Application of FeCl₃/Diorganyl Diselenides to Cyclization of o-Alkynyl Anilines: Synthesis of 3-Organoselenyl-(N-methyl)indoles

Abstract

In this manuscript we described the FeCl₃/diorganyl di­selenides promoted intramolecular cyclization of o-alkynyl anilines, as an alternative for the construction of functionalized 3-organoselenyl indoles. The cyclization reactions proceeded smoothly at room temperature in the presence of air giving the 3-organoselenyl indoles in good yields. Additionally, the 3-organo­selenyl indoles proved to be quite useful as synthetic intermediates for the construction of more functionalized indole units through a selenium–lithium exchange reaction followed by trapping the lithium intermediate with different electrophiles.

Key words

indole - iron salt - cyclization - selenium

• References and Notes

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• 21 General Procedure for the FeCl₃/Diorganyl Diselenide Promoted Cyclization of o-Alkynyl Anilines: In a Schlenk tube, open to the air, containing CH₂Cl₂ (3 mL) were added FeCl₃ (0.081 g, 2 equiv) and the diorganyl diselenide (0.061 g, 0.75 equiv). The reaction mixture was stirred for 20 min at r.t. After this time, o-alkynyl aniline (0.25 mmol) was added diluted in CH₂Cl₂ (2 mL). The reaction mixture was stirred at r.t. for the required time. After that, the reaction mixture was diluted with CH₂Cl₂ (20 mL) and washed with a sat. aq solution of NaHCO₃ (3 × 10 mL). The organic phase was separated, dried over MgSO₄, and concentrated under vacuum. The residue was purified by flash chromatography, using hexane as eluent. N-Methyl-2-phenyl-3-(phenylselenyl)-1H-indole (2a): obtained as a pale yellow oil; yield: 0.073 g (81%). ¹H NMR (200 MHz, CDCl₃): δ = 7.64–7.68 (m, 1 H), 7.26–7.44 (m, 7 H), 7.04–7.22 (m, 6 H), 3.70 (s, 3 H). ¹³C NMR (100 MHz, CDCl₃): δ = 145.8, 137.7, 134.5, 131.2, 130.7, 130.6, 128.8, 128.6, 128.4, 128.0, 125.2, 122.6, 120.8, 120.6, 109.6, 96.5, 31.6. MS (relative intensity): m/z = 363 (19), 283 (100), 267 (12), 204 (12), 165 (7), 141 (7), 77 (3), 51 (2). HRMS: m/z calcd for C₂₁H₁₇NSe: 363.0526; found: 363.0539.
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