Visible-Light-Induced Iron(III)-Catalyzed Synthesis of Unsymmetrical Bis(indolyl)methanes through Hydrogen Atom Transfer

Dedicated to Professor B. C. Ranu on the occasion of his 75^th birthday

Abstract

We report a visible-light-mediated, FeCl₃-catalyzed, one-pot tandem strategy for the regioselective synthesis of unsymmetrically substituted tertiary and quaternary carbon-containing 3,3′-bis(indolyl)methanes under aerobic conditions. This strategy involves the coupling of 3-arylideneindolines with indoles through a photoinduced chlorine-radical-mediated hydrogen-atom-transfer reaction. The present strategy features mild and environmentally benign reaction conditions, low cost, high yields, and tolerance of a wide range of functional groups. Furthermore, to demonstrate the synthetic value of the reaction, a naturally occurring bioactive bisindolyl(phenyl)methane was synthesized.

Key words

iron catalysis - hydrogen atom transfer - photoredox reaction - bisindolylmethanes

Publication History

Received: 27 July 2024

Accepted after revision: 26 August 2024

Accepted Manuscript online:
26 August 2024

Article published online:
25 September 2024

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• 28 1-Methyl-3-[(1-tosyl-1H-indol-3-yl)(phenyl)methyl]-1H-indole (4a); Typical Procedure An oven-dried 20 mL reaction tube equipped with a magnetic stirrer bar was charged with indoline 2a (75 mg, 0.20 mmol), N-methylindole (3a) (30 mg, 0.22 mmol), anhyd FeCl₃ (9.7 mg, 30 mol%), activated anhyd MgSO₄ (24 mg, 1 equiv), and anhyd MeCN (2 mL). The mixture was then irradiated with a 32 W CFL under O₂ (balloon) at 60 °C for 24 h. When the reaction was complete (TLC), the mixture was extracted with EtOAc (3 × 20 mL), and the organic phase was dried (Na₂SO₄) and concentrated. The resulting crude product was purified by column chromatography [silica gel (60–120 mesh), hexane–EtOAc (97:3)] to give a white solid; yield: 87 mg (89%); mp 68–71 °C. ¹H NMR (400 MHz, CDCl₃): δ = 8.00 (d, J = 8.3 Hz, 1 H), 7.63 (d, J = 7.0 Hz, 2 H), 7.36–7.29 (m, 5 H), 7.29 (s, 1 H), 7.27 (d, J = 2.3 Hz, 2 H), 7.25 (d, J = 3.7 Hz, 2 H), 7.22 (d, J = 8.2 Hz, 2 H), 7.12 (t, J = 7.6 Hz, 1 H), 7.05 (s, 1 H), 7.01 (t, J = 7.4 Hz, 1 H), 6.41 (s, 1 H), 5.74 (s, 1 H), 3.72 (s, 3 H), 2.40 (s, 3 H). ¹³C NMR (75 MHz, CDCl₃): δ = 144.6, 142.2, 137.5, 135.8, 135.0, 130.6, 129.7, 128.6, 128.5, 128.2, 127.03, 126.9, 126.6, 126.5, 125.6, 124.6, 123.1, 121.7, 120.4, 119.6, 118.8, 116.5, 113.9, 109.4, 40.0, 32.8, 21.6. HRMS (ESI): m/z [M + H]⁺ calcd for C₃₁H₂₇N₂O₂S: 491.1793; found: 491.1791.