Visible-Light-Induced Oxidative Generation of o-Quinone Methides for Inverse-Electron-Demand [4+2] Cycloaddition Reactions

Abstract

Organophotoredox-catalyzed oxidative generation of o-quinone methides (o-QMs) for inverse-electron-demand [4+2] cycloaddition reactions has been developed. One-electron oxidation of 2-(sulfanylmethyl)phenols by thioxanthylium photoredox catalyst generated o-QMs, which reacted with various styrenes to produce chromanes with high regioselectivity. This reaction offers a valuable approach for in situ generating o-QMs via one-electron oxidation process under irradiation with mild green light.

Key words

o-quinone methide - photoredox - visible light - chromane - [4+2] cycloaddition

Publication History

Received: 20 June 2023

Accepted after revision: 22 August 2023

Accepted Manuscript online:
22 August 2023

Article published online:
09 October 2023

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• 11 2,4-Diphenylchoroman (3a): Typical Procedure 2-(Sulfanylmethyl)phenol (1a, 58.3 mg, 0.20 mmol), styrene (2a, 62.5 mg, 0.60 mmol), TXT (5.0 mg, 9.0 μmol, 5.0 mol%), DCE (2.0 mL), and TFE (2.0 mL) were added into an 8 mL borosilicate vial. The resulting solution was stirred at room temperature under air and green LED irradiation for 24 h. The desired cycloadduct 3a was isolated by column chromatography on silica gel (hexane/ethyl acetate = 50:1). (2S*,4R*)- and (2R*,4R*)-2,4-Diphenylchromane (3a) White solid (42.4 mg, 74% yield). ¹H NMR (500 MHz, CDCl₃): δ = 7.52–7.48 (m, 2 H) (major), 7.42–7.38 (m, 2 H) (mixture), 7.37–7.29 (m, 8 H) (mixture), 7.29–7.19 (m, 6 H) (mixture), 7.17–7.12 (m, 2 H) (mixture), 7.02 (ddd, J = 14.1, 7.9, 1.5 Hz, 2 H) (minor), 6.97–6.95 (m, 1 H) (major), 6.90 (td, J = 7.4, 1.1 Hz, 1 H) (minor), 6.83–6.76 (m, 2 H) (major), 5.23 (dd, J = 11.2, 2.1 Hz, 1 H) (major), 5.05 (dd, J = 10.5, 2.3 Hz, 1 H) (minor), 4.37 (q, J = 6.1 Hz, 1 H) (major), 4.25 (q, J = 2.9 Hz, 1 H) (mixture), 2.51–2.46 (m, 1 H) (minor), 2.42 (ddd, J = 13.7, 5.7, 2.1 Hz, 1 H) (major), 2.33–2.24 (m, 1 H) (major). ¹³C{¹H} NMR (126 MHz, CDCl₃) (mixture): δ = 155.5, 155.4, 146.0, 144.5, 141.4, 141.2, 130.8, 129.8, 128.6, 128.6, 128.4, 128.1, 128.0, 127.7, 126.8, 126.4, 126.1, 126.0, 125.7, 123.1, 120.6, 120.5, 117.0, 117.0, 78.1, 73.2, 43.5, 40.6, 40.2, 38.3.
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• 13 See the Supporting Information.