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

Autor(es)

Ali, Sajjad ^[1] ; Milanezi, Henrique ^[1] ; Alves, Tania M. F. ^[1] ; Tormena, Claudio Francisco ^[2] ; Ferreire, Marco A. B. ^[1]

Afiliação do(s) autor(es)

^[1] Fed Univ Sao Carlos UFSCar, Dept Chem, Ctr Excellence Res Sustainable Chem CERSusChem, BR-13565905 Sao Carlos, SP - Brazil

^[2] Univ Estadual Campinas, Inst Chem, BR-13083970 Campinas, SP - Brazil

• Tipo de documento: Artigo Científico
• Fonte: Journal of Organic Chemistry; v. 83, n. 15, p. 7694-7713, AUG 3 2018.
• Citações Web of Science: 2

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: 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
• 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 em Engenharia