A Facile and Expeditious One-Pot Synthesis of α-Keto-1,3,4-oxadiazoles

Dalip Kumar; Meenakshi Pilania; V. Arun; Bhupendra Mishra

doi:10.1055/s-0033-1340981

Synlett, Table of Contents

Synlett 2014; 25(08): 1137-1141
DOI: 10.1055/s-0033-1340981

letter

A Facile and Expeditious One-Pot Synthesis of α-Keto-1,3,4-oxadiazoles

Authors

Dalip Kumar*

Department of Chemistry, Birla Institute of Technology and Science, Pilani – 333 031, Rajasthan, India Fax: +44(113)3436565 Email: dalipk@pilani.bits-pilani.ac.in
Meenakshi Pilania

Department of Chemistry, Birla Institute of Technology and Science, Pilani – 333 031, Rajasthan, India Fax: +44(113)3436565 Email: dalipk@pilani.bits-pilani.ac.in
V. Arun

Department of Chemistry, Birla Institute of Technology and Science, Pilani – 333 031, Rajasthan, India Fax: +44(113)3436565 Email: dalipk@pilani.bits-pilani.ac.in
Bhupendra Mishra

Department of Chemistry, Birla Institute of Technology and Science, Pilani – 333 031, Rajasthan, India Fax: +44(113)3436565 Email: dalipk@pilani.bits-pilani.ac.in

Abstract

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Abstract

An efficient and high-yielding protocol for the preparation of α-keto-1,3,4-oxadiazoles has been developed. Formation of α-keto-1,3,4-oxadiazoles involves the 2-iodoxybenzoic acid/tetraethylammonium bromide mediated oxidative cyclization of hydrazide-hydrazones generated in situ from the reaction of aryl glyoxal and hydrazides. This one-pot protocol is reasonably general for the preparation of α-keto-1,3,4-oxadiazoles under mild conditions in short reaction times.

Key words

nitrogen heterocycles - hypervalent iodine reagents - oxidation - cyclization

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References

References and Notes

1a Amir M, Shikha K. Eur. J. Med. Chem. 2004; 39: 535
1b Rapolu S, Alla M, Bommena VR, Murthy R, Jain N, Bommareddy VR, Bommineni MR. Eur. J. Med. Chem. 2013; 66: 91
1c de Oliveira CS, Lira BF, Barbosa-Filho JM, Lorenzo JG. F, de Athayde-Filho PF. Molecules 2012; 17: 10192

2a Xie Y, Liu J, Yang P, Shi X, Li J. Tetrahedron 2011; 67: 5369
2b Stabile P, Lamonica A, Ribecai A, Castoldi D, Guercio G, Curcuruto O. Tetrahedron Lett. 2010; 51: 4801

3 Guin S, Ghosh T, Rout SK, Banerjee A, Patel BK. Org. Lett. 2011; 13: 5976

4a Dohi T, Ito M, Yamaoka N, Morimoto K, Fujioka H, Kita Y. Tetrahedron 2009; 65: 10797
4b Zhdankin VV, Stang PJ. Chem. Rev. 2008; 108: 5299
4c Silva JL. F, Olofsson B. Nat. Prod. Rep. 2011; 28: 1722
4d Zhdankin VV. J. Org. Chem. 2011; 76: 1185
4e Kumar D, Arun V, Maruthi Kumar N, Acosta G, Noel B, Shah K. ChemMedChem 2012; 7: 1915
4f Tantak MP, Kumar A, Noel B, Shah K, Kumar D. ChemMedChem 2013; 8: 1468
4g Duschek A, Kirsch SF. Angew. Chem. Int. Ed. 2011; 50: 1524
4h Satam V, Harad A, Rajule R, Pati H. Tetrahedron 2010; 66: 7659

5a Ghosh H, Yella R, Ali AR, Sahoo SK, Patel BK. Tetrahedron Lett. 2009; 50: 2407
5b Singh CB, Ghosh H, Murru S, Patel BK. J. Org. Chem. 2008; 73: 2924
5c Vaddula B, Leazer J, Varma RS. Adv. Synth. Catal. 2012; 354: 986

6a Moriarty RM. J. Org. Chem. 2005; 70: 2893
6b Prabhu G, Sureshbabu VV. Tetrahedron Lett. 2012; 53: 4232
6c Stang PJ, Zhdankin VV. Chem. Rev. 1996; 96: 1123

7 Donohoe TJ, Kabeshov MA, Rathi AH, Smith IE. D. Org. Biomol. Chem. 2012; 10: 1093
8 Moorthy JN, Neogi I. Tetrahedron Lett. 2011; 52: 3868
9 Wagh YS, Tiwari NJ, Bhanage BM. Tetrahedron Lett. 2013; 54: 1290
10 Prabhu G, Sureshbabu VV. Tetrahedron Lett. 2012; 53: 4232
11 Palmer JT, Hirschbein BL, Cheung H, McCarter J, Janc JW, Yu ZW, Wesolowski G. Bioorg. Med. Chem. Lett. 2006; 16: 2909
12 Ohmoto K, Yamamoto T, Okuma M, Horiuchi T, Imanishi H, Odagaki Y, Kawabata K, Sekioka T, Hirota Y, Matsuoka S, Nakai H, Toda M, Cheronis JC, Spruce LW, Gyorkos A, Wieczorek M. J. Med. Chem. 2001; 44: 1268
13 Otrubova K, Boger DL. ACS Chem. Neurosci. 2011; 3: 340
14 Rydzewski RM, Burrill L, Mendonca R, Palmer JT, Rice M, Tahilramani R, Bass KE, Leung L, Gjerstad E, Janc JW, Pan L. J. Med. Chem. 2006; 49: 2953

15a Lu Y, Li C.-M, Wang Z, Ross CR, Chen J, Dalton JT, Li W, Miller DD. J. Med. Chem. 2009; 52: 1701
15b Xiao M, Ahn S, Wang J, Chen J, Miller DD, Dalton JT, Li W. J. Med. Chem. 2013; 56: 3318

16 El Sayed KA. Phytochemistry 2000; 53: 675
17 Kudelko A. Tetrahedron 2011; 67: 8502
18 Zarudnitskii EV, Pervak II, Merkulov AS, Yurchenko AA, Tolmachev AA. Tetrahedron 2008; 64: 10431
19 Cui L, Liu Q, Yu J, Ni C, Yu H. Tetrahedron Lett. 2011; 52: 5530
20 Bellale EV, Bhalerao DS, Akamanchi KG. J. Org. Chem. 2008; 73: 9473
21 One-Pot Synthesis of 4a–m; General Procedure: A mixture of arylglyoxal (1 mmol) and arylhydrazide (1 mmol) was stirred in acetonitrile at r.t. for 3 h. After consumption of the starting materials, IBX (1 mmol) was added to the reaction mixture followed by addition of TEAB (1.2 mmol) and stirring was continued at r.t. for another 3 h. Upon completion of the reaction, solvent was removed in vacuo and the crude material thus obtained was diluted with H₂O and extracted with EtOAc (3 × 25 mL). The combined organic layers were washed with saturated NaHCO₃ (20 mL), brine (20 mL), and dried over anhydrous Na₂SO₄. After filtration, the solvent was evaporated under reduced pressure and the residue was recrystallized from ethanol to afford analytically pure α-keto-1,3,4-oxadiazoles 4a–m in excellent yields. Phenyl(5-phenyl-1,3,4-oxadiazol-2-yl)methanone (4a): Yield: 90%; white solid; mp 143–144 °C (Lit.¹⁹ 143–145 °C). IR (KBr): 1666, 1535, 1411, 1380, 1280, 1180 cm^–1. ¹H NMR (400 MHz, DMSO-d ₆): δ = 8.45 (dd, J = 8.3, 1.1 Hz, 2 H), 8.15 (dd, J = 8.2, 1.3 Hz, 2 H), 7.74 (t, J = 7.4 Hz, 1 H), 7.64–7.56 (m, 5 H). ¹³C NMR (101 MHz, DMSO-d ₆): δ = 182.13, 170.13, 165.71, 139.76, 139.31, 137.90, 135.60, 134.48, 133.78, 132.43, 127.70. MS (ESI): m/z [M + H]⁺ calcd for C₁₅H₁₀N₂O₂: 251.08; found: 251.1. Phenyl(5-p-tolyl-1,3,4-oxadiazol-2-yl)methanone (4b): Yield: 91%; white solid; mp 142–143 °C (Lit.¹⁹ 139–141 °C). IR (KBr): 1659, 1489, 1450, 1381, 1265, 1173 cm^–1. ¹H NMR (400 MHz, DMSO-d ₆): δ = 8.47 (dd, J = 8.4, 1.2 Hz, 2 H), 8.06–8.04 (m, 2 H), 7.79–7.75 (m, 1 H), 7.65–7.61 (m, 2 H), 7.45 (d, J = 8 Hz, 2 H), 2.46 (s, 3 H). ¹³C NMR (101 MHz, DMSO-d ₆): δ = 176.85, 165.49, 160.26, 143.13, 134.36, 133.64, 130.27, 129.66, 128.39, 127.13, 119.47, 21.17. MS (ESI): m/z [M + H]⁺ calcd for C₁₆H₁₂N₂O₂: 265.1; found: 265.2. [5-(4-Methoxyphenyl)-1,3,4-oxadiazol-2-yl]phenyl-methanone (4c): Yield: 91%; white crystalline solid; mp 169.6–170 °C. IR (KBr): 1612, 1574, 1551, 1489, 1380, 1285 cm^–1. ¹H NMR (500 MHz, DMSO-d ₆): δ = 8.41 (d, J = 7.7 Hz, 2 H), 8.10 (d, J = 8.5 Hz, 2 H), 7.81 (t, J = 7.2 Hz, 1 H), 7.68 (t, J = 7.5 Hz, 2 H), 7.23 (d, J = 8.5 Hz, 2 H), 3.89 (s, 3 H). MS (ESI): m/z [M + H]⁺ calcd for C₁₆H₁₂N₂O₃: 281.09; found: 281.2.
22 One-Pot Synthesis of 7a–e; General Procedure: A mixture of arylglyoxal (1 mmol) and 2-hydrazinopyridine (1 mmol) was stirred in acetonitrile at r.t. for 5 min. Subsequently, IBX (1 mmol) was added to the reaction mixture, followed by the addition of TEAB (1.2 mmol) in portions. The resulting mixture was stirred at r.t. for 15 min. Upon completion of the reaction, solvent was removed in vacuo, the contents were diluted with H₂O, and the mixture was extracted with EtOAc (3 × 25 mL). The combined organic layers were washed with saturated NaHCO₃ (20 mL), brine (20 mL), and dried over anhydrous Na₂SO₄. After filtration, the solvent was removed under reduced pressure and the residue thus obtained was recrystallized from ethanol to afford α-keto-1,2,4-triazolo[4,3-a]pyridines 7a–e in excellent yields. (1,2,4-Triazolo[4,3-a]pyridine-3-yl)phenylmethanone (7a): Yield: 90%; light-yellow solid; mp 167 °C. IR (KBr): 1658, 1573, 1496, 1450, 1411, 1380 cm^–1. ¹H NMR (400 MHz, DMSO-d ₆): δ = 9.51 (dd, J = 7.0, 1.0 Hz, 1 H), 8.51 (dd, J = 5.2, 3.3 Hz, 2 H), 8.05 (dd, J = 8.1, 1.0 Hz, 1 H), 7.73–7.67 (m, 2 H), 7.62–7.57 (m, 2 H), 7.32 (t, J = 7.4 Hz, 1 H). MS (ESI): m/z [M + H]⁺ calcd for C₁₃H₁₀N₃O: 224.08; found: 224.2.