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Intrinsic relative nucleophilicity of indoles

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Abstract

The range of applicability of intrinsic (i.e., electronic) relative indices for quantifying electrophilicity and nucleophilicity responses (Chamorro et al. in J Phys Chem A 117(12):2636–2643, 2013) is extended to the characterization of coupling reactions of indoles with benzhydrylium ions and with the strongly electron-deficient heteroarene 4,6-dinitrobenzofuroxan. The reactivity categorization based on experimental kinetic evidence for such a electrophile/nucleophile coupling (Lakhdar et al. in J Org Chem 71(24):9088–9095, 2006) is rationalized in terms of purely electronic descriptors, revealing the polar nucleophilic activation of indole as a key factor associated with the initial rate-determining C–C coupling process.

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Acknowledgments

This work is dedicated to Professor Alberto Vela on the occasion of his 65th birthday. The continuous support from FONDECYT (Chile) through Projects 1140343(E.C.), 1140341(P.P.), and 11130589 (M.D.-N.) is gratefully acknowledged. We also are indebted to the Ministerio de Economía y Competitividad (Spain) Project CTQ2013-45646-P (L.R.D.) and the predoctoral contract from the European Social Fund BES-2014-068258 (M.R.-G.). Prof L.R.D. thanks FONDECYT for the continuous support received through the Cooperación Internacional programs. Finally, E.C. and P.P. thank the Millennium Nucleus Chemical Processes and Catalysis (CPC), Grant Number NC 120082, and the Universidad Andres Bello (UNAB) for support through research Grants DI-806-15/R and DI-793-15/R, respectively. We acknowledged the anonymous reviewers whose constructive criticism has helped us to improve the quality of our presentation.

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  1. Departamento de Ciencias Químicas, Millennium Nucleus Chemical Processes and Catalysis (CPC), Facultad de Ciencias Exactas, Universidad Andres Bello, Avenida República 275, 8370146, Santiago, Chile

    Eduardo Chamorro, Mario Duque-Noreña & Patricia Pérez

  2. Departamento de Química Orgánica, Universidad de Valencia, Dr. Moliner 50, 46100, Burjassot, Valencia, Spain

    Mar Ríos-Gutiérrez & Luis R. Domingo

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  1. Eduardo Chamorro
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  2. Mario Duque-Noreña
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Correspondence to Eduardo Chamorro.

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Published as part of the special collection of articles “Festschrift in honour of A. Vela”.

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Chamorro, E., Duque-Noreña, M., Ríos-Gutiérrez, M. et al. Intrinsic relative nucleophilicity of indoles. Theor Chem Acc 135, 202 (2016). https://doi.org/10.1007/s00214-016-1974-x

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