Silver-catalyzed direct selanylation of indoles: synthesis and mechanistic insights
Elise Ane Maluf Rios1, Carla M B Gomes1, Gabriel L Silvério1
1Department of Chemistry, Laboratory of Polymers and Catalysis (LaPoCa), Federal University of Paraná - UFPR P. O. Box 19061 Curitiba PR 81531-990 Brazil danielrampon@ufpr.br.
Abstract:
Herein we describe the Ag(i)-catalyzed direct selanylation of indoles with diorganoyl diselenides. The reaction gave 3-selanylindoles with high regioselectivity and also allowed direct access to 2-selanylindoles when the C3 position of the indole ring was blocked via a process similar to Plancher rearrangement. Experimental analyses and density functional theory calculations were carried out in order to picture the reaction mechanism. Among the pathways considered (via concerted metalation-deprotonation, Ag(iii), radical, and electrophilic aromatic substitution), our findings support a classic electrophilic aromatic substitution via Lewis adducts between Ag(i) and diorganoyl diselenides. The results also afforded new insights into the interactions between Ag(i) and diorganoyl diselenides.
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