Relationship between the electrophilicity and σp Hammett constant in Baeyer–Villiger reactions

Meneses, Lorena; Araya, A.; Pilaquinga, Fernanda; Fuentealba, Patricio

doi:10.1016/j.cplett.2008.05.044

Cited by 21 publications

(22 citation statements)

References 25 publications

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“…In fact, good correlations have been obtained by various groups, between the global electrophilicities of a family of substituted compounds and some constant related with their reactivity. Examples include linear relationships involving global or group electrophilicities in a variety of processes, such as the reactivity of benzhydryl carbocations, 19,22 in the Baeyer-Villiger reaction of aldehydes and ketones, 23 in the hydride affinities of quinones, 24 in the reaction of aryl benzoates with cyanide, 25 or of a,b-unsaturated carbonyl compounds with glutathione. 26 These examples only add to the ones presented in the present work.…”

Section: Discussionmentioning

confidence: 99%

Theoretical substituent electrophilicities

Rezende¹,

Millán²

2011

J. Braz. Chem. Soc.

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Uma equação de tipo Hammett, relacionando as eletrofilicidades teóricas globais e de substituinte, foi derivada para etilenos e ácidos benzóicos substituídos, permitindo o cálculo de constantes eletrofílicas para substituintes s w . As constantes teóricas foram correlacionadas com parâmetros cinéticos ou termodinâmicos para vários processos químicos da literatura. Embora formalmente semelhantes às constantes de Hammett, as constantes eletrofílicas para substituintes são obtidas a partir de postulados teóricos inteiramente distintos. As semelhanças e diferenças entre os dois conjuntos de constantes são discutidas e racionalizadas em termos da definição do poder eletrofílico de uma espécie química.A Hammett-like equation, relating theoretical global and substituent electrophilicities, is derived for substituted ethylenes and benzoic acids, allowing the calculation of electrophilic substituent constants s w . Correlations are given between the theoretical s w constants and kinetic or thermodynamic parameters of various chemical processes from the literature. Though electrophilic substituent constants are formally similar to the Hammett constants, they are derived from entirely different theoretical postulates. The similarities and differences between the two sets of constants are discussed and rationalized in terms of the definition of the electrophilic power of a chemical species.

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Section: Discussionmentioning

confidence: 99%

Theoretical substituent electrophilicities

Rezende¹,

Millán²

2011

J. Braz. Chem. Soc.

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“…The properties of interest are usually response functions with respect to perturbations. The DFT has been successful in the development of global and local reactivity indices [1,2] that have helped significantly in the study of reactivity and selectivity for a wide number of systems [3][4][5][6]. A comprehensive review about this theme has been published [7] together with a specific review about the electrophilicity index [8].…”

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confidence: 98%

“…However, in those works, they do not classify the substrates in order of their reactivity, which is the aim of this work. We show here the first reactivity study for substrates involved in Baeyer-Villiger oxidations by using DFT reactivity index [6].…”

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confidence: 99%

Theoretical studies of reactivity and selectivity in some organic reactions

Meneses

Araya

Pilaquinga

et al. 2010

Int J of Quantum Chemistry

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Some organic reactions with biological or commercial interest have been studied by using reactivity and selectivity indices proposed in the density functional theory. The reactions studied include the electrophilic additions, the BaeyerVilliger oxidations, and the nucleophilic substitutions. For the study, the concepts of electrophilicity and nucleophilicity have been applied as reactivity descriptors. The local hardness has been applied as well as a selectivity descriptor. In this way, the reactivity and selectivity patterns have been studied for the reactants involved in these organic reactions. They have been ranked in theoretical scales which are comparable with experimental scales obtained from kinetic data.

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“…Electrophilicity stems from electron structure and is independent of interventions by nuclei. Domingo et al studied relationship between electron effects of substituents, electrophilicity, and Hammett constant for ethylene [18][19][20][21][22][23][24][25][26][27][28][29][30][31][32][33][34] . Electrophilicity, largest amount of charge transferred by electrons, chemical hardness, and chemical potential were calculated using Equations (1) to (6), where I denotes ionization potential and A is electron affinity.…”

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confidence: 99%