Pentannulation of N-heterocycles by a tandem gold-catalyzed [3,3]-rearrangement/Nazarov reaction of propargyl ester derivatives: a computational study on the crucial role of the nitrogen atom

Beilstein Journal of Organic Chemistry

Giovanna Zanella¹  Enrique Gómez-Bengoa¹  Ernesto G. Occhiato²  Dina Scarpi²  Martina Petrović² 

[1] Departamento de Química Orgánica I, University of the Basque Country, UPV-EHU, Manuel Lardizabal 3, 20018 Donostia, San Sebastián, Basque Country, Spain;Dipartimento di Chimica “U. Schiff”, Università degli Studi di Firenze, Via della Lastruccia 13, 50019 Sesto Fiorentino, Florence, Italy;

关键词: dft calculations;    gold catalysis;    nazarov reaction;    n-heterocycles;   

DOI  :  10.3762/bjoc.16.255

来源: DOAJ

【 摘 要 】

The tandem gold(I)-catalyzed rearrangement/Nazarov reaction of enynyl acetates in which the double bond is embedded in a piperidine ring was computationally and experimentally studied. The theoretical calculations predict that the position of the propargylic acetate substituent has a great impact on the reactivity. In contrast to our previous successful cyclization of the 2-substituted substrates, where the nitrogen favors the formation of the cyclized final product, the substitution at position 3 was computed to have a deleterious effect on the electronic properties of the molecules, increasing the activation barriers of the Nazarov reaction. The sluggish reactivity of 3-substituted piperidines predicted by the calculations was further confirmed by the results obtained with some designed substrates.

【 授权许可】

Unknown