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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
a   Green 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
a   Green 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
a   Green 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
a   Green 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
a   Green 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
b   School of Mechanics and Engineering Science, Zhengzhou University, Zhengzhou, Henan 450001, P. R. of China
,
Yuting Leng  ∗
a   Green 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  ∗
a   Green 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 AffiliationsWe gratefully acknowledge the financial support for this research provided by the National Science Foundation of China (51603192, 21172200) and the Natural Science Foundation of Henan Province (182300410211).
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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

Supporting Information

    Supporting information for this article is available online at https://doi.org/10.1055/a-1707-0965.
  • Supporting Information


Publication History

Received: 16 October 2021

Accepted after revision: 25 November 2021

Accepted Manuscript online:
25 November 2021

Article published online:
20 December 2021

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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.