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Metal-free selective aryl C–H formylation co-controlled by 1,2,3-triazole and hydroxyl using DMSO as formyl source

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Abstract

Abstract

A facile and efficient method for direct C–H formylation of phenolated 1,4-disubstituted 1,2,3-triazoles using DMSO as the formyl source has been developed. The reaction proceeded smoothly under metal-free conditions with good functional group tolerance and high selectivity co-controlled by the triazole ring and hydroxyl group.

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Synopsis Direct C–H formylation of phenolated 1,4-disubstituted 1,2,3-triazoles using DMSO as the formyl source has been developed under metal-free conditions with good functional group tolerance and high selectivity.

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References

  1. Olah G A, Ohannesianm L and Arvanaghi M 1987 Formylating agents Chem. Rev. 87 671

    Article  CAS  Google Scholar 

  2. Zhu C, Pinkert T, Greßies S and Glorius F 2018 One-pot C–H formylation enabled by relay catalysis of manganese(I) and iron(III) ACS Catal. 8 10036

    Article  CAS  Google Scholar 

  3. Lauchli R and Shea K J 2006 A synthesis of the welwistatin core Org. Lett. 8 5287

    Article  CAS  Google Scholar 

  4. Roudias M, Vallée F, Martel J and Paquin J -F 2018 Use of XtalFluor-E as an alternative to POCl\(_{3}\) in the Vilsmeier-Haack formylation of C-2-glycals J. Org. Chem. 83 8731

    Article  CAS  Google Scholar 

  5. Zaman A, Ahmad I, Pervaiz M, Ahmad S, Kiran S, Khan M A, Gulzar T and Kamal T 2019 A novel synthetic approach for the synthesis of pyrano[3, 2-c] quinolone-3carbaldehydes by using modified Vilsmeier Haack reaction, as potent antimicrobial agents J. Mol. Struct. 1180 227

    Article  CAS  Google Scholar 

  6. Duff J C and Bills E J 1932 Reactions between hexamethylenetetramine and phenolic compounds. Part I. A new method for the preparation of 3- and 5-aldehydosalicylic acids J. Chem. Soc. 1987

  7. Grimblat N, Sarotti A M, Kaufman T S and Simonetti S O 2016 A theoretical study of the Duff reaction: insights into its selectivity Org. Biomol. Chem. 14 10496

    Article  CAS  Google Scholar 

  8. Weclawski M K, Deperasińska I, Leniak A, Banasiewicz M, Kozankiewicz B and Gryko D T 2016 Unexpected formation of \(\pi \)-expanded isoquinoline from anthracene possessing four electron-donating groups via the Duff reaction Org. Biomol. Chem. 14 7046

    Article  CAS  Google Scholar 

  9. Yamabe S and Fukuda T 2011 A significant role of alkaline cations on the Reimer-Tiemann reaction Org. Biomol. Chem. 9 5109

    Article  CAS  Google Scholar 

  10. Ren S, Wu Z, Guo Q and Shen B 2015 Zeolites as shape-selective catalysts: highly selective synthesis of vanillin from Reimer–Tiemann reaction of guaiacol and chloroform Catal. Lett. 145 712

    Article  CAS  Google Scholar 

  11. Kolanowska A, Kuziel A, Li Y, Jurczykb S and Boncel S 2017 Rieche formylation of carbon nanotubes—one-step and versatile functionalization route RSC Adv. 7 51374

    Article  CAS  Google Scholar 

  12. Katritzky A R, Suzuki K, Singh S K and He H -Y 2003 Regiospecific \(C\)-acylation of pyrroles and indoles using \(N\)-acylbenzotriazoles J. Org. Chem. 68 5720

    Article  CAS  Google Scholar 

  13. Chakiri A B and Hodge P 2017 Synthesis of isopropyl-substituted anthraquinones via Friedel–Crafts acylations: migration of isopropyl groups R. Soc. Open Sci. 4 170451

    Article  Google Scholar 

  14. (a) Qian J, Zhang Z, Liu Q, Liu T and Zhang G 2014 Dimethyl sulfoxide participating in copper(I) iodide-catalyzed cascade oxidation/formylation reactions: the synthesis of \(a\)-formylpyrroles from 2, 3-dihydro-1\(H\)-pyrroles Adv. Synth. Catal. 356 3119; (b) Cui X, Zhang Y, Deng Y and Shi F 2014 Amine formylation via carbon dioxide recycling catalyzed by a simple and efficient heterogeneous palladium catalyst Chem. Commun. 50 189

  15. (a) Pummerer R 1909 Uber phenyl-sulfoxyessigsaure Ber. Dtsch. Chem. Ges. 42 2282; (b) Bur S K and Padwa A 2004 The Pummerer reaction: methodology and strategy for the synthesis of heterocyclic compounds Chem. Rev. 104 2401; (c) Hu G, Xu J and Li P 2018 Synthesis of \(N\)-alkylated 2-pyridones through Pummerer type reactions of activated sulfoxides and 2-fluoropyridine derivatives Org. Biomol. Chem. 16 4151

  16. Parnes R, Reiss H and Pappo D 2018 \(\text{ Cu }(\text{ OTf })_{2}\)-catalyzed Pummerer coupling of \(\beta \)-ketosulfoxides J. Org. Chem. 83 723

    Article  CAS  Google Scholar 

  17. Zhang Z, Tian Q, Qian J, Liu Q, Liu T, Shi L and Zhang G 2014 Dimethyl sulfoxide participant iron-mediated cascade oxidation/\(\alpha \)-formylation reaction of substituted 2, 3-dihydropyrroles under air and protonic acid free condition J. Org. Chem. 79 8182

    Article  CAS  Google Scholar 

  18. Cao H, Lei S, Li N, Chen L, Liu J, Cai H, Qiu S and Tan J 2015 Cu-catalyzed selective \(\text{ C }_{3}\)-formylation of imidazo[1, 2-\(a\)]pyridine C–H bonds with DMSO using molecular oxygen Chem. Commun. 51 1823

    Article  CAS  Google Scholar 

  19. (a) Rostovtsev V V, Green L G, Fokin V V and Sharpless B K 2002 A stepwise huisgen cycloaddition process: copper(I)-catalyzed regioselective “ligation” of azides and terminal alkynes Angew. Chem. Int. Ed. 41 2596; (b) Deraedt C, Pinaud N and Astruc D 2014 Recyclable catalytic dendrimer nanoreactor for part-per-million CuI catalysis of “click” chemistry in water J. Am. Chem. Soc. 136 12092; (c) Song W and Zheng N 2017 Iridium-catalyzed highly regioselective azide-ynamide cycloaddition to access 5-amido fully substituted 1, 2, 3-triazoles under mild, air, aqueous, and bioorthogonal conditions Org. Lett. 19 6200; (d) Luo G, Sun C, Li Y, Li X and Zhao Z 2018 N\(_{2}\)-Selective alkylation of NH-1, 2, 3-triazoles with vinyl ethers via gold catalysis RSC Adv. 8 27610

  20. (a) Yu X, Huang Z, Liu W, Shi S and Kuang C 2015 Palladium-catalyzed oxidative C–H/C–H cross-coupling of 1-substituted 1, 2, 3-triazoles with furans and thiophenes Org. Biomol. Chem. 13 4459; (b) He P, Tian Q and Kuang C 2015 Palladium-catalyzed ortho-C–H alkenylation of 2-benzyl-1, 2, 3-triazoles Org. Biomol. Chem. 13 7146

  21. (a) He C and Shreeve J M 2015 Energetic materials with promising properties: synthesis and characterization of 4, 4’-bis(5-nitro-1, 2, 3-2\(H\)-triazole) derivatives Angew. Chem. Int. Ed. 54 6260; (b) Johansson J R, Beke-Somfai T, Stalsmeden A S and Kann N 2016 Ruthenium-catalyzed azide alkyne cycloaddition reaction: scope, mechanism, and applications Chem. Rev. 116 14726

  22. (a) Emileh A, Duffy C, Holmes A P, Bastian A R, Aneja R, Tuzer F, Rajagopal S, Li H, Abrams C F and Chaiken I M 2014 Covalent conjugation of a peptide triazole to HIV1 gp120 enables intramolecular binding site occupancy Biochemistry 53 3403; (b) Kuntala N, Telu J R, Banothu V, Nallapati S B, Anireddy J S and Pal S 2015 Novel benzoxepine-1, 2, 3-triazole hybrids: synthesis and pharmacological evaluation as potential antibacterial and anticancer agents Med. Chem. Comm. 6 1612

  23. (a) Kumar P, Joshi C, Srivastava A K, Gupta P, Boukherroub R and Jain S L 2016 Visible light assisted photocatalytic [3 + 2] azide–alkyne “click” reaction for the synthesis of 1, 4-substituted 1, 2, 3-triazoles using a novel bimetallic Ru–Mn complex ACS Sustain. Chem. Eng. 4 69; (b) Rostovskii N V, Ruvinskaya J O, Novikov M S, Khlebnikov A F, Smetanin I A and Agafonova A V 2017 Switchable synthesis of pyrroles and pyrazines via Rh(II)-catalyzed reaction of 1, 2, 3-triazoles with isoxazoles: experimental and DFT evidence for the 1, 4-diazahexatriene intermediate J. Org. Chem. 82 256

  24. (a) Lal K, Yadav P and Kumar A 2016 Synthesis, characterization and antimicrobial activity of 4-((1-benzyl/phenyl-1\(H\)-1, 2, 3-triazol-4-yl)methoxy) benzaldehyde analogues Med. Chem. Res. 25 644; (b) Dhamodharan P, Sathya K and Dhandapani M 2017 Studies on synthesis, structural, luminescent and thermal properties of a new non-linear optical crystal: 4-amino-4\(H\)-1, 2, 4-triazol-1-ium-3-hydroxy-2, 4, 6-trinitrophenolate Physica B. 508 33; (c) Radhakrishna L, Pandey M K and Balakrishna M S 2018 1, 2, 3-Triazole based bisphosphine, 5-(diphenylphosphanyl)-1-(2-(diphenylphosphanyl)-phenyl)-4-phenyl-1\(H\)-1, 2, 3-triazole: an ambidentate ligand with switchable coordination modes RSC Adv. 8 25704

  25. Rastegari A, Nadri H, Mahdavi M, Moradi A, Mirfazli S S, Edraki N, Moghadam F H, Larijani B, Akbarzadeh T and Saeedi M 2019 Design, synthesis and anti-Alzheimer’s activity of novel 1, 2, 3-triazole-chromenone carboxamide derivatives Bioorg. Chem. 83 391

    Article  CAS  Google Scholar 

  26. Saeedi M, Mohammadi-Khanaposhtani M, Pourrabia P, Razzaghi N, Ghadimi R, Imanparast S, Faramarzi M A, Bandarian F, Esfahani E N, Safavi M, Rastegar H, Larijani B, Mahdavi M and Akbarzadeh T 2019 Design and synthesis of novel quinazolinone-1, 2, 3-triazole hybrids as new anti-diabetic agents: in vitro \(\alpha \)-glucosidase inhibition, kinetic, and docking study Bioorg. Chem. 83 161

    Article  CAS  Google Scholar 

  27. (a) Pagliai F, Pirali T, Grosso E D, Brisco R D, Tron G C, Sorba G and Genazzani A A 2006 Rapid synthesis of triazole-modified resveratrol analogues via click chemistry J. Med. Chem. 49 467; (b) Aouad M R, Soliman M A, Alharbi M O, Bardaweel S K, Sahu P K, Ali A A, Messali M, Rezki N and Al-Soud Y A 2018 Design, synthesis and anticancer screening of novel benzothiazole-piperazine-1, 2, 3-triazole hybrids Molecules 23 2788

  28. (a) Jana S, Iram S, Thomas J, Hayat M Q, Pannecouque C and Dehaen W 2017 Application of the triazolization reaction to afford dihydroartemisinin derivatives with anti-HIV activity Molecules 22 303; (b) Pribut N, Veale C G L, Basson A E, van Otterlo W A L and Pelly S C 2016 Application of the Huisgen cycloaddition and ‘click’ reaction toward various 1, 2, 3-triazoles as HIV non-nucleoside reverse transcriptase inhibitors Bioorg. Med. Chem. Lett. 26 3700

  29. (a) Ackermann L, Althammer A and Fenner S 2009 Palladium-catalyzed direct arylations of heteroarenes with tosylates and mesylates Angew. Chem. Int. Ed. 48 201; (b) Ackermann L, Jeyachandran R, Potukuchi H, Novak P and Buttner L 2010 Palladium-catalyzed dehydrogenative direct arylations of 1, 2, 3-triazoles Org. Lett. 12 2056; (c) Tirler C and Ackermann L 2015 Ruthenium(II)-catalyzed cross-dehydrogenative C–H alkenylations by triazole assistance Tetrahedron 71 4543; (d) Ackermann L, Vicente R and Born R 2008 Palladium-catalyzed direct arylations of 1, 2, 3-triazoles with aryl chlorides using conventional heating Adv. Synth. Catal. 350 741

  30. Li X, Liu K, Zou G and Liu P 2014 Ruthenium-catalyzed alkenylation of arenes with alkynes or alkenes by 1, 2, 3-triazole-directed C–H activation Eur. J. Org. Chem. 7878

    Article  CAS  Google Scholar 

  31. Zhao S, Yu R, Chen W, Liu M and Wu H 2015 Efficient approach to mesoionic triazolo[5, 1-\(a\)]isoquinolium through rhodium-catalyzed annulation of triazoles and internal alkynes Org. Lett. 17 2828

    Article  CAS  Google Scholar 

  32. (a) Zhao F, Chen Z, Huang S and Jiang Y 2016 Palladium-catalyzed nitration of arenes by 1, 2, 3-triazole-directed C–H activation Synthesis 48 2105; (b) Zhao F, Chen Z, Liu Y, Xie K and Jiang Y 2016 Palladium-catalyzed acylation of arenes by 1, 2, 3-triazole-directed C–H activation Eur. J. Org. Chem. 5971; (c) Zhao F, Liu Y, Yang S, Xie K and Jiang Y 2017 Pd-catalyzed selective N(3)-ortho C–H arylation of 1, 4-disubstituted 1, 2, 3-triazoles Org. Chem. Front. 4 1112; (d) Zhao F, Chen Z, Ma X, Huang S and Jiang Y 2017 Palladium-catalyzed acetoxylation of arenes by 1, 2, 3-triazole-directed C–H activation Tetrahedron Lett. 58 614; (e) Liu Y, Zhang W, Xie K and Jiang Y 2017 Silver-catalyzed intramolecular C(5)–H acyloxylation of 1, 4-disubstituted 1, 2, 3-triazoles Synlett 28 1496; (f) Ma X, Huang H, Yang J, Feng X and Xie K 2018 Pd-catalyzed decarboxylative N(3)-ortho C–H acylation of 1, 4-disubstituted 1, 2, 3-triazoles with \(\alpha \)-oxocarboxylic acids Synthesis 50 2567; (g) Ma X, Mo Q, Chang J and Xie K 2018 Pd-catalyzed regioselective C–H chlorination of disubstituted 1, 2, 3-triazoles Synth. Commun. 48 1403; (h) Ma X, Liu Y, Xie K and Jiang Y 2018 Pd-catalyzed selective decarboxylation/C–H activation coupling of aryl acid with thiazole and oxazole directed by 1, 2, 3-triazole Tetrahedron Lett. 59 3624; (i) Yang J, Zhao F, Liu Y, Luo F, Cheng H and Jiang Y 2018 Selective diacetoxylation of disubstituted 1, 2, 3-triazoles through palladium-catalyzed C–H activation Synlett  29 1373

  33. CCDC 1884642 contains the supplementary crystallographic data for this paper. The data can be obtained free of charge from The Cambridge Crystallographic Data Centre via https://www.ccdc.cam.ac.uk

  34. Burdon M G and Moffatt J G 1966 Sulfoxide-carbodiimide reactions. IV. acid-catalyzed reactions of phenols with sulfoxides and carbodiimides J. Am. Chem. Soc. 88 5855

    Article  CAS  Google Scholar 

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Acknowledgements

This work is supported by the National Natural Science Foundation of China (Nos. 21662020 and 21801101) and the Analysis and Testing Fund of Kunming University of Science and Technology (No. 2017M20162111052).

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Authors and Affiliations

  1. Faculty of Science, Kunming University of Science and Technology, Kunming, 650500, China

    Xinyuan Ma, Weigen Du, Yaowen Liu, Tiebo Xiao & Yubo Jiang

  2. School of Pharmacy, Nantong University, Nantong, 226001, China

    Wei Liu

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  1. Xinyuan Ma
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  2. Weigen Du
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  3. Wei Liu
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Correspondence to Tiebo Xiao or Yubo Jiang.

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Ma, X., Du, W., Liu, W. et al. Metal-free selective aryl C–H formylation co-controlled by 1,2,3-triazole and hydroxyl using DMSO as formyl source. J Chem Sci 131, 55 (2019). https://doi.org/10.1007/s12039-019-1631-8

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