Visible-Light-Driven Selenyl-Radical-Mediated Cascade Spirocyclization of 3-(2-Isocyanobenzyl)indoles with Diselenides

Abstract

We present a facile, visible-light-driven, selenyl-radical-mediated, cascade spirocyclization of 3-(2-isocyanobenzyl)indoles with diselenides that affords various selenylated spiro[indole-3,3′-quinoline] derivatives under mild conditions. This protocol has good functional-group tolerance and a broad substrate scope; both diaryl and dialkyl diselenides are tolerated.

Key words

photochemical reaction - visible light - cascade reaction - spirocyclization - spiroindolequinoline selenides - diselenides

Publication History

Received: 28 May 2023

Accepted after revision: 17 July 2023

Accepted Manuscript online:
17 July 2023

Article published online:
31 August 2023

• References and Notes

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• 31 2-Methyl-2′-(phenylselanyl)-4′H-spiro[indole-3,3′-quinoline] (3a) DCM (2 mL) was added to 1a (0.2 mmol) and 2a (0.6 equiv) under air, and the stirred mixture was irradiated by a 455 nm blue COB LED at 25 ℃ for 18 h. When the reaction was complete (TLC), the reaction was quenched with H₂O, and the mixture was extracted with EtOAc (3 × 25 mL). The combined organic layers were washed with H₂O (25 mL) and sat. brine (25 mL), then dried (Na₂SO₄), concentrated in vacuo, and purified by chromatography [silica gel, EtOAc–PE (1:10 to 1:3)] to give a yellow liquid; yield: 52.2 mg (65%). ¹H NMR (400 MHz, CDCl₃): δ = 7.61 (d, J = 7.6 Hz, 1 H), 7.51–7.49 (m, 2 H), 7.44 (td, J = 7.6, 1.6 Hz, 1 H), 7.34–7.31 (m, 3 H), 7.26–7.23 (m, 3 H), 7.15–7.11 (m, 2 H), 7.06 (d, J = 7.2 Hz, 1 H), 3.28 (d, J = 16.4 Hz, 1 H), 2.89 (d, J = 16.4 Hz, 1 H), 2.12 (s, 3 H). ¹³C {¹H} NMR (100 MHz, CDCl₃): δ = 180.4, 166.1, 156.1, 143.4, 139.9, 136.0, 129.8, 129.1, 128.7, 128.4, 127.9, 127.3, 127.0, 126.3, 126.3, 124.5, 123.7, 120.6, 65.1, 34.0, 18.0. HRMS (ESI-TLQ): m/z [M + H]⁺ calcd for C₂₃H₁₉N₂Se: 403.0708; found: 403.0708.