Oxidative Cross-Dehydrogenative C–H Bond Amination of Imidazo[1,2-a]pyridines in Aqueous Media under Metal-Free Conditions

Abstract

The metal-free direct oxidative cross-dehydrogenative C–H bond amination of imidazopyridines with pyrazole in water as solvent has been developed under K₂S₂O₈-promoted mild conditions. This strategy was applied to variable imidazoheterocycles to give amination products in moderate to good yields. The described protocol also offers scale-up synthesis for the construction of C–N bonds, which makes it suitable for the synthesis of biologically active compounds and pharmaceuticals.

Key words

Heterocycles - Green solvent - Metal-Free - Oxidative coupling - CDC

Publication History

Received: 27 March 2024

Accepted after revision: 19 June 2024

Accepted Manuscript online:
19 June 2024

Article published online:
10 July 2024

• References

• 1a Ricci A. Modern Amination Methods . Wiley; New York: 2008
• 1b Ricci A. Amino Group Chemistry: From Synthesis to the Life Sciences. Wiley; New York: 2008
• 1c Thansandote P, Lautens M. Chem. Eur. J. 2009; 15: 5874
• 1d Pandey G, Singh D, Laha R. Asian J. Org. Chem. 2017; 6: 469
• 1e Lim T, Byun S, Kim BM. Asian J. Org. Chem. 2017; 6: 1222
• 1f Henry MC, Mostafa MA, Sutherland A. Synthesis 2017; 49: 4586
• 1g Hirano K, Miura M. J. Synth. Org. Chem. Jpn 2018; 76: 1206
• 1h Ravindar L, Hasbullah SA, Hassan NI, Qin HL. Eur. J. Org. Chem. 2022; e202200596
• 2a Fan R, Li W, Pu D, Zhang L. Org. Lett. 2009; 11: 1425
• 2b Beukeaw D, Udomsasporn K, Yotphan S. J. Org. Chem. 2015; 80: 3447
• 2c Lucchetti N, Scalone M, Fantasia S, Muniz K. Adv. Synth. Catal. 2016; 358: 2093
• 2d Martínez C, Bosnidou AE, Allmendinger S, Muniz K. Chem. Eur. J. 2016; 22: 9929
• 2e Duhamel T, Stein CJ, Martinez C, Reiher M, Muniz K. ACS Catal. 2018; 8: 3918
• 3a Li C, Kawamata Y, Nakamura H, Vantourout JC, Liu Z, Hou Q, Bao D, Starr JT, Chen J, Yan M, Baran PS. Angew. Chem. Int. Ed. 2017; 56: 13088
• 3b Wu J, Zhou Y, Zhou Y, Chiang C.-W, Lei A. ACS Catal. 2017; 7: 8320
• 3c Zhao Y, Xia W. Chem. Soc. Rev. 2018; 47: 2591
• 3d Zhang H, Lei A. Synthesis 2019; 51: 83
• 3e Wang J.-H, Lei T, Nan X.-L, Wu H.-L, Li X.-B, Chen B, Tung C.-H, Wu L.-Z. Org. Lett. 2019; 21: 5581
• 3f Wang H, Zheng Y, Xu H, Zou J, Jin C. Front. Chem. 2022; 10: 950635
• 4a Margrey KA, McManus JB, Bonazzi S, Zecri F, Nicewicz DA. J. Am. Chem. Soc. 2017; 139: 11288
• 4b An X.-D, Yu S. Tetrahedron Lett. 2018; 59: 1605
• 5a Guram AS, Rennels RA, Buchwald SL. Angew. Chem., Int. Ed. Eng. 1995; 34: 1348
• 5b Wolfe JP, Buchwald SL. J. Org. Chem. 1997; 62: 1264
• 5c Yang BH, Buchwald SL. J. Organomet. Chem. 1999; 576: 125
• 5d Tsang WP, Zheng N, Buchwald SL. J Am. Chem. Soc. 2005; 127: 14560
• 5e Dick AR, Sanford MS. Tetrahedron 2006; 62: 2439
• 5f Surry DS, Buchwald SL. Angew. Chem. Int. Ed. 2008; 47: 6338
• 5g Bariwal J, Van der Eycken E. Chem. Soc. Rev. 2013; 42: 9283
• 5h Park Y, Kim Y, Chang S. Chem. Rev. 2017; 117: 9247
• 6a Antonchick AP, Samanta R, Kulikov K, Lategahn J. Angew. Chem. Int. Ed. 2011; 50: 8605
• 6b Xue Q, Xie J, Li H, Cheng Y, Zhu C. Chem. Commun. 2013; 49: 3700
• 6c Kielesiński Ł, Tasior M, Gryko DT. Org. Chem. Front. 2015; 2: 21
• 6d Song SZ, Meng YN, Li Q, Wei WT. Adv. Synth. Catal. 2020; 362: 2120
• 7a Davies H, Long MS. Angew. Chem. Int. Ed. 2005; 44: 3518
• 7b Liang C, Robert-Peillard F, Fruit C, Müller P, Dodd RH, Dauban P. Angew. Chem. Int. Ed. 2006; 45: 4641
• 7c Davies HM. Angew. Chem. Int. Ed. 2006; 45: 6422
• 7d Wang H, Wang Y, Peng C, Zhang J, Zhu Q. J. Am. Chem. Soc. 2010; 132: 13217
• 7e Kantak AA, Potavathri S, Barham RA, Romano KM, DeBoef B. J. Am. Chem. Soc. 2011; 133: 19960
• 7f Yoo EJ, Ma S, Mei TS, Chan KS, Yu J.-Q. J. Am. Chem. Soc. 2011; 133: 7652
• 7g Ng K.-H, Zhou Z, Yu W.-Y. Org. Lett. 2012; 14: 272
• 7h Wan J.-P, Hu D, Liu Y, Li L, Wen C. Tetrahedron Lett. 2016; 57: 2880
• 8a Fisher MH, Lusi A. J. Med. Chem. 1972; 15: 982
• 8b Shao N, Pang G.-X, Yan C.-X, Shi G.-F, Cheng Y. J. Org. Chem. 2011; 76: 7458
• 8c Shukla NM, Salunke DB, Yoo E, Mutz CA, Balakrishna R, David SA. Bioorg. Med. Chem. 2012; 20: 5850
• 8d Stasyuk AJ, Banasiewicz M, Cyrański MK, Gryko DT. J. Org. Chem. 2012; 77: 5552
• 8e Mondal S, Samanta S, Jana S, Hajra A. J. Org. Chem. 2017; 82: 4504
• 8f Patel OP, Nandwana NK, Legoabe LJ, Das BC, Kumar A. Adv. Synth. Catal. 2020; 362: 4226
• 8g Bagdi AK, Hajra A. Org. Biomol. Chem. 2020; 18: 2611
• 8h Shi L, Li T, Mei G.-J. Green Synth. Catal. 2022; 3: 227
• 8i Tran C, Hamze A. Molecules 2022; 27: 3461
• 9a Devi N, Singh D, Rawal RK, Bariwal J, Singh V. Curr. Top. Med. Chem. 2016; 16: 2963
• 9b Tashrifi Z, Mohammadi-Khanaposhtani M, Larijani B, Mahdavi M. Eur. J. Org. Chem. 2020; 269
• 10 Lian G, Li J, Liu P, Sun P. J. Org. Chem. 2019; 84: 16346
• 11a Samanta S, Ravi C, Rao SN, Joshi A, Adimurthy S. Org. Biomol. Chem. 2017; 15: 9590
• 11b Chen H, Yi H, Tang Z, Bian C, Zhang H, Lei A. Adv. Synth. Catal. 2018; 360: 3220
• 11c Yu Y, Yuan Y, Liu H, He M, Yang M, Liu P, Yu B, Dong X, Lei A. Chem. Commun. 2019; 55: 1809
• 12 Sarothiya D, Bhawale RT, Kshirsagar UA. J. Org. Chem. 2022; 87: 14915
• 13a Abdel-Kader M, Mosaad M, El-Kabbany F. Physica Status Solidi (a) 1992; 130: 351
• 13b Jiang H, Zang N, Qian X, Fu Z. J. Chem. Ind. Eng. (China) 2006; 57: 2798
• 13c Abduahadi S, Bonku EM, Qin H, Odilov A, Zhu F, Aisa HA, Shen J. Synlett 2024; in press
• 14a Romero NA, Margrey KA, Tay NE, Nicewicz DA. Science 2015; 349: 1326
• 14b Mandal S, Bera T, Dubey G, Saha J, Laha JK. ACS Catal. 2018; 8: 5085
• 14c Bhattacharjee S, Laru S, Ghosh P, Hajra A. J Org. Chem. 2021; 86: 10866
• 14d Wang K, Wei T, Zhang Y, Hou J, Bai R, Xie Y. Org. Biomol. Chem. 2021; 19: 1787
• 15a Chandra Mohan D, Reddy Donthiri R, Nageswara Rao S, Adimurthy A. Adv. Synth. Catal. 2013; 355: 2217
• 15b Pericherla K, Kaswan P, Khedar P, Khungar B, Parang K, Kumar A. RSC Adv. 2013; 3: 18923
• 15c Mohan DC, Rao SN, Ravi C, Adimurthy S. Asian J. Org. Chem. 2014; 3: 609