Silver-Mediated Homocoupling of Arylboronic Acids

Abstract

Here we describe a homocoupling reaction of arylboronic acid facilitated by silver carbonate, which proceeds smoothly in MeOH even at ambient temperature. The reaction exhibits broad functional group compatibility, affording a variety of symmetrical biaryls in satisfactory yields. Silver nanoparticles formed in situ serve as an accelerator in this process. Moreover, initial mechanistic investigations suggest that this transformation may occur via a radical mechanism.

Key words

silver-mediated - homocoupling - arylboronic acids - nanoparticles - oxidative coupling

Publication History

Received: 12 April 2024

Accepted after revision: 27 April 2024

Accepted Manuscript online:
27 April 2024

Article published online:
14 May 2024

• References and Notes

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• 15 Reaction time was optimized. See the Supporting Information for more detail.
• 16 4,4′-Dimethylbiphenyl was quantitatively recovered following the stirring of its MeOH solution at 60 °C for 18 h in the presence of Ag₂CO₃, indicating that the coupling product remained stable under the reaction conditions.
• 17 No coupling product was obtained when anisole was employed as a substrate. 4-Methoxy-4′-nitrobiphenyl did not form at all from the reaction of 4-nitrophenylboronic acid with Ag₂CO₃ in the presence of anisole. These results suggest that the product of hydrodeboronation does not serve as an intermediate in the homocoupling reaction.
• 18 Thiophene was detected by GC (95% yield with tetradecane as an internal standard) in the reaction of 2-thienylboronic acid.
• 19 The reaction of 4-biphenylboronic acid with Ag₂CO₃ in CD₃OD or CH₃OD at 60 °C for 18 h gave deuterized biphenyl (78%D or 81%D). In contrast, no deuterium was introduced in biphenyl from the reaction in CD₃OH. This indicated that methanol serves as a hydrogen donor in hydrodeboronation.
• 20 See the Supporting Information for more detail.
• 21 Typical Procedures for Homocoupling Reaction of Arylboronic Acid 4-Methoxyphenylboronic acid (76.0 mg, 0.50 mmol), Ag₂CO₃ (68.5 mg, 0.25 mmol), and 1.0 mL MeOH were added to a screw caped vial (no. 02, Maruemu Co., Osaka, Japan) with stirring bar. After stirring at 60 °C for 3 h, the reaction mixture was cooled to room temperature. After the reaction the mixture was extracted eight times with diethyl ether and H₂O. Then the organic layer was separated. The organic extracts were dried over MgSO₄ and concentrated under reduced pressure. The product was analyzed by ¹H NMR spectroscopy (¹H: 400 MHz; ¹³C: 100 MHz). The crude material was purified with silica gel column chromatography (hexane) to give 4,4′-dimethoxybiphenyl in 91% yield. 4,4′-Dimethoxybiphenyl [CAS Reg. No. 2132-80-1] White solid (49 mg, 91%). ¹H NMR (CDCl₃): δ = 7.48 (d, J = 8.4 Hz, 4 H), 6.96 (d, J = 8.8 Hz, 4 H), 3.84 (s, 6 H). ¹³C NMR (CDCl₃): δ = 158.8, 133.6, 127.8, 55.4. 4,4′-Dimethylbiphenyl [CAS Reg. No. 613-33-2] White solid (39 mg, 85%). ¹H NMR (CDCl₃): δ = 7.48 (d, J = 8.0 Hz, 4 H), 7.24 (d, J = 8.4 Hz, 4 H), 2.39 (s, 6 H). ¹³C NMR (CDCl₃): δ = 138.4, 136.8, 129.6, 126.9, 21.2. Biphenyl [CAS Reg. No. 92-52-4] White solid (26 mg, 67%). ¹H NMR (CDCl₃): δ = 7.61–7.59 (m, 4 H), 7.44 (t, J = 8.0 Hz, 4 H), 7.35 (t, J = 7.2 Hz, 2 H). ¹³C NMR (CDCl₃): δ = 141.3, 128.9, 127.4, 127.3. 4,4′-Dichlorobiphenyl [CAS Reg. No. 2050-68-2] White solid (39 mg, 70%). ¹H NMR (CDCl₃): δ = 7.48 (d, J = 8.4 Hz, 4 H), 7.41 (d, J = 8.4 Hz, 4 H). ¹³C NMR (CDCl₃): δ = 138.5, 133.8, 129.1, 128.3. 4,4′-Diiodobiphenyl [CAS Reg. No. 2050-68-2] Yellow solid (70 mg, 69%). ¹H NMR (CDCl₃): δ = 7.48 (d, J = 8.4 Hz, 4 H), 7.41 (d, J = 8.4 Hz, 4 H). ¹³C NMR (CDCl₃): δ = 138.5, 133.8, 129.1, 128.3. 4,4′-Diformylbiphenyl [CAS Reg. No. 66-98-8] White solid (33 mg, 63%). ¹H NMR (CDCl₃): δ = 10.10 (s, 2 H), 8.01 (d, J = 8.0 Hz, 4 H), 7.81 (d, J = 8.0 Hz, 4 H). ¹³C NMR (CDCl₃): δ = 191.9, 145.6, 136.0, 130.5, 128.1. 4,4′-Diacetylbiphenyl [CAS Reg. No. 787-69-9] White solid (35 mg, 59%). ¹H NMR (CDCl₃): δ = 8.07 (d, J = 8.8 Hz, 4 H), 7.73 (d, J = 8.8 Hz, 4 H), 2.66 (s, 6 H). ¹³C NMR (CDCl₃): δ = 197.8, 144.4, 136.6, 129.1, 127.6, 26.9. 4,4′-Di(trifluoromethyl)biphenyl [CAS Reg. No. 581-80-6] White solid (20 mg, 28%). ¹H NMR (CDCl₃): δ = 7.75–7.69 (m, 8 H). ¹³C NMR (CDCl₃): δ = 43.3, 130.3 (q, J = 32.6 Hz), 127.7, 126.0 (q, J = 32.6 Hz), 124.2 (q, J = 270.2 Hz). ¹⁹F NMR (CDCl₃): δ = –62.4. 4,4′-Dinitrobiphenyl [CAS Reg. No. 1528-74-1] Yellow solid (32 mg, 48%). ¹H NMR (CDCl₃): δ = 8.37 (d, J = 9.2 Hz, 4 H), 7.79 (d, J = 8.8 Hz, 4 H). ¹³C NMR (CDCl₃): δ = 148.1, 145.1, 128.4, 124.5. 3,3′-Dimethylbiphenyl [CAS Reg. No. 612-75-9] Colorless oil (44 mg, 98%). ¹H NMR (CDCl₃): δ = 7.34 (d, J = 8.8 Hz, 4 H), 7.30 (t, J = 7.2 Hz, 2 H), 7.14 (d, J = 7.6 Hz, 2 H), 2.41 (s, 3 H). ¹³C NMR (CDCl₃): δ = 141.5, 138.4, 128.7, 128.1, 128.0, 124.4, 21.7. 3,3′-Dicyclopropylbiphenyl Colorless oil (25 mg, 92%: from 0.23 mmol of 3-cyclopropylphenylboronic acid). ¹H NMR (CDCl₃): δ = 7.36–7.27 (m, 3 H), 7.03 (d, J = 6.8 Hz, 1 H), 1.99–1.92 (m, 1 H), 1.01–0.93 (m, 2 H), 0.77–0.73 (m, 2 H). ¹³C NMR (CDCl₃): δ = 144.5, 141.6, 128.7, 124.9, 124.5, 124.5, 15.6, 9.4. 4,4′-Divinylbiphenyl [CAS Reg. No. 4433-13-0] White solid (25 mg, 49%). ¹H NMR (CDCl₃): δ = 7.57 (d, J = 8.0 Hz, 4 H), 7.48 (d, J = 8.4 Hz, 4 H), 6.75 (dd, J = 17.2 Hz, 6.8 Hz, 2 H), 5.80 (d, J = 17.6 Hz, 2 H), 5.28 (d, J = 10.8 Hz, 2 H). ¹³C NMR (CDCl₃): δ = 140.1, 136.7, 136.5, 127.1, 126.8, 114.1. 2,2′-Binaphthyl [CAS Reg. No. 612-78-2] White solid (35 mg, 55%). ¹H NMR (CDCl₃): δ = 8.17 (s, 2 H), 7.97–7.93 (m, 4 H), 7.90–7.87 (m, 4 H), 7.55–7.48 (m, 4 H). ¹³C NMR (CDCl₃): δ = 138.5, 133.8, 132.8, 128.6, 128.3, 127.8, 126.5, 126.2, 126.1, 125.8.