Premium
Reinvestigation of the Noncatalyzed Coupling of Aryllithium with Haloarene: A Novel Aromatic Nucleophilic Substitution Pathway
Author(s) -
Becht JeanMichel,
Gissot Arnaud,
Wagner Alain,
Mioskowski Charles
Publication year - 2003
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.200204373
Subject(s) - regioselectivity , chemistry , nucleophilic substitution , yield (engineering) , nucleophile , combinatorial chemistry , nucleophilic aromatic substitution , stereochemistry , organic chemistry , catalysis , materials science , metallurgy
Noncatalyzed coupling reactions of aryllithiums and haloarenes proceed not only through the well‐known aryne route but also, in some cases, through a novel addition–elimination pathway. Indeed, ortho ‐chloro‐ and ortho ‐bromomethoxyarenes lead selectively to the corresponding ortho ‐biaryls through a chelation‐driven aromatic nucleophilic substitution pathway. Contrary to common belief, such noncatalyzed coupling reactions often proceed with high regioselectivity and high yield. These results underline the potency of such simple reactions and open up a straightforward access to a wide range of biaryl structures; this also appears particularly useful for large‐scale and biaryl building‐block syntheses, as only cheap and readily available substrates are involved.