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An insight into a base-free Michael addition reaction as catalyzed by a bifunctional nickel N-heterocyclic carbene complex using density functional theory studies

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Title An insight into a base-free Michael addition reaction as catalyzed by a bifunctional nickel N-heterocyclic carbene complex using density functional theory studies
 
Creator KATARI, M
RAJARAMAN, G
GHOSH, P
 
Subject POLARIZABLE CONTINUUM MODEL
RING-OPENING POLYMERIZATION
CONJUGATE ADDITION
ASYMMETRIC ORGANOCATALYSIS
ENANTIOSELECTIVE SYNTHESIS
COMPUTATIONAL INSIGHT
GOLD(I) COMPLEXES
MOLECULES
LIGAND
HYDROAMINATION
Nickel
N-Heterocyclic carbene
Michael reaction
Base-free
DFT studies
 
Description A proposed catalytic pathway for a base-free Michael addition reaction mediated by a N/O-functionalized N-heterocyclic carbene (NHC) based bifunctional nickel precatalyst has been probed using density functional theory (DFT) studies. In particular, the base-free Michael addition of a beta-dicarbonyl compound namely, 2-acetyl-cyclopentanone (a) with methyl vinyl ketone (b) as catalyzed by a representative bifunctional nickel precatalyst viz. [1-(Me)-3-N-(methylacetamido) imidazol-2-ylidene](2)Ni (A) has been investigated. The modeling studies reveal that the nucleophilic attack of a metal bound enolate moiety of a 1,3-dicarbonyl adduct species (B) to the approaching activated olefinic substrate, methyl vinyl ketone (b), is the crucial rate-limiting step of the reaction yielding a Michael addition product adduct species (C). Interestingly, the subsequent intramolecular rearrangement of (C) to a different O-bound intermediate (D) exhibit nearly equal activation barrier. (C) 2014 Elsevier B.V. All rights reserved.
 
Publisher ELSEVIER SCIENCE SA
 
Date 2016-01-15T04:19:26Z
2016-01-15T04:19:26Z
2015
 
Type Article
 
Identifier JOURNAL OF ORGANOMETALLIC CHEMISTRY, 775,109-116
0022-328X
1872-8561
http://dx.doi.org/10.1016/j.jorganchem.2014.02.012
http://dspace.library.iitb.ac.in/jspui/handle/100/17740
 
Language en