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Mechanism of Cooperative Catalysis in a Lewis Acid Promoted Nickel-Catalyzed Dual C-H Activation Reaction

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Field Value
 
Title Mechanism of Cooperative Catalysis in a Lewis Acid Promoted Nickel-Catalyzed Dual C-H Activation Reaction
 
Creator ANAND, M
SUNOJ, RB
 
Subject BOND ACTIVATION
ENANTIOSELECTIVE CYANATION
ORGANOMETALLIC CHEMISTRY
ASYMMETRIC CATALYSIS
HETEROCYCLIC CARBENE
TITANIUM CATALYST
FUNCTIONALIZATION
INSERTION
LIGANDS
 
Description The mechanism of cooperativity offered by AlMe3 in a Ni-catalyzed dehydrogenative cycloaddition between substituted formamides and an alkyne is investigated by using DFT(SMDtoluence/M06/6-31G**) methods. The preferred pathway is identified to involve dual C-H activation, with first a higher barrier formyl C(sp(2))-H oxidative insertion followed by benzylic methyl C(sp(3))-H activation. The cooperativity is traced to be of kinetic origin as evidenced by stabilized transition states when AlMe3 is bound to the formyl group, particularly in the oxidative insertion step.
 
Publisher AMER CHEMICAL SOC
 
Date 2014-10-17T05:44:05Z
2014-10-17T05:44:05Z
2012
 
Type Article
 
Identifier ORGANIC LETTERS, 14(17)4584-4587
http://dx.doi.org/10.1021/ol302047c
http://dspace.library.iitb.ac.in/jspui/handle/100/16098
 
Language en