2003
DOI: 10.1021/ja035729x
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Control of Kinetics and Thermodynamics of [1,5]-Shifts by Aromaticity:  A View through the Prism of Marcus Theory

Abstract: The effects of aromatic stabilization on the rates of [1,5]-hydrogen shifts in a series of carbo- and heterocyclic dihydroaromatic compounds were estimated by B3LYP/6-31G computations. The aromatic stabilization energy of the product is directly translated into increased exothermicity of these reactions. Relative trends for a significant range of endothermic and exothermic [1,5]-shifts with different intrinsic activation energies are reliably described by Marcus theory. The effects of aromaticity or antiaromat… Show more

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Cited by 134 publications
(138 citation statements)
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“…1 In this class of reactions, [1,n] hydrogen shifts have attracted attention from both experimental and computational chemists. Suprafacial migrations are allowed by WoodwardHoffmann orbital symmetry considerations 2 for conjugated pentadienes ( [1,5] shifts), but not for propenes ( [1,3] shifts), or for conjugated heptatrienes ( [1,7] shifts), although the latter have an allowed antarafacial pathway theoretically available to them. Again, these and other pericyclic processes have been discussed in great detail in organic texts 3 , and the extensive secondary literature.…”
Section: Introductionmentioning
confidence: 99%
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“…1 In this class of reactions, [1,n] hydrogen shifts have attracted attention from both experimental and computational chemists. Suprafacial migrations are allowed by WoodwardHoffmann orbital symmetry considerations 2 for conjugated pentadienes ( [1,5] shifts), but not for propenes ( [1,3] shifts), or for conjugated heptatrienes ( [1,7] shifts), although the latter have an allowed antarafacial pathway theoretically available to them. Again, these and other pericyclic processes have been discussed in great detail in organic texts 3 , and the extensive secondary literature.…”
Section: Introductionmentioning
confidence: 99%
“…Again, these and other pericyclic processes have been discussed in great detail in organic texts 3 , and the extensive secondary literature. 4 A particularly useful computational paper by Alabugin and coworkers deals with [1,5] shifts, and contains extensive references to the primary literature. 5 One of several issues discussed there is the presence of aromatic character in the transition states (TSs) of [1,5] hydrogen shifts, a factor increasing kinetic reactivity.…”
Section: Introductionmentioning
confidence: 99%
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