩. ⟨hal-01248096⟩

Export

BibTeX TEI DC DCterms EndNote

Share

Metrics

Record views

731

Files downloads

154