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Cobalt-Catalyzed Stereoselective Synthesis of 2,5-trans-THF Nitrile Derivatives as a Platform for Diversification: Development and Mechanistic Studies

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Autor(es):
Ali, Sajjad ; Milanezi, Henrique ; Alves, Tania M. F. ; Tormena, Claudio Francisco ; Ferreira, Marco A. B.
Número total de Autores: 5
Tipo de documento: Artigo Científico
Fonte: Journal of Organic Chemistry; v. 83, n. 15, p. 20-pg., 2018-08-03.
Resumo

A straightforward protocol integrating a sustainable approach for the synthesis of new 2,S-trans-THF nitrile derivatives enabling an easy diversification of its side chain scaffolds is described. The reaction tolerated different aromatic and alkyl substituents, affording the corresponding 2,5-trans-THFs in high diastereoselectivity. A detailed mechanistic study using DFT calculation reveals details of the ligand-exchange step, suggesting an inner-sphere syn attack to form the 2,5-trans stereochemistry as the most likely pathway, excluding the previous cation radical intermediate. The formation of a Co-C intermediate is suggested on the basis of the homolytic cleavage to give the previously proposed free carbon radical intermediate. (AU)

Processo FAPESP: 14/50249-8 - Green chemistry: sustainable synthetic methods employing benign solvents, safer reagents, and bio-renewable feedstock
Beneficiário:Arlene Gonçalves Corrêa
Modalidade de apoio: Auxílio à Pesquisa - Programa Centros de Pesquisa Aplicada
Processo FAPESP: 13/02311-3 - Novas abordagens na síntese assimétrica de tetraidrofuranos e tetraidropiranos substituídos com potencial aplicação na preparação de moléculas bioativas
Beneficiário:Marco Antonio Barbosa Ferreira
Modalidade de apoio: Auxílio à Pesquisa - Regular
Processo FAPESP: 15/08541-6 - Ressonância magnética nuclear: além da determinação estrutural
Beneficiário:Claudio Francisco Tormena
Modalidade de apoio: Auxílio à Pesquisa - Temático