Palladium-catalyzed allylic substitution between C-based nucleophiles and 6-azabicyclo[3.1.0]-hex-3-en-2-oxy derivatives: A new selectivity paradigm

Oliveira, João; Kiala, Gredy; Siopa, Filipa; Bernard, Aurélie; Gontard, Geoffrey; Oble, Julie; Afonso, Carlos; Poli, Giovanni

http://hdl.handle.net/10451/59203

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Resumo(s)

The reaction between α-hydroxy-(or α-acetoxy) cyclopenten-aziridines (6-azabicyclo[3.1.0]hex-3-en-2-ols or acetates) and C-based nucleophiles in the presence of Pd(0)-catalysis was investigated. In all the cases studied, the reaction was totally regio- and diastereo-selective, affording a single adduct in moderate to good yields. Specifically, attack of the nucleophile at position 3 of the cyclopentene moiety, anti to the vicinal oxy group, with vinylogous ring opening of the aziridine ring, was observed. When the carbon acid is a very acidic methylene (pKa (DMSO) ≤ 7.3), the resulting adduct is a zwitterion, resulting from an intramolecular proton transfer between the amino group and the carbon acid moiety taking place after the C–C bond formation. A plausible mechanism for this transformation is put forward.

Palavras-chave

Palladium catalysis Bicyclic aziridine Tsuji-trost reaction

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http://hdl.handle.net/10451/59203

Citação

Oliveira JAC, Kiala G, Siopa F, Bernard A, Gontard G, Oble J, et al. Palladium-catalyzed allylic substitution between C-based nucleophiles and 6-azabicyclo[3.1.0]-hex-3-en-2-oxy derivatives: A new selectivity paradigm. Tetrahedron [Internet]. 18 de dezembro de 2020;76(51):131182. Disponível em: https://www.sciencedirect.com/science/article/pii/S0040402020303173