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Chiappe C, De Rubertis A, Jaber A, et al. Reactivity of homoallylic substituted adamantylideneadamantanes with bromine. Substituent effects on the stability of the ionic and nonionic intermediates. J Org Chem. 2002;67(20):7066-74doi: 10.1021/jo0203490.
Chiappe, C., De Rubertis, A., Jaber, A., Lenoir, D., Wattenbach, C., & Pomelli, C. S. (2002). Reactivity of homoallylic substituted adamantylideneadamantanes with bromine. Substituent effects on the stability of the ionic and nonionic intermediates. The Journal of organic chemistry, 67(20), 7066-74. https://doi.org/10.1021/jo0203490
Chiappe, Cinzia, et al. "Reactivity of homoallylic substituted adamantylideneadamantanes with bromine. Substituent effects on the stability of the ionic and nonionic intermediates." The Journal of organic chemistry vol. 67,20 (2002): 7066-74. doi: https://doi.org/10.1021/jo0203490
Chiappe C, De Rubertis A, Jaber A, Lenoir D, Wattenbach C, Pomelli CS. Reactivity of homoallylic substituted adamantylideneadamantanes with bromine. Substituent effects on the stability of the ionic and nonionic intermediates. J Org Chem. 2002 Oct 04;67(20):7066-74. doi: 10.1021/jo0203490. PMID: 12354001.
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J Org Chem. 2002 Oct 04;67(20):7066-74. doi: 10.1021/jo0203490.

Reactivity of homoallylic substituted adamantylideneadamantanes with bromine. Substituent effects on the stability of the ionic and nonionic intermediates.

The Journal of organic chemistry

Cinzia Chiappe, Antonietta De Rubertis, Ali Jaber, Dieter Lenoir, Carsten Wattenbach, Christian Silvio Pomelli

Affiliations

  1. Dipartimento di Chimica Bioorganica e Biofarmacia, Università di Pisa, Via Bonanno 33, I-56126 Pisa, Italy. [email protected]

PMID: 12354001 DOI: 10.1021/jo0203490

Abstract

Sterically congested adamantylideneadamantanes (1b-g) (X = Br, Cl, F, OH, OEt, OCOCH(3)), homoallylically substituted with equatorial groups (X), react with bromine in 1,2-dichloroethane to give a stable bromonium ion intermediate or a substitution product depending on the nature of the substituent and on the bromine concentration. The nature of the substituent markedly affects the formation constant of the 1:1 pi-complexes, as well as of the formation constant and reactivity of bromonium ion intermediates. The different reactivity of the ionic intermediates, which depends on the nature of substituents, is attributed to bromonium or bromocarbenium character of the intermediate, with the support of theoretical investigations. Ab initio calculations on 1:1 adamatylideneadamantane-Br(2) complexes (2a-f) show that the substituent affects the stability of these species through electrostatic and dispersion effects. Solvent effects may also contribute to modulate the relative stability of these species.

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