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The mechanism of catalytic methylation of 2-phenylpyridine using di-tert-butyl peroxide

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Title The mechanism of catalytic methylation of 2-phenylpyridine using di-tert-butyl peroxide
 
Creator SHARMA, AK
ROY, D
SUNOJ, RB
 
Subject C-H BOND
CROSS-COUPLING REACTIONS
GRIGNARD-REAGENTS
CARBON-CARBON
ALKYL-HALIDES
COMPUTATIONAL PERSPECTIVE
REDUCTIVE ELIMINATION
PALLADIUM CATALYSIS
ARYL ACYLPEROXIDES
ORGANIC-SYNTHESIS
 
Description The mechanism of palladium chloride-catalyzed direct methylation of arenes with peroxides is elucidated by using the energetics computed at the M06 density functional theory. The introduction of a methyl group by tert-butyl peroxides at the ortho-position of a prototypical 2-phenyl pyridine, a commonly used substrate in directed C-H functionalization reactions, is examined in detail by identifying the key intermediates and transition states involved in the reaction sequence. Different possibilities that differ in terms of the site of catalyst coordination with the substrate and the ensuing mechanism are presented. The important mechanistic events involved are (a) an oxidative or a homolytic cleavage of the peroxide O-O bond, (b) C-H bond activation, (c) C-C bond activation, and (d) reductive elimination involving methyl transfer to the aromatic ring. We have examined both radical and non-radical pathways. In the non-radical pathway, the lowest energy pathway involves C-H bond activation prior to the coordination of the peroxide to palladium, which is subsequently followed by the O-O bond cleavage of the peroxide and the C-C bond activation. Reductive elimination in the resulting intermediate leads to the vital C-C bond formation between methyl and aryl carbon atoms. In the non-radical pathway, the C-C bond activation is higher in energy and has been identified as the rate-limiting step of this reaction. In the radical pathway, however, the activation barrier for the C-C bond cleavage is lower than for the peroxide O-O bond cleavage. A combination of a radical pathway up to the formation of a palladium methyl intermediate and a subsequent non-radical pathway has been identified as the most favored pathway for the title reaction. The predicted mechanism is in good agreement with the experimental observations on PdCl2 catalyzed methylation of 2-phenyl pyridine using tert-butyl peroxide.
 
Publisher ROYAL SOC CHEMISTRY
 
Date 2014-12-28T12:17:42Z
2014-12-28T12:17:42Z
2014
 
Type Article
 
Identifier DALTON TRANSACTIONS, 43(26)10183-10201
1477-9226
1477-9234
http://dx.doi.org/10.1039/c4dt00250d
http://dspace.library.iitb.ac.in/jspui/handle/100/16482
 
Language English