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. 2023 Jan 4;13(2):914-925.
doi: 10.1039/d2ra06813c. eCollection 2023 Jan 3.

Silver-catalyzed direct selanylation of indoles: synthesis and mechanistic insights

Elise Ane Maluf Rios  1 , Carla M B Gomes  1 , Gabriel L Silvério  1 , Eduardo Q Luz  1 , Sher Ali  2 , Caroline da Ros Montes D'Oca  1 , Breidi Albach  3 , Renan B Campos  4 , Daniel S Rampon  1
Affiliations

Silver-catalyzed direct selanylation of indoles: synthesis and mechanistic insights

Elise Ane Maluf Rios et al. RSC Adv. .

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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Conflict of interest statement

There are no conflicts to declare.

Figures

Fig. 1
Fig. 1. Biologically relevant selenium or sulfur-functionalized indoles.
Scheme 1
Scheme 1. Control experiments for mechanistic studies.
Fig. 2
Fig. 2. Potential energy surface (PES) of the CMD mechanism (i) proposed for the formation of 3a obtained using M062X functional combined with LANL2DZ (for Ag atom) and 6-311++G(d,p) (for additional atoms). Atom color: S-yellow, O-red, Se-orange, N-blue, C-gray, and H-white.
Fig. 3
Fig. 3. Potential energy surface (PES) of the electrophilic substitution mechanism (ii) proposed for the formation of 3a obtained using M062X functional combined with LANL2DZ (for Ag atom) and 6-311++G(d,p) (for additional atoms).
Scheme 2
Scheme 2. Full catalytic cycle.
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