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Substrate and Positional Selectivity in Electrophilic Substitution Reactions of Pyrrole, Furan, Thiophene, and Selenophene Derivatives

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Chemistry of Heterocyclic Compounds Aims and scope

Abstract

The relative reactivity (substrate selectivity) of five-membered heterocycles on electrophilic substitution (pyrrole >> furan > selenophene > thiophene) and their positional selectivity (furan > selenophene ≥ thiophene > pyrrole) are not consistent. The indicated differences in positional selectivity (α : β ratios) of the parent heterocycles show up essentially in orientation on electrophilic substitution reactions of their derivatives and the corresponding benzannelated systems. It was shown that the positional selectivity was reduced in a sequence corresponding to the change in relative stability of the onium states of the elements (O+ < Se+ ≤ S+ < N+) and reflects the predominant role of the heteroatoms in stabilizing the σ-complexes formed on β-substitution, in which the positive charge is distributed between the heteroatom and one α-carbon atom (in α -isom ers four atoms of the ring participate in delocalization of the charge). This interpretation was confirmed by quantum-chemical calculations carried out by the RHF/6-31G(d), MP2/6-31G(d)//RHF(6)-31G(d), and B3LYP/6-31G(d) ab initio methods.

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Authors and Affiliations

  1. Russian Academy of Sciences, N. D. Zelinsky Institute of Organic Chemistry, Moscow, 119991, Russia

    L. I. Belen'kii & N. D. Chuvylkin

  2. Russian Academy of Sciences, Higher Chemical College, Moscow, 125820, Russia

    I. A. Suslov

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  1. L. I. Belen'kii
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  2. I. A. Suslov
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  3. N. D. Chuvylkin
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Belen'kii, L.I., Suslov, I.A. & Chuvylkin, N.D. Substrate and Positional Selectivity in Electrophilic Substitution Reactions of Pyrrole, Furan, Thiophene, and Selenophene Derivatives. Chemistry of Heterocyclic Compounds 39, 36–48 (2003). https://doi.org/10.1023/A:1023060406534

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