Synthesis of 1,3,4-Oxadiazoles by Iodine-Mediated Oxidative Cyclization of Methyl Ketones with 4-Phenylsemicarbazide

Shanshan Zhang; Chuang Liu; Xiaojun Wu; Wen Li; He Li; Shiwei Wang; Yuting Leng; Yangjie Wu

doi:10.1055/a-1707-0965

Synlett, Table of Contents

Synlett 2022; 33(03): 269-272
DOI: 10.1055/a-1707-0965

letter

Synthesis of 1,3,4-Oxadiazoles by Iodine-Mediated Oxidative Cyclization of Methyl Ketones with 4-Phenylsemicarbazide

Shanshan Zhang

^aGreen Catalysis Center, and College of Chemistry, Key Laboratory of Chemical Biology and Organic Chemistry of Henan Province, Zhengzhou University, Zhengzhou 450001, P. R. of China

,

Chuang Liu

^aGreen Catalysis Center, and College of Chemistry, Key Laboratory of Chemical Biology and Organic Chemistry of Henan Province, Zhengzhou University, Zhengzhou 450001, P. R. of China

,

Xiaojun Wu

^aGreen Catalysis Center, and College of Chemistry, Key Laboratory of Chemical Biology and Organic Chemistry of Henan Province, Zhengzhou University, Zhengzhou 450001, P. R. of China

,

Wen Li

^aGreen Catalysis Center, and College of Chemistry, Key Laboratory of Chemical Biology and Organic Chemistry of Henan Province, Zhengzhou University, Zhengzhou 450001, P. R. of China

,

He Li

^aGreen Catalysis Center, and College of Chemistry, Key Laboratory of Chemical Biology and Organic Chemistry of Henan Province, Zhengzhou University, Zhengzhou 450001, P. R. of China

,

Shiwei Wang

^bSchool of Mechanics and Engineering Science, Zhengzhou University, Zhengzhou, Henan 450001, P. R. of China

,

Yuting Leng ∗

^aGreen Catalysis Center, and College of Chemistry, Key Laboratory of Chemical Biology and Organic Chemistry of Henan Province, Zhengzhou University, Zhengzhou 450001, P. R. of China

,

Yangjie Wu ∗

^aGreen Catalysis Center, and College of Chemistry, Key Laboratory of Chemical Biology and Organic Chemistry of Henan Province, Zhengzhou University, Zhengzhou 450001, P. R. of China

› Author Affiliations

Abstract

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Abstract

An efficient one-pot method has been developed to access 5-amino-2-(het)aroyl-1,3,4-oxadiazoles through I₂/DMSO-promoted oxidative cyclization of 4-phenylsemicarbazide with (het)aryl methyl ketones under mild conditions. This reaction proceeds smoothly with a wide range of methyl ketones containing various functional groups to give the corresponding products in moderate yields under mild conditions.

Keywords

one-pot reaction - oxadiazoles - oxidative cyclization - phenylsemicarbazide - methyl ketones

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References

References and Notes

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19 1,3,4-Oxadiazoles 3aa–ka; General Procedure A 25 mL Schlenk-flask equipped with a magnetic stirrer bar was charged with the appropriate methyl ketone 1 (0.2 mmol, 1.0 equiv.), I₂ (0.5 mmol), and DMSO (1.0 mL), and the mixture was heated at 110 °C for 1 h. 4-Phenylsemicarbazide (2; 0.24 mmol), K₂CO₃ (0.6 mmol), and DMSO (1.0 mL) were added, and the resulting mixture was stirred at 110 °C for 15 h. The reaction was then quenched with 5% aq Na₂S₂O₃ (20 mL), and the mixture was extracted with CH₂Cl₂ (3 × 20 mL). The organic layer was dried (Na₂SO₄) and concentrated, and the residue was purified by chromatography (silica gel). [5-(Phenylamino)-1,3,4-oxadiazol-2-yl](4-tolyl)methanone (3aa) Yellow solid; yield: 44.5 mg (80%); mp 201–203 °C. ¹H NMR (400 MHz, DMSO-d ₆): δ = 11.13 (s, 1 H), 8.23 (d, J = 8.4 Hz, 2 H), 7.58 (d, J = 8.0 Hz, 2 H), 7.37–7.32 (m, 4 H), 7.01 (t, J = 7.2 Hz, 1 H), 2.36 (s, 3 H). ¹³C NMR (100 MHz, DMSO-d ₆): δ = 176.6, 161.3, 156.6, 145.5, 138.3, 132.4, 130.8, 129.8, 129.7, 123.2, 118.0, 21.8. HRMS (ESI-TOF): m/z [M + H]⁺ calcd for C₁₆H₁₄N₃O₂: 280.1081; found: 280.1081. [5-(Phenylamino)-1,3,4-oxadiazol-2-yl](2-thienyl)methanone (3ca) Yellow solid; yield: 28.5 mg (53%); mp 199–202 °C. ¹H NMR (400 MHz, DMSO-d ₆): δ = 11.20 (s, 1 H), 8.54 (dd, J = 4.0, 1.2 Hz, 1 H), 8.24 (dd, J = 4.8, 1.2 Hz, 1 H), 7.66–7.63 (m, 2 H), 7.44–7.37 (m, 3 H), 7.09 (tt, J = 7.6, 1.2 Hz, 1 H). ¹³C NMR (100 MHz, DMSO-d ₆): δ = 169.0, 161.5, 156.0, 140.1, 138.3, 138.2, 137.1, 129.7, 129.6, 123.3, 118.1. HRMS (ESI-TOF) m/z [M + H]⁺ calcd for C₁₃H₁₀N₃O₂S: 272.0488; found: 272.0491. (3,4-Difluorophenyl)[5-(phenylamino)-1,3,4-oxadiazol-2-yl]methanone (3ka) Yellow solid; yield: 37.3 mg (62%); mp 199–202 °C. ¹H NMR (400 MHz, DMSO-d ₆): δ = 11.25 (s, 1 H), 8.39–8.34 (m, 1 H), 8.32–8.28 (m, 1 H), 7.76–7.69 (m, 1 H), 7.65–7.62 (m, 2 H), 7.43–7.39 (m, 2 H), 7.12–7.07 (m, 1 H). ¹³C NMR (100 MHz, DMSO-d ₆): δ = 174.5 (d, J _C–F = 1.4 Hz), 161.5, 156.4, 152.4 (d, J _C-F = 12.4 Hz), 148.4 (d, J _C-F = 13.0 Hz), 138.2, 132.3 (dd, J _C–F = 5.5, 3.3 Hz), 129.7, 128.7 (dd, J _C–F = 8.1, 3.3 Hz), 123.4, 119.8 (d, J _C–F = 18.8 Hz), 118.6 (d, J _C–F = 17.7 Hz), 118.1. ¹⁹F NMR (376 MHz, DMSO-d ₆): δ = –129.4 (d, J _F–F = 22.56 Hz), –137.1 (d, J _F–F = 22.18 Hz). HRMS (ESI-TOF): m/z [M + H]⁺ calcd for C₁₅H₁₀F₂N₃O₂: 302.0736; found: 302.0737.

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