Abstract
Pentacoordination of carbon atom in bicyclic organic compounds of the pentalene type was studied by theab initio RHF/6-31G** and MP2(full)/6-31G** methods. It was shown that intramolecularS N 2 reactions with energy barriers within the energy scale of NMR spectroscopy can occur in systems in which a linear orientation of the attacking and leaving groups is realized. The barrier to the intramolecular nucleophilic substitution reaction in 2,3-dihydro-3-formylmethylenefuran is 36.9 (RHF) and 27.7 kcal mol−1 (MP2) and decreases to 16.4 and 19.4 kcal mol−1, respectively, in the case of diprotonation at the O atoms in this system. For model pentalene type compounds containing electron-deficient B atoms in the ring, theab initio calculations predict a further decrease in the barrier height (down to less than 10 kcal mol−1).
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Translated fromIzvestiya Akademii Nauk, Seriya Khimicheskaya, No. 7, pp. 1246–1256, July, 1999.
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Minyaev, R.M., Minkin, V.I. Intramolecular nucleophilicS N 2 substitution at the tetrahedral carbon atom: Anab initio study. Russ Chem Bull 48, 1234–1245 (1999). https://doi.org/10.1007/BF02495282
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DOI: https://doi.org/10.1007/BF02495282