Palladium-Catalyzed Phosphine-Free Direct C–H Arylation of Benzothiophenes and Benzofurans Involving MIDA Boronates

Zhiwei Wang; Yabo Li; Beiqi Yan; Mengmeng Huang; Yangjie Wu

doi:10.1055/s-0034-1379606

Synlett, Table of Contents

Synlett 2015; 26(04): 531-536
DOI: 10.1055/s-0034-1379606

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Palladium-Catalyzed Phosphine-Free Direct C–H Arylation of Benzothiophenes and Benzofurans Involving MIDA Boronates

Zhiwei Wang

College of Chemistry and Molecular Engineering, Henan Key Laboratory of Chemical Biology and Organic Chemistry, Key Laboratory of Applied Chemistry of Henan Universities, Zhengzhou University, Zhengzhou 450052, P. R. of China Fax: +86(371)67979408 Email: wyj@zzu.edu.cn Email: hmm@zzu.edu.cn

,

Yabo Li

College of Chemistry and Molecular Engineering, Henan Key Laboratory of Chemical Biology and Organic Chemistry, Key Laboratory of Applied Chemistry of Henan Universities, Zhengzhou University, Zhengzhou 450052, P. R. of China Fax: +86(371)67979408 Email: wyj@zzu.edu.cn Email: hmm@zzu.edu.cn

,

Beiqi Yan

College of Chemistry and Molecular Engineering, Henan Key Laboratory of Chemical Biology and Organic Chemistry, Key Laboratory of Applied Chemistry of Henan Universities, Zhengzhou University, Zhengzhou 450052, P. R. of China Fax: +86(371)67979408 Email: wyj@zzu.edu.cn Email: hmm@zzu.edu.cn

,

Mengmeng Huang*

College of Chemistry and Molecular Engineering, Henan Key Laboratory of Chemical Biology and Organic Chemistry, Key Laboratory of Applied Chemistry of Henan Universities, Zhengzhou University, Zhengzhou 450052, P. R. of China Fax: +86(371)67979408 Email: wyj@zzu.edu.cn Email: hmm@zzu.edu.cn

,

Yangjie Wu*

College of Chemistry and Molecular Engineering, Henan Key Laboratory of Chemical Biology and Organic Chemistry, Key Laboratory of Applied Chemistry of Henan Universities, Zhengzhou University, Zhengzhou 450052, P. R. of China Fax: +86(371)67979408 Email: wyj@zzu.edu.cn Email: hmm@zzu.edu.cn

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Abstract

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Abstract

With high regioselectivity, a series of benzoheterocyclic compounds were synthesized via palladiium-catalyzed phosphine-free C–H arylation of benzothiophenes/benzofurans with aryl MIDA boronates at 30–50 °C in moderate to excellent yields. MIDA boronates were used in C–H arylation of heterocycles for the first time. Under the optimal conditions, the benzothiophenes could be transformed into the β-arylbenzothiophenes, and the benzofurans gave only α-aryl-substituted products.

Key words

C–H arylation - benzothiophene - benzofuran - MIDA boronate - bis(alkoxo)palladium(II) complex

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References

References and Notes

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12 Preparation of 3aa; Typical ProcedureTo a 10 mL round-bottom flask were added III (3.2 mg, 0.005 mmol, 2 mol%), Ag₂O (116 mg, 0.5 mmol, 2 equiv), benzoquinone (14 mg, 0.125 mmol, 0.5 equiv), Cs(tfa) (64 mg, 0.25 mmol, 1 equiv.), benzothiophene (1a; 34 mg, 0.25 mmol, 1 equiv), phenyl MIDA boronate (2a; 86 mg, 0.375 mmol, 1.5 equiv), and H₂O–CF₃SO₃H–TFA (15:2:83; 1 mL). The reaction mixture was stirred at 30–50 °C for 20 h. The suspension was cooled to r.t. and extracted with CH₂Cl₂ (3 × 10 mL). The combined organic layers were washed with 20% aq NaHCO₃ solution (40 mL). After evaporation of the solvent the crude product was purified by chromatography on silica gel to give 3-phenylbenzo[b]thiophene (3aa; 46.7 mg, 89% isolated yield) as a yellow oil. This product has been reported previously.^4f 3-Phenylbenzo[b]thiophene (3aa) ¹H NMR (400 MHz, CDCl₃): δ = 7.95–7.88 (m, 2 H), 7.61–7.56 (m, 2 H), 7.51–7.45 (m, 2 H), 7.43–7.35 (m, 4 H) ppm. ¹³C NMR (100 MHz, CDCl₃): δ = 140.65, 138.06, 137.86, 135.98, 128.70, 128.69, 127.52, 124.38, 124.30, 123.39, 122.90 ppm. MS (EI): m/z calcd for C₁₅H₁₂S [M]⁺: 210.1; found: 210.0.
13 CCDC-1008524 (3fa) contains the supplementary crystallographic data for this paper. These data can be obtained free of charge from The Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/data_request/cif.
14 CCDC-1008525 (3ia) contains the supplementary crystallographic data for this paper. These data can be obtained free of charge from The Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/data_request/cif.
15 Preparation of 5; Typical ProcedureTo a 10 mL round-bottom flask were added III (3.2 mg, 0.005 mmol, 2 mol%), Ag₂O (116 mg, 0.5 mmol, 2 equiv), benzoquinone (14 mg, 0.125 mmol, 0.5 equiv), Cs(tfa) (64 mg, 0.25 mmol, 1 equiv), 3aa (52.5 mg, 0.25 mmol, 1 equiv), phenyl MIDA boronate (115 mg, 0.5 mmol, 2.0 equiv), and H₂O–CF₃SO₃H–TFA (15:2:83; 1 mL). The reaction mixture was stirred at 30 °C and 80 °C for 20 h. The suspension was cooled to r.t. and extracted with CH₂Cl₂ (3 × 10 mL). The combined organic layers were washed with 20% aq NaHCO₃ solution (40 mL). After evaporation of the solvent the crude product was purified by chromatography on silica gel to give 2,3-diphenylbenzo[b]thiophene (5; 6.4 mg, 9% at 30 °C/25.0 mg, 35% at 80 °C isolated yield) as a white solid; mp 111–113 °C. This product has been reported previously.¹⁷ 2,3-Diphenylbenzo[b]thiophene (5) ¹H NMR (400 MHz, CDCl₃): δ = 7.88–7.84 (m, 1 H), 7.61–7.56 (m, 1 H), 7.42–7.28 (m, 9 H), 7.25–7.20 (m, 3 H) ppm. ¹³C NMR (100 MHz, CDCl₃): δ = 140.88, 139.54, 138.85, 135.52, 134.24, 133.24, 130.43, 129.61, 128.63, 128.33, 127.68, 127.36, 124.51, 124.42, 123.34, 122.05 ppm. MS (EI): m/z calcd for C₂₀H₁₄S [M]⁺: 286.1; found: 286.0.
16 Preparation of 6; Typical ProcedureTo a 10 mL round-bottom flask were added III (3.2 mg, 0.005 mmol, 2 mol%), Ag₂O (116 mg, 0.5 mmol, 2 equiv), benzoquinone (14 mg, 0.125 mmol, 0.5 equiv), Cs(tfa) (64 mg, 0.25 mmol, 1 equiv), 6 (56mg, 0.25 mmol, 1 equiv), phenyl MIDA boronates (115 mg, 0.5 mmol, 2.0 equiv), and H₂O–CF₃SO₃H–TFA (15:2:83; 1 mL). The reaction mixture was stirred at 30 °C and 80 °C for 20 h. The suspension was cooled to r.t. and extracted with CH₂Cl₂ (3 × 10 mL). The combined organic layers were washed with 20% aq NaHCO₃ solution (40 mL). After evaporation of the solvent the crude product was purified by chromatography on silica gel to give 3-phenyl-2-(p-tolyl)benzo[b]thiophene (6.0 mg, 8% at 30 °C/14.3 mg, 19% at 80 °C isolated yield) as a white solid; mp 149–151 °C. This product has been reported previously.¹⁸ 3-Phenyl-2-(p-tolyl)benzo[b]thiophene (7) ¹H NMR (400 MHz, CDCl₃): δ = 7.90–7.85 (m, 1 H), 7.59 (d, J = 8.2 Hz, 1 H), 7.45–7.31 (m, 7 H), 7.27–7.21 (m, 2 H), 7.10–7.04 (m, 2 H), 2.33 (s, 3 H) ppm. ¹³C NMR (100 MHz, CDCl₃): δ = 141.00, 139.73, 138.73, 137.61, 135.72, 132.80, 131.33, 130.46, 129.44, 129.08, 128.62, 127.30, 124.37, 123.22, 122.01, 21.17 ppm. MS (EI): m/z calcd for C₂₁H₁₆S [M]⁺: 300.1; found: 300.0.
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18 Lu W.-D, Wu M.-J. Tetrahedron 2007; 63: 356

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