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

Kush Mandal; Gopal Rana; Asadujjaman Nur; Sourav Ghosh; Umasish Jana

doi:10.1055/a-2403-5390

Synlett, Table of Contents

Synlett 2024; 35(20): 2525-2531
DOI: 10.1055/a-2403-5390

letter

Special Issue to Celebrate the 75th Birthday of Prof. B. C. Ranu

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

Authors

Kush Mandal
Gopal Rana
Asadujjaman Nur
Sourav Ghosh
Umasish Jana

Abstract

All articles of this category

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

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References

References and Notes

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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.

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