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Synlett 2019; 30(19): 2131-2135
DOI: 10.1055/s-0039-1690227
letter
© Georg Thieme Verlag Stuttgart · New York

Base-Controlled One-Pot Chemoselective Suzuki–Miyaura Reactions for the Synthesis of Unsymmetrical Terphenyls

Xinmin Li∗
School of Pharmacy, Zunyi Medical University, Zunyi, 563000, P. R. of China   eMail: lixm@zmu.edu.cn
,
Fangfang Feng
,
Changyue Ren
,
Yong Teng
,
Qinghong Hu
,
Zeli Yuan∗
School of Pharmacy, Zunyi Medical University, Zunyi, 563000, P. R. of China   eMail: lixm@zmu.edu.cn
› InstitutsangabenThis work was financially supported by NSFC (81660575 and 81360471), the United Scientific Research Foundation of Zunyi Medical University (E-234), and the Natural Science and Technology Foundation of Guizhou Province ([2018]1187).
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Publikationsverlauf

Received: 29. August 2019

Accepted after revision: 14. Oktober 2019

Publikationsdatum:
04. November 2019 (online)

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Abstract

We report a chemoselective Suzuki–Miyaura reaction protocol of using bromophenyl fluorosulfonate as building block for the preparation of unsymmetrical terphenyls. The chemoselective cross-coupling of bromophenyl fluorosulfonate and arylboronic acids can be achieved by controlling base species without using any ligands. Under this methodology, various of m- and p-unsymmetrical terphenyls were obtained in moderate to good yields.

Key words

chemoselective - Suzuki–Miyaura reactions - unsymmetrical terphenyls - one-pot - ligand-free

Supporting Information

    Supporting information for this article is available online at https://doi.org/10.1055/s-0039-1690227.
  • Supporting Information
 

  • References and Notes

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  • 14 General Procedure for the Preparation of Biaryl Fluorosulfonates A mixture of bromophenyl fluorosulfonates (0.5 mmol), arylboronic acid (0.55 mmol), K2CO3 (1 mmol), Pd(OAc)2 (1 mol%), and EtOH/H2O (2 mL/2 mL) was stirred at 25 °C under air for the indicated time. After the reaction, the mixture was added to brine (10 mL) and extracted with ethyl acetate (3 × 15 mL). The combined organic layers were concentrated in vacuo, and the product was isolated by short chromatography on a silica gel (200–300 mesh) column using petroleum ether (60–90 °C). 3′,4′-Dimethoxybiphenyl-4-yl fluorosulfate (2f) Colorless liquid (140.8 mg, 90%). 1H NMR (400 MHz, CDCl3): δ = 7.62 (d, J = 6.4 Hz, 2 H), 7.38 (d, J = 6.7 Hz, 2 H), 7.08 (d, J = 19.1 Hz, 2 H), 6.96 (s, 1 H), 3.93 (s, 6 H). 13C NMR (101 MHz, CDCl3): δ = 149.3, 149.2, 149.0, 141.8, 132.1, 128.6, 121.1, 119.6, 111.5, 110.3, 55.9. 19F NMR (376 MHz, CDCl3): δ = 37.4 (s, 1 F). 3′,4′-Dimethoxybiphenyl-3-yl fluorosulfate (2m) Colorless liquid (140.1 mg, 89%). 1H NMR (400 MHz, CDCl3): δ = 7.50 (d, J = 7.8 Hz, 1 H), 7.40 (s, 2 H), 7.18 (d, J = 7.3 Hz, 1 H), 7.03 (d, J = 8.2 Hz, 1 H), 6.97 (s, 1 H), 6.86 (d, J = 8.3 Hz, 1 H), 3.84 (d, J = 11.5 Hz, 6 H). 13C NMR (101 MHz, CDCl3): δ = 150.4, 149.4, 149.3, 143.8, 131.6, 130.5, 126.8, 119.60, 118.9, 118.6, 111.5, 110.1, 55.9. 19F NMR (376 MHz, CDCl3): δ = 37.1 (s, 1 F).
  • 15 General Procedure for the Preparation of Unsymmetrical Terphenyls A mixture of bromophenyl fluorosulfonate (0.5 mmol), arylboronic acid (0.5 mmol), K2CO3 (1 mmol), Pd(OAc)2 (1 mol%), and EtOH/H2O (5 mL/5 mL) was stirred at 25 °C under air for 0.5 h. Then, arylboronic acid (0.5 mmol), (i-Pr)2NH (1 mmol), and Pd(OAc)2 (1 mol%) were added to the reaction mixture and stirred for 3.5 h at 80 °C. Afterwards, the mixture was cooled to room temperature and concentrated in vacuo. The terphenyl product was isolated by short chromatography on a silica gel (200–300 mesh) column using petroleum ether and ethyl acetate. 4′′-Fluoro-3,4-dimethoxy-1,1′:4′,1′′-terphenyl (3l) White solid (126.7 mg, 82%); mp 149–150 °C. 1H NMR (400 MHz, CDCl3): δ = 7.69–7.51 (m, 6 H), 7.19 (dd, J = 8.3, 2.1 Hz, 1 H), 7.17–7.10 (m, 3 H), 6.97 (d, J = 8.3 Hz, 1 H), 3.97 (s, 3 H), 3.94 (s, 3 H). 13C NMR (101 MHz, CDCl3): δ = 149.2, 148.7, 139.9, 138.7, 133.6, 128.5, 128.5, 127.3, 127.2, 119.3, 115.8, 115.5, 111.5, 110.3, 56.0, 55.9. 5-[3′,4′-Dimethoxy-(1,1′-biphenyl)-4-yl]pyrimidine (3v) White solid (50.2 mg, 38%); mp 85–86 °C. 1H NMR (400 MHz, CDCl3): δ = 9.18 (d, J = 21.5 Hz, 1 H), 8.96 (d, J = 32.8 Hz, 2 H), 7.68 (dd, J = 27.4, 8.2 Hz, 3 H), 7.56 (dd, J = 24.1, 8.4 Hz, 2 H), 7.03 (dd, J = 12.6, 8.8 Hz, 2 H), 3.87 (s, 3 H). 13C NMR (101 MHz, CDCl3): δ = 160.4, 159.5, 157.3, 156.8, 154.6, 154.4, 141.5, 133.9, 132.4, 132.3, 128.1, 127.6, 127.2, 114.9, 114.3, 55.3.