Synlett 2018; 29(17): 2283-2287
DOI: 10.1055/s-0037-1610271
letter
© Georg Thieme Verlag Stuttgart · New York

Copper-Catalyzed Synthesis of Substituted 4-Acylpyrazole Derivatives through a Cascade Transformation from N-Propargylic Sulfonylhydrazones and Diaryliodonium Salts

Ren-Hao Li
a   Department of Chemistry and Key Laboratory for Chemical Biology of Fujian Province, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen, Fujian, P. R. of China   eMail: yhchen@xmu.edu.cn
,
Xin-Yang Fan
a   Department of Chemistry and Key Laboratory for Chemical Biology of Fujian Province, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen, Fujian, P. R. of China   eMail: yhchen@xmu.edu.cn
,
Zi-Lin Hu
a   Department of Chemistry and Key Laboratory for Chemical Biology of Fujian Province, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen, Fujian, P. R. of China   eMail: yhchen@xmu.edu.cn
,
Zhi-Kai Liu
a   Department of Chemistry and Key Laboratory for Chemical Biology of Fujian Province, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen, Fujian, P. R. of China   eMail: yhchen@xmu.edu.cn
,
Ying Yang
a   Department of Chemistry and Key Laboratory for Chemical Biology of Fujian Province, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen, Fujian, P. R. of China   eMail: yhchen@xmu.edu.cn
,
Hai-Tao Tang
b   State Key Laboratory for the Chemistry and Molecular Engineering of Medicinal Resources, School of Chemistry and Pharmaceutical Sciences of Guangxi Normal University, Guilin 541004, P. R. of China
,
Yi-Hui Chen*
a   Department of Chemistry and Key Laboratory for Chemical Biology of Fujian Province, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen, Fujian, P. R. of China   eMail: yhchen@xmu.edu.cn
,
Li Chen
a   Department of Chemistry and Key Laboratory for Chemical Biology of Fujian Province, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen, Fujian, P. R. of China   eMail: yhchen@xmu.edu.cn
,
Zhuang-Ping Zhan
a   Department of Chemistry and Key Laboratory for Chemical Biology of Fujian Province, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen, Fujian, P. R. of China   eMail: yhchen@xmu.edu.cn
› Institutsangaben
Financial support from the National Natural Science Foundation of China (no. 21772166) and the NFFTBS (no. J1310024) is gratefully acknowledged.
Weitere Informationen

Publikationsverlauf

Received: 02. Juli 2018

Accepted after revision: 14. August 2018

Publikationsdatum:
03. September 2018 (online)


Abstract

A concise strategy for the synthesis of substituted 4-acylpyrazole derivatives from N-propargylic sulfonylhydrazones and diaryliodonium salts has been developed. The pyrazole derivatives are formed through a five-step cascade sequence that includes intramolecular cyclization, hydroxylation, elimination, copper-catalyzed aerobic oxidation, and intramolecular rearrangement.

Supporting Information

 
  • References and Notes

    • 1a Bekhit AA. Abdel-Aziem T. Bioorg. Med. Chem. 2004; 12: 1935
    • 1b Manna F. Chimenti F. Fioravanti R. Bolasco A. Secci D. Chimenti P. Ferlini C. Scambia G. Bioorg. Med. Chem. Lett. 2005; 15: 4632
    • 1c Fahmy HH. Khalifa NM. Ismail MM. El-Sahrawy HM. Nossier ES. Molecules 2016; 21: 271
    • 1d Venância Faria J. Fazolin Vegi P. Carvalho Miguita AG. Silva Dos Santos M. Boechat N. Rolim Bernardino AM. Bioorg. Med. Chem. 2017; 25: 5891
  • 2 Ralph JM. Faitg TH. Silva DJ. Feng Y. Blackledge CW. Adams JL. Tetrahedron Lett. 2009; 50: 1377
    • 3a Schmink JR. Krska SW. J. Am. Chem. Soc. 2011; 133: 19574
    • 3b Weires NA. Baker EL. Garg NK. Nat. Chem. 2016; 8: 75
    • 3c Lian Z. Nielsen DU. Lindhardt AT. Daasbjerg K. Skrydstrup T. Nat. Commun. 2016; 7: 13782
  • 4 Bagley MC. Davis T. Dix MC. Murziani PG. Rokicki MJ. Kipling D. Bioorg. Med. Chem. Lett. 2008; 18: 3745
  • 5 Nishiwaki N. Matsushima K. Chatani M. Tamura M. Ariga M. Synlett 2004; 703
  • 6 Taydakov I. Krasnoselskiy S. Synthesis 2013; 45: 2188
  • 7 Tian M. Shi X. Zhang X. Fan X. J. Org. Chem. 2017; 82: 7363
  • 8 Young TL. Young KC. J. Org. Chem. 2008; 73: 4698
  • 9 Zhu Y. Lu W.-T. Sun H.-C. Zhan Z.-P. Org. Lett. 2013; 15: 4146
  • 10 Wen JJ. Tang HT. Xiong K. Ding ZC. Zhan ZP. Org. Lett. 2014; 16: 5940
  • 11 Wen J.-J. Ding C.-K. Ding Z.-C. Li T. Zhan Z.-P. Eur. J. Org. Chem. 2015; 2015: 5230
    • 12a Merritt EA. Olofsson B. Angew. Chem. Int. Ed. 2009; 48: 9052
    • 12b Sasaki T. Miyagi K. Moriyama K. Togo H. Org. Lett. 2016; 18: 944
    • 12c Pérez-Saavedra B. Vázquez-Galiñanes N. Saá C. Fañanás-Mastral M. ACS Catal. 2017; 7: 6104
    • 12d Miralles N. Romero RM. Fernández E. Muñiz K. Chem. Commun. 2015; 51: 14068
    • 12e Huang Z. Sam QP. Dong G. Chem. Sci. 2015; 6: 5491
    • 12f Wang G. Chen C. Peng J. Chem. Commun. 2016; 52: 10277
    • 12g Wen L.-R. Shen Q.-Y. Guo W.-S. Li M. Org. Chem. Front. 2016; 3: 870
    • 12h Ma X.-P. Li K. Wu S.-Y. Liang C. Su G.-F. Mo D.-L. Green Chem. 2017; 19: 5761
    • 12i Guo J. Dong S. Zhang Y. Kuang Y. Liu X. Lin L. Feng X. Angew. Chem. Int. Ed. 2013; 52: 10245
    • 12j Gao P. Guo W. Xue J. Zhao Y. Yuan Y. Xia Y. Shi Z. J. Am. Chem. Soc. 2015; 137: 12231
  • 13 Chen B. Hou X.-L. Li Y.-X. Wu Y.-D. J. Am. Chem. Soc. 2011; 133: 7668
  • 14 Pyrazoles 3am; General Procedure A 10 mL round-bottomed flask was charged with the appropriate N-propargylic sulfonylhydrazone 1 (0.5 mmol), diaryliodonium salt 2 (0.75 mmol), and Cu(OTf)2 (18.1 mg, 0.05 mmol). Undried DBE (5 mL) was added, and the mixture was stirred at 80 °C in air until the reaction was complete (TLC). The solvent was removed under vacuum, and the crude residue was purified by column chromatography (silica gel, eluent: petroleum ether/EtOAc = 30/1). (1,3-Diphenyl-1H-pyrazol-4-yl)(phenyl)methanone (3a) White solid; yield: 92 mg (57%); mp 117–119 °C. 1H NMR (500 MHz, CDCl3): δ = 7.34–7.37 (m, 2 H), 7.43 (t, J = 7.7 Hz, 2 H), 7.50–7.56 (m, 4 H), 7.74–7.77 (m, 2 H), 7.80–7.88 (m, 5 H), 8.31 (s, 1 H). 13C NMR (125 MHz, CDCl3): δ = 119.6, 121.2, 127.5, 128.1, 128.3, 128.6, 128.9, 129.4, 129.6, 132.1, 132.2, 132.6, 138.9, 139.2, 154.0, 190.0. HRMS (ESI): m/z [M + Na] calcd for C22H16N2NaO: 347.1155; found: 347.1160. [3-(4-Bromophenyl)-1-(4-tolyl)-1H-pyrazol-4-yl](phenyl)-methanone (3b) White solid; yield: 102 mg (49%); mp 139–141 °C. 1H NMR (400 MHz, CDCl3): δ = 2.43 (s, 3 H), 7.30 (d, J = 8.0 Hz, 2 H), 7.44–7.52 (m, 4 H), 7.58 (t, J = 7.3 Hz, 1 H), 7.64–7.72 (m, 4 H), 7.86 (d, J = 7.7 Hz, 2 H), 8.23 (s, 1 H). 13C NMR (100 MHz, CDCl3): δ = 21.0, 119.5, 120.8, 122.8, 128.4, 129.4, 130.1, 130.5, 131.1, 131.2, 132.5, 132.6, 136.8, 137.7, 138.9, 152.6, 189.7. HRMS (ESI): m/z [M + Na] calcd for C23H17BrN2NaO: 439.0416 and 441.0396; found: 439.0419 and 441.0399.