Copper-Catalyzed One-Pot Synthesis of Chalcogen-Benzothiazoles/Imidazo[1,2-a]pyridines with Sulfur/Selenium Powder and Aryl Boronic Acids

Tao Guo; Xu-Ning Wei; Ying-Li Zhu; Huan Chen; Shu-Lei Han; Yong-Cheng Ma

doi:10.1055/s-0037-1609758

Synlett, Table of Contents

Synlett 2018; 29(11): 1530-1536
DOI: 10.1055/s-0037-1609758

letter

Copper-Catalyzed One-Pot Synthesis of Chalcogen-Benzothiazoles/Imidazo[1,2-a]pyridines with Sulfur/Selenium Powder and Aryl Boronic Acids

Tao Guo*

^aCollege of Chemistry, Chemical and Environmental Engineering, Henan University of Technology, Zhengzhou, Henan 450001, P. R. of China Email: taoguo@haut.edu.cn

,

Xu-Ning Wei

^aCollege of Chemistry, Chemical and Environmental Engineering, Henan University of Technology, Zhengzhou, Henan 450001, P. R. of China Email: taoguo@haut.edu.cn

,

Ying-Li Zhu

^bClinical Pharmacology Laboratory, Zhengzhou University People’s Hospital, No. 7, Wei Wu Road, Zhengzhou, Henan 450002, P. R. of China

,

Huan Chen

^cChina National Tobacco Quality Supervision & Test Center, No. 2 Fengyang Street, Zhengzhou, Henan 450001, P. R. of China

,

Shu-Lei Han*

^cChina National Tobacco Quality Supervision & Test Center, No. 2 Fengyang Street, Zhengzhou, Henan 450001, P. R. of China

,

Yong-Cheng Ma*

^bClinical Pharmacology Laboratory, Zhengzhou University People’s Hospital, No. 7, Wei Wu Road, Zhengzhou, Henan 450002, P. R. of China

› Author Affiliations

Abstract

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Abstract

An efficient and convenient copper-catalyzed oxidative chalcogenation of benzothiazoles and imidazo[1,2-a]pyridines with sulfur/selenium powder and aryl boronic acids was developed. This procedure allows access to a wide range of structurally diverse arylchalcogen-substituted benzothiazoles/imidazo[1,2-a]pyridines in good yields and with good functional group tolerance. A biological evaluation revealed that some of the obtained products exhibited in vitro antiproliferative activities on human-derived lung, stomach, esophageal, and breast cancer cell lines.

Key words

benzothiazoles - imidazoheterocycles - chalcogenation - C–H activation - copper

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References

References and Notes

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17 General procedure: DMF (1 mL) was added into a flask charged with benzothiazole (1; 0.25 mmol), S₈ or Se (0.75 mmol), aryl boronic acid (2; 0.5 mmol), CuI (0.05 mmol), phen (0.05 mmol), Cs₂CO₃ (0.5 mmol), and Ag₂CO₃ (0.5 mmol). The mixture was stirred at 130 °C in air for 10 h. Then, the reaction was cooled to room temperature, diluted with ethyl acetate (20 mL) and washed with H₂O (10 mL). The aqueous layer was extracted twice with ethyl acetate (5 mL) and the combined organic phase was dried over Na₂SO₄. After evaporation of the solvents, the residue was purified by flash column chromatography (silica gel, PE–EtOAc, 15: 1 to 10: 1) to afford the desired products.2-(Phenylthio)benzo[d]thiazole (3a): Purified by using a flash chromatography column (PE/EtOAc, 15: 1); yellow oil. ¹H NMR (400 MHz, CDCl₃): δ = 7.88 (d, J = 8.4 Hz, 1 H), 7.75–7.73 (m, 2 H), 7.64 (d, J = 8.0 Hz, 1 H), 7.52–7.46 (m, 3 H), 7.42–7.38 (m, 1 H), 7.28–7.24 (m, 1 H); ¹³C NMR (100 MHz, CDCl₃): δ = 169.8, 154.1, 135.7, 135.5, 130.6, 130.1, 130.1, 126.3, 124.5, 122.1, 120.9; IR (KBr): 2922, 1581, 1456, 1425, 1309, 1236, 1080, 1007, 752 cm^–1; HRMS m/z [M⁺+H] calcd. for C₁₃H₁₀NS₂ ⁺: 244.02492; found: 244.024413-((4-Fluorophenyl)thio)-2-phenylimidazo[1,2-a]pyridine (5a): Purified by using a flash chromatography column (PE/EtOAc, 5:1); white solid; mp 128–130 °C. ¹H NMR (500 MHz, CDCl₃): δ = 8.27 (d, J = 7.0 Hz, 1 H), 8.20 (d, J = 8.0 Hz, 2 H), 7.72 (d, J = 9.0 Hz, 1 H), 7.46–7.31 (m, 4 H), 6.99–6.86 (m, 5 H); ¹³C NMR (125 MHz, CDCl₃): δ = 161.7 (d, J _C–F = 244.9 Hz), 151.5, 147.2, 133.4, 130.2 (d, J _C–F = 3.6 Hz), 128.8, 128.6, 128.5, 127.7 (d, J _C–F = 7.8 Hz), 126.9, 124.5, 117.9, 116.7 (d, J _C–F = 21.0 Hz), 113.3, 106.7; IR (KBr): 2924, 2852, 1489, 1346, 1219, 1080, 735 cm^–1; HRMS: m/z [M⁺+H] calcd. for C₁₉H₁₄FN₂S⁺: 321.08562; found: 321.08527.

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