Nitration of α, β-unsaturated esters. Evidence for positive charge build-up adjacent to carbonyl carbon

…, JA Murphy, J Lin, DE Hibbs, MB Hursthouse

Index: Hewlins, Stuart A.; Murphy, John A.; Lin, Jian; Hibbs, David E.; Hursthouse, Michael B. Journal of the Chemical Society - Perkin Transactions 1, 1997 , # 10 p. 1559 - 1570

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Abstract

Reactive intermediates formed in the nitration of certain α, β-unsaturated esters with nitronium tetrafluoroborate exhibit behaviour expected of highly reactive α-carbonyl cations. Three diagnostic reaction types have been observed which indicate the presence of these destabilised cations:(i) trapping in a Ritter reaction,(ii) cyclopropane formation from propyl cations,(iii) Wagner–Meerwein migration of alkyl groups. Semi-empirical calculations of ...