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

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 re...

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Published in:Beilstein journal of organic chemistry 2015-08, Vol.11 (1), p.1475-1485
Main Authors: Messaoud, Mohamed Yacine Ameur, Bentabed-Ababsa, Ghenia, Hedidi, Madani, Derdour, Aïcha, Chevallier, Floris, Halauko, Yury S, Ivashkevich, Oleg A, Matulis, Vadim E, Picot, Laurent, Thiéry, Valérie, Roisnel, Thierry, Dorcet, Vincent, Mongin, Florence
Format: Article
Language:English
Subjects:
CH acidity
Chemical Sciences
Chemistry
Full Research Paper
indoles
iodolysis
mixed lithium–zinc bases
pyrroles
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Summary: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.
ISSN:1860-5397
1860-5397
DOI:10.3762/bjoc.11.160