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Deprotonative Metalation of Chloro‐ and Bromopyridines Using Amido‐Based Bimetallic Species and Regioselectivity‐Computed CH Acidity Relationships
Author(s) -
Snégaroff Katia,
Nguyen Tan Tai,
Marquise Nada,
Halauko Yury S.,
Harford Philip J.,
Roisnel Thierry,
Matulis Vadim E.,
Ivashkevich Oleg A.,
Chevallier Floris,
Wheatley Andrew E. H.,
Gros Philippe C.,
Mongin Florence
Publication year - 2011
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.201101993
Subject(s) - lithium (medication) , regioselectivity , chemistry , metalation , bimetallic strip , zinc , copper , metal , medicinal chemistry , inorganic chemistry , naphthalene , organic chemistry , catalysis , medicine , endocrinology
A series of chloro‐ and bromopyridines have been deprotometalated by using a range of 2,2,6,6‐tetramethylpiperidino‐based mixed lithium–metal combinations. Whereas lithium–zinc and lithium–cadmium bases afforded different mono‐ and diiodides after subsequent interception with iodine, complete regioselectivities were observed with the corresponding lithium–copper combination, as demonstrated by subsequent trapping with benzoyl chlorides. The obtained selectivities have been discussed in light of the CH acidities of the substrates, determined both in the gas phase and as a solution in THF by using the DFT B3LYP method.