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Hamed EM, Doai H, McLaughlin CK, et al. Regioselective bond cleavage in the dissociative electron transfer to benzyl thiocyanates: the role of radical/ion pair formation. J Am Chem Soc. 2006;128(20):6595-604doi: 10.1021/ja056730u.
Hamed, E. M., Doai, H., McLaughlin, C. K., & Houmam, A. (2006). Regioselective bond cleavage in the dissociative electron transfer to benzyl thiocyanates: the role of radical/ion pair formation. Journal of the American Chemical Society, 128(20), 6595-604. https://doi.org/10.1021/ja056730u
Hamed, Emad M, et al. "Regioselective bond cleavage in the dissociative electron transfer to benzyl thiocyanates: the role of radical/ion pair formation." Journal of the American Chemical Society vol. 128,20 (2006): 6595-604. doi: https://doi.org/10.1021/ja056730u
Hamed EM, Doai H, McLaughlin CK, Houmam A. Regioselective bond cleavage in the dissociative electron transfer to benzyl thiocyanates: the role of radical/ion pair formation. J Am Chem Soc. 2006 May 24;128(20):6595-604. doi: 10.1021/ja056730u. PMID: 16704259.
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J Am Chem Soc. 2006 May 24;128(20):6595-604. doi: 10.1021/ja056730u.

Regioselective bond cleavage in the dissociative electron transfer to benzyl thiocyanates: the role of radical/ion pair formation.

Journal of the American Chemical Society

Emad M Hamed, Hanh Doai, Christopher K McLaughlin, Abdelaziz Houmam

Affiliations

  1. Electrochemical Technology Center, Department of Chemistry, University of Guelph, Guelph, Ontario, Canada N1G 2W1.

PMID: 16704259 DOI: 10.1021/ja056730u

Abstract

Important aspects of the electrochemical reduction of a series of substituted benzyl thiocyanates were investigated. A striking change in the reductive cleavage mechanism as a function of the substituent on the aryl ring of the benzyl thiocyanate was observed, and more importantly, a regioselective bond cleavage was encountered. A reductive alpha-cleavage (CH(2)-S bond) was seen for cyano and nitro-substituted benzyl thiocyanates leading to the formation of the corresponding nitro-substituted dibenzyls. With other substituents (CH(3)O, CH(3), H, Cl, and F), both the alpha (CH(2)-S) and the beta (S-CN) bonds could be cleaved as a result of an electrochemical reduction leading to the formation of the corresponding substituted monosulfides, disulfides, and toluenes. These final products are generated through either a protonation or a nucleophilic reaction of the two-electron reduction-produced anion on the parent molecule. The dissociative electron transfer theory and its extension to the formation/dissociation of radical anions, as well as its extension to the case of strong in-cage interactions between the produced fragments ("sticky" dissociative electron transfer (ET)), along with the theoretical calculation results helped rationalize (i) the observed change in the ET mechanism, (ii) the dissociation of the radical anion intermediates formed during the electrochemical reduction of the nitro-substituted benzyl thiocyanates, and more importantly (iii) the regioselective reductive bond cleavage.

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