Organophotocatalytic Radical–Polar Cross-Coupling of Styrylboronic Acids and Redox-Active Esters

 

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Abstract

We report the development of a radical–polar cross-coupling reaction using styrylboronic acids and redox-active esters under organophotoredox catalysis. The reaction proceeds through a formal polarity-mismatched radical addition. The use of an organic photocatalyst permitted very low loadings of the electron-shuttle additive and accelerated reaction times compared with established processes. The scope of the reaction was explored, and the utility of the products is demonstrated.

Publication History

Received: 01 September 2023

Accepted: 21 September 2023

Accepted Manuscript online:
21 September 2023

Article published online:
23 October 2023

© 2023. The Author(s). This is an open access article published by Thieme under the terms of the Creative Commons Attribution License, permitting copying and reproduction so long as the original work is given appropriate credit. Contents may not be used for commercial purposes or adapted, remixed, transformed or built upon. (https://creativecommons.org/licenses/by/4.0/)

Georg Thieme Verlag KG
Rüdigerstraße 14, 70469 Stuttgart, Germany

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• 19 Alkenes 3–34; General Procedure An oven-dried photoreactor vial equipped with a Teflon-coated stirrer bar was charged with the appropriate NHPI ester (200 μmol, 1.0 equiv) and styrylboronic acid (400 μmol, 2.0 equiv), together with 4CzIPN (1.6 mg, 2.0 μmol, 1 mol%) and Ph₃N (1.0 mg, 4.0 μmol, 2 mol%). The vial was then sealed, purged by using N₂–vacuum cycles (×3), and backfilled with N₂. Degassed dry DMSO-d ₆ (2.0 mL, 0.1 M) was then added from a syringe. The cap was wrapped with Parafilm, and the mixture was stirred under blue LEDs at RT (~20 °C) for 1 h. The mixture was then partitioned between Et₂O (5 mL) and brine (5 mL), and the organics were extracted with Et₂O (2 × 10 mL). The organic phases were combined, washed with brine (15 mL), dried (Na₂SO₄), filtered, and concentrated under vacuum. The crude residue was purified by flash chromatography (silica gel; hexane, hexane–EtOAc, or hexane–Et₂O). [(E)-2-Cyclohexylvinyl]benzene (3) Prepared according to the general procedure from 1,3-dioxoisoindolin-2-yl cyclohexanecarboxylate (2; 54.7 mg, 200 μmol, 1.0 equiv), [(E)-2-phenylvinyl]boronic acid (1; 59.2 mg, 400 μmol, 2.0 equiv), 4CzIPN (1.6 mg, 2.0 μmol, 1 mol%), and Ph₂N (1.0 mg, 4.0 μmol, 2 mol%) in DMSO-d ₆ (2 mL, 0.1 M). The crude residue (95% ¹H NMR yield) was purified by flash chromatography (silica gel, hexane) to give a colorless oil; yield: 31.8 mg (85%, E/Z > 20:1). ¹H NMR (500 MHz, CDCl₃): δ = 7.37–7.33 (m, 2 H), 7.31–7.27 (m, 2 H), 7.21–7.16 (m, 1 H), 6.35 (d, J = 16.01 Hz, 1 H), 6.18 (dd, J = 15.98, 6.96 Hz, 1 H), 2.18–2.08 (m, 1 H), 1.86–1.74 (m, 4 H), 1.72–1.65 (m, 1 H), 1.39–1.25 (m, 2 H), 1.25–1.14 (m, 3 H). ¹³C NMR (126 MHz, CDCl₃): δ = 138.2, 137.0, 128.6, 127.3, 126.9, 126.1, 41.3, 33.1, 26.3, 26.2.

• Supplementary Material