(3+2) Cycloadditions of Vinyl Sulfonyl Fluorides with Ethyl Diazoacetate or Azides: Metal-Free Synthesis of Pyrazole and Triazole Scaffolds via SO₂ Elimination

Abstract

A (3+2) cycloaddition reaction between substituted vinyl sulfonyl fluorides and ethyl diazoacetate or azides for the rapid construction of pyrazole or triazole cores via Michael addition and SO₂ gas elimination is developed. Trimethylsilyl azide or organic azide selectively attacks at the β-carbon of vinyl sulfonyl fluoride rather than at the S(VI) center and generates C-substituted or C,N-disubstituted triazole. In contrast, vinyl sulfonyl fluorides react with ethyl diazoacetate to generate pyrazoles in good to high yields.

Key words

azides - cycloaddition - diazo compounds - Michael addition - pyrazole - triazole - vinyl sulfonyl fluoride

Publikationsverlauf

Eingereicht: 26. März 2022

Angenommen: 19. April 2022

Artikel online veröffentlicht:
09. Juni 2022

• References


Selected reviews:
• 1a Dong J, Krasnova L, Finn MG, Sharpless KB. Angew. Chem. Int. Ed. 2014; 53: 9430
• 1b Barrow AS, Smedley CJ, Zheng Q, Li S, Dong J, Moses JE. Chem. Soc. Rev. 2019; 48: 4731
• 1c Lee C, Cook AJ, Elisabeth JE, Friede NC, Sammis GM, Ball ND. ACS Catal. 2021; 11: 6578

Selected articles:
• 2a Qin H.-L, Zheng Q, Bare GA. L, Wu P, Sharpless KB. Angew. Chem. Int. Ed. 2016; 55: 14155
• 2b Moku B, Fang W.-Y, Leng J, Kantchev EA. B, Qin HL. ACS Catal. 2019; 9: 10477
• 2c Liu J, Wang S.-M, Qin H.-L. Org. Biomol. Chem. 2020; 18. 4019
• 2d Fang W.-Y, Wang SM, Zhang W, Qin HL. Org. Lett. 2020; 22: 8904
• 2e Chen H.-R, Hu Z.-Y, Qin H.-L, Tang H. Org. Chem. Front. 2021; 8: 1185
• 2f Mykhalchuk VL, Yarmolchuk VS, Doroschuk RO, Tolmachev AA, Grygorenko OO. Eur. J. Org. Chem. 2018; 2870

For 1,3-bi-electrophiles, see:
• 3a Chinthakindi PK, Govender KB, Kumar AS, Kruger HG, Govender T, Naicker T, Arvidsson PI. Org. Lett. 2017; 19: 480
• 3b Chen X, Zha GF, Fang W.-Y, Rakesh KP, Qin H.-L. Chem. Commun. 2018; 54: 9011
• 3c Ungureanu A, Levens A, Candish L, Lupton DW. Angew. Chem. Int. Ed. 2015; 54: 11780

For 1,2-bi-electrophiles, see:
• 3d Liu H, Moku B, Li F, Ran J, Han J, Long S, Zha G.-F, Qin H.-L. Adv. Synth. Catal. 2019; 361: 4596
• 4a Thomas J, Fokin VV. Org. Lett. 2018; 20: 3749
• 4b Giel MC, Smedley CC. J, Mackie ER. R, Guo T, Dong J, Soares da Costa TP, Moses JE. Angew. Chem. Int. Ed. 2020; 59: 1181
• 4c Zhang ZW, Wang S.-M, Fang W.-Y, Lekkala R, Qin H.-L. J. Org. Chem. 2020; 85: 13721
• 4d Nair D, Pavashe P, Namboothiri IN. N. Tetrahedron 2018; 74: 2716

For pyrazoles, see:
• 5a Singer RA, Caron S, McDermott RE, Arpin P, Do NM. Synthesis 2003; 1727
• 5b Kowalczyk R, Skarzewski J. Tetrahedron 2005; 61: 623
• 5c Singer RA, Dore M, Sieser JE, Berliner MA. Tetrahedron Lett. 2006; 47: 3727
• 5d Lahm GP, Cordova D, Barry JD. Bioorg. Med. Chem. 2009; 17: 4127
• 5e Fustero S, Román R, Sanz-Cervera JF, Simón-Fuentes A, Bueno J, Villanova S. J. Org. Chem. 2008; 73: 8545
• 5f Chowdhury MA, Abdellatif KR. A, Dong Y, Yu G, Huang Z, Rahman M, Das D, Velazquez CA, Suresh MR, Knaus EE. Bioorg. Med. Chem. Lett. 2010; 20: 1324
• 5g Thirunavukkarasu VS, Raghuvanshi K, Ackermann L. Org. Lett. 2013; 15: 3286
• 5h Liu PM, Frost CG. Org. Lett. 2013; 15: 5862

For triazoles, see:
• 6a Angell YL, Burgess K. Chem. Soc. Rev. 2007; 36: 1674
• 6b Tam A, Arnold U, Soellner MB, Raines RT. J. Am. Chem. Soc. 2007; 129: 12670
• 6c Ito S, Satoh A, Nagatomi Y, Hirata Y, Suzuki G, Kimura T, Satow A, Maehara S, Hikichi H, Hata M, Kawamoto H, Ohta H. Bioorg. Med. Chem. 2008; 16: 9817
• 6d Tsuritani T, Mizuno H, Nonoyama N, Kii S, Akao A, Sato K, Yasuda N, Mase T. Org. Process Res. Dev. 2009; 13: 1407
• 6e Ito S, Hirata Y, Nagatomi Y, Satoh A, Suzuki G, Kimura T, Satow A, Maehara S, Hikichi H, Hata M. Bioorg. Med. Chem. Lett. 2009; 19: 5310
• 6f Holub JM, Kirshenbaum K. Chem. Soc. Rev. 2010; 39: 1325
• 6g Agalave SG, Maujan SR, Pore VS. Chem. Asian J. 2011; 6: 2696
• 6h Fujinaga M, Yamasaki T, Kawamura K, Kumata K, Hatori A, Yui J, Yanamoto K, Yoshida Y, Ogawa M, Nengaki N, Maeda J, Fukumura T, Zhang M.-R. Bioorg. Med. Chem. 2011; 19: 102
• 6i Valverde IE, Bauman A, Kluba CA, Vomstein S, Walter MA, Mindt TL. Angew. Chem. Int. Ed. 2013; 52: 8957
• 6j Thirumurugan P, Matosiuk D, Jozwiak K. Chem. Rev. 2013; 113: 4905

For classical bioisosteres, see:
• 7a Mohammed I, Kummetha IR, Singh G, Sharova N, Lichinchi G, Dang J, Stevenson M, Rana TM. J. Med. Chem. 2016; 59: 7677
• 7b Bonandi E, Christodoulou MS, Fumagalli G, Perdicchia D, Rastelli G, Passarella D. Drug Discov. Today 2017; 22: 1572

For classical bioisosteres see:
• 7c Tseng S.-L, Hung MS, Chang CP, Song J.-S, Tai C-L, Chiu H.-H, Hsieh W.-P, Lin Y, Chung WL, Kuo C-W, Wu C.-H, Chu C.-M, Tung Y.-S, Chao Y.-S, Shia K.-S. J. Med. Chem. 2008; 51: 5397
• 8a Fustero S, María S.-R, Barrio P, Antonio S.-F. Chem. Rev. 2011; 111: 6984 (pyrazole)
• 8b Chen Z, Liu Z, Cao G, Li H, Ren H. Adv. Synth. Catal. 2017; 359: 202 (triazole)
• 8c Surendra GR, Anebouselvy K, Ramachary DB. Chem. Asian J. 2020; 15: 2960 (triazole)
• 8d Mo F, Qiu D, Zhang L, Wang J. Chem. Rev. 2021; 121: 5741 (pyrazole)

For triazoles, see:
• 9a Reddy RJ, Waheed M, Karthik T, Shankar A. New J. Chem. 2018; 42: 980
• 9b Mali M, Jayaram V, Sharma GV. M, Ghosh S, Berreé F, Dorcet V, Carboni B. J. Org. Chem. 2020; 85: 15104
• 9c Cui X, Zhang X, Wang W, Zhong X, Tan Y, Wang Y, Zhang J, Li Y, Wang X. J. Org. Chem. 2021; 86: 4071
• 9d Majeed K, Wang L, Liu B, Guo Z, Zhou F, Zhang Q. J. Org. Chem. 2021; 86: 207

For pyrazoles see:
• 9e Xie J.-W, Wang Z, Yang W.-J, Kong L.-C, Xu D.-C. Org. Biomol. Chem. 2009; 7: 4352
• 9f Specklin S, Decuypere E, Plougastel L, Aliani S, Taran F. J. Org. Chem. 2014; 79: 7772
• 9h Yi F, Zhao W, Wang Z, Bi X. Org. Lett. 2019; 21: 3158

For triazoles, see:
• 10a Huisgen R. Angew. Chem., Int. Ed. Engl. 1963; 2: 565
• 10b Huisgen R. Angew. Chem., Int. Ed. Engl. 1963; 2: 633
• 10c Kolb HC, Finn MG, Sharpless KB. Angew. Chem. Int. Ed. 2001; 40: 2004
• 10d Rostovtsev VV, Green LG, Fokin VV, Sharpless KB. Angew. Chem. Int. Ed. 2002; 41: 2596
• 10e Tornøe CW, Christensen C, Meldal MP. J. Org. Chem. 2002; 67: 3057

For pyrazoles, see:
• 10f Bonnert RV. J. Org. Chem. 2003; 68: 5381
• 10g Jiang N, Li C.-J. Chem. Commun. 2004; 394

For triazoles, see:
• 11a Boren BC, Narayan S, Rasmussen LK, Zhang L, Zhao H, Lin Z, Jia G, Fokin VV. J. Am. Chem. Soc. 2008; 130: 8923
• 11b Ding S, Jia G, Sun J. Angew. Chem. Int. Ed. 2014; 53: 1877
• 11c Lal S, Rzepa HS, Díez-González S. ACS Catal. 2014; 4: 2274
• 11d Liao Y, Lu Q, Chen G, Yu Y, Li C, Huang X. ACS Catal. 2017; 7: 7529
• 11e Song W, Zheng N, Li M, Dong K, Li J, Ullah K, Zheng Y. Org. Lett. 2018; 20: 6705

For pyrazoles, see:
• 11f Zhou Q, Du F, Chen Y, Fu Y, Sun W, Wu Y, Chen G. J. Org. Chem. 2019; 84: 8160
• 11g Fan Z, Feng J, Hou Y, Rao M, Cheng J. Org. Lett. 2020; 22: 7981
• 11h Schmitt DC, Taylor AP, Flick AC, Kyne RE. Jr. Org. Lett. 2015; 17: 1405
• 11i Ding Y, Zhang T, Chen Q.-Y, Zhu C. Org. Lett. 2016; 18: 4206
• 11j Li DY, Mao XF, Chen HJ, Chen GR, Liu PN. Org. Lett. 2014; 16: 3476
• 12a Chakravarty M, Bhuvan Kumar NN, Sajna KV, Kumara Swamy KC. Eur. J. Org. Chem. 2008; 4500
• 12b Reddy MN, Kumara Swamy KC. Eur. J. Org. Chem. 2012; 2013
• 12c Sajna KV, Kumara Swamy KC. J. Org. Chem. 2012; 77: 8712
• 12d Reddy MN, Kumara Swamy KC. Org. Biomol. Chem. 2013; 11: 7350
• 12e Reddy AS, Reddy MN, Kumara Swamy KC. RSC Adv. 2014; 4: 28359
• 12f Kumari AL. S, Kumara Swamy KC. J. Org. Chem. 2016; 81: 1425
• 12g Anitha M, Kumara Swamy KC. Org. Biomol. Chem. 2019; 17: 5736
• 12h Qureshi AA, Kumar AS, Chauhan S, Kumara Swamy KC. Synthesis 2022; 54: 965
• 13 CCDC numbers 2141604 (3g) and 2141605 (7ac) contain the supplementary crystallographic data for this paper. The data can be obtained free of charge from The Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/structures
• 14a Pinna GA, Pirisi MA, Mussinu J.-M, Murineddu G, Loriga G, Pau A, Grella GE. Farmaco 2003; 58: 749
• 14b Kallander LS, Lu Q, Chen W, Tomaszek T, Yang G, Tew D, Meek TD, Hofmann GA, Schulz-Pritchard CK, Smith WW, Janson CA, Ryan MD, Zhang F, Johanson KO, Kirkpatrick RB, Ho TF, Fisher PW, Mattern MR, Johnson RK, Hansbury MJ, Winkler JD, Ward KW, Veber DF, Thompson SK. J. Med. Chem. 2005; 48: 5644
• 14c Hui R, Zhao M, Chen M, Ren Z, Guan Z. Chin. J. Chem. 2017; 12: 1808
• 14d Tomé AC. Science of Synthesis 2004; 13: 415
• 14e Hong L, Lin W, Zhang F, Liu R, Zho X. Chem. Commun. 2013; 49: 5589
• 14f Cheng G, Zeng X, Shen J, Wang X, Cui X. Angew. Chem. Int. Ed. 2013; 52: 13265