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Formation and sigmatropic rearrangement of PhCOC(NO2)=CH2 cycloadducts of 1,3-cyclohexadiene: a theoretical study
Journal article   Peer reviewed

Formation and sigmatropic rearrangement of PhCOC(NO2)=CH2 cycloadducts of 1,3-cyclohexadiene: a theoretical study

Hanying Xu, Peter A. Wade and Karl Sohlberg
Tetrahedron, v 66(4), pp 845-851
23 Jan 2010
DOI: https://doi.org/10.1016/j.tet.2009.11.075
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Abstract

Chemistry Chemistry, Organic Physical Sciences Science & Technology
Competing cycloaddition pathways for the reaction of 2-nitro-1-plienyl-2-propen-1-one with 1,3-cyclohexadiene were investigated employing computational methods. A bifurcating pathway was found for formation of nitroketone 3 and nitronic ester 5. A second bifurcating pathway was found for the formation of nitroketone 4 and enol ether 6. Signiatropic rearrangements of two cycloadducts, nitronic ester 5 and enol ether 6, were also studied computationally. The reaction pathways were mapped using the B3-LYP/6-311G(d) method and relative energies for species 3-6 were calculated at the same level. Solution-phase corrections were performed by the PCM method. The calculations for both bifurcating cycloaddition pathways indicate kinetic control with similar rate-determining activation energies. The nitroketone 3 is more stable than nitronic ester 5 by 5.3 kcal/mol and nitroketone 4 is more stable than enol ether 6 by 3.9 kcal/mol, consistent with the observed direction of sigmatropic rearrangement. (C) 2009 Elsevier Ltd. All rights reserved.

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Collaboration types
Domestic collaboration
Web of Science research areas
Chemistry, Organic
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