Metal- and Oxidant-Free Electrochemical Oxidative Desulfurization C–O Coupling of Thiourea-Type Compounds with Alcohols

Abstract

An efficient desulfurization C–O coupling reaction of 3,4-dihydropyrimidine-2(1H)-thiones (including thioureas) with alcohols was developed under electrochemical oxidation conditions. Herein, transition­-metal catalysts and additives are not required and the alcohol is both the solvent and the alkoxy donor.

Key words

electrochemical oxidation - alkoxylation - alcohols - thioureas - desulfurization

• References

• 1a Frontana-Uribe BA, Little RD, Ibanez JG, Palma A, Vasquez-Medrano R. Green Chem. 2010; 12: 2099
• 1b Wiebe A, Gieshoff T, Möhle S, Rodrigo E, Zirbes M, Waldvogel SR. Angew. Chem. Int. Ed. 2018; 57: 5594; Angew. Chem. 2018, 130, 5694
• 1c Folgueiras-Amador AA, Qian X.-Y, Xu H.-C, Wirth T. Chem. Eur. J. 2018; 24: 487
• 1d Huang C, Qian X.-Y, Xu H.-C. Angew. Chem. Int. Ed. 2019; 58: 6650; Angew. Chem. 2019, 131, 6722
• 1e Jiao K.-J, Xing Y.-K, Yang Q.-L, Qiu H, Mei T.-S. Acc. Chem. Res. 2020;
• 1f Qiu Y.-A, Struwe JL, Ackermann L. Synlett 2019; 30: 1164
• 1g Meyer TH, Finger LH, Gandeepan P, Ackermann L. Trends Chem. 2019; 1: 63
• 1h Laudadio G, de A Bartolomeu A, Verwijlen LM. H. M, Cao Y, de Oliveira KT, Noël T. J. Am. Chem. Soc. 2019; 141: 11832
• 2 Pan F, Shi Z.-J. ACS Catal. 2014; 4: 280
• 3a Yeh VS. C. Tetrahedron 2004; 60: 11995
• 3b Palmer DC. Oxazoles: Synthesis, Reactions, and Spectroscopy, Vol. 1. Wiley; New Jersey: 2003
• 3c Turchi IJ, Dewar MJ. S. Chem. Rev. 1975; 75: 389
• 4a Block E. Advances in Sulfur Chemistry . JAI Press; Greenwich: 1994
• 4b Cremlyn RJ. An Introduction to Organosulfur Chemistry . Wiley; Chichester: 1996
• 4c Organic Sulfur Chemistry: Structure and Mechanism. Oae S. CRC Press; Boca Raton: 1991
• 5a Furukawa N, Sato S. In Organosulfur Chemistry II . Page PC. B. Springer; Heidelberg: 1999: 89
• 5b Rayner CM. Advances in Sulfur Chemistry, Vol. 2. JAI Press; Greenwich: 2000
• 5c Wei J, Liang H.-M, Ni C.-F, Sheng R. Org. Lett. 2019; 21: 937
• 6 Cherkasov A, Jonsson M. J. Chem. Inf. Comput. Sci. 2000; 40: 1222
• 7a Alberico D, Scott ME, Lautens M. Chem. Rev. 2007; 107: 174
• 7b Lyons TW, Sanford MS. Chem. Rev. 2010; 110: 1147
• 7c Ackermann L. Chem. Commun. 2010; 46: 4886
• 7d Xu L.-M, Li B.-J, Yang Z, Shi Z.-J. Chem. Soc. Rev. 2010; 39: 712
• 8 Otsuka S, Nogi K, Yorimitsu H. Top. Curr. Chem. 2018; 376: 199
• 9 Liebeskind LS, Srogl J. J. Am. Chem. Soc. 2000; 122: 11260
• 10 Metzger A, Melzig L, Despotopoulou C, Knochel P. Org. Lett. 2009; 11: 4228
• 11 Sugahara T, Murakami K, Yorimitsu H, Osuka A. Angew. Chem. Int. Ed. 2014; 53: 9329; Angew. Chem. 2014, 126, 9483
• 12 Lian Z, Bhawal BN, Yu P, Morandi B. Science 2017; 356: 1059
• 13a Dubbaka SR, Vogel P. Angew. Chem. Int. Ed. 2005; 44: 7674; Angew. Chem. 2005, 117, 7848
• 13b Prokopcov H, Kappe CO. Angew. Chem. Int. Ed. 2008; 47: 3674; Angew. Chem. 2008, 120, 3732
• 13c Wang L, He W, Yu Z. Chem. Soc. Rev. 2013; 42: 599
• 14 Otsuka S, Yorimitsu H, Osuka A. Chem. Eur. J. 2015; 21: 14703
• 15a Mehta VP, Modha SG, Van der Eycken E. J. Org. Chem. 2009; 74: 6870
• 15b Hintermann L, Schmitz M, Chen Y. Adv. Synth. Catal. 2010; 352: 2411
• 15c Eberhart AJ, Imbriglio JE, Procter DJ. Org. Lett. 2011; 13: 5882
• 15d Murakami K, Yorimitsu H, Osuka A. Angew. Chem. Int. Ed. 2014; 53: 7510; Angew. Chem. 2014, 126, 7640
• 16a Liebeskind LS, Srogl J. Org. Lett. 2002; 4: 979
• 16b Alphonse F.-A, Suzenet F, Keromnes A, Lebret B, Guillaumet G. Org. Lett. 2003; 5: 803
• 16c Counceller KL, Stambuli JP. C. M. Org. Lett. 2009; 11: 1457
• 16d Begouin J.-M, Gosmini C. Chem. Commun. 2010; 46: 5972
• 16e Melzig L, Metzger A, Knochel P. Chem. Eur. J. 2011; 17: 2948
• 16f Modha SG, Trivedi JC, Mehta VP, Ermolat’ev DS, Van der Eycken E. J. Org. Chem. 2011; 76: 846
• 17a Hooper JF, Young RD, Pernik I, Weller AS, Willis MC. Chem. Sci. 2013; 4: 1568
• 17b Pan F, Wang H, Shen P.-X, Shi Z.-J. Chem. Sci. 2013; 4: 1573
• 17c Creech GS, Kwon O. Chem. Sci. 2013; 4: 2670
• 18 Zhang L.-M, Si X.-J, Yang Y.-Y, Witzel S, Sekine K, Rudolph M, Rominger F, Hashmi AS. K. ACS Catal. 2019; 9: 6118
• 19 Watanabe M, Koike H, Ishiba T, Okada T. Bioorg. Med. Chem. 1997; 5: 437
• 20a Capdeville R, Buchdunger E, Zimmermann J, Matter A. Nat. Rev. Drug Discovery 2002; 1: 493
• 20b Quan Z.-J, Zhang Z, Da Y.-X. Chin. J. Org. Chem. 2009; 29: 876
• 21a Quan Z.-J, Hu W.-H, Jia X.-D, Zhang Z, Da Y.-X. Adv. Synth. Catal. 2012; 354: 2939
• 21b Yan Z.-F, Quan Z.-J, Da Y.-X, Zhang Z. Chem. Commun. 2014; 50: 13555
• 21c Quan Z.-J, Lv Y, Jing F.-Q, Jia X.-D, Huo C.-D. Adv. Synth. Catal. 2014; 356: 325
• 22a Phan NH. T, Kim H, Shin H, Lee H.-S, Sohn J.-H. Org. Lett. 2016; 18: 5154
• 22b Kim H, Lee J, Shin H, Sohn J.-H. Org. Lett. 2018; 20: 1961
• 22c Matloobi M, Kappe CO. J. Comb. Chem. 2007; 9: 275
• 22d Gershon H, Grefig AT, Scala AA. J. Heterocycl. Chem. 1983; 20: 219
• 23a Quan Z.-J, Jing F.-Q, Zhang Z, Da Y.-X, Wang X.-C. Chin. J. Chem. 2013; 31: 1495
• 23b Wang X.-C, Yang G.-J, Jia X.-D, Zhang Z, Da Y.-X, Quan Z.-J. Tetrahedron 2011; 67: 3267
• 24a Theil F. Angew. Chem. Int. Ed. 1999; 38: 2345; Angew. Chem. 1999, 111, 2493
• 24b Tolnai GL, Petho B, Krall P, Novk Z. Adv. Synth. Catal. 2014; 356: 125
• 25 Ai C.-R, Shen H.-W, Song D.-G, Li Y.-J, Yi X, Wang Z, Ling F, Zhong W.-H. Green Chem. 2019; 21: 5528
• 26a Berlinck RG. S, Kossuga MH. Nat. Prod. Rep. 2005; 22: 516
• 26b Berlinck RG. S, Burtoloso AC. B, Trindade-Silva AE, Romminger S. Nat. Prod. Rep. 2010; 27: 1871
• 27 Sauermann N, Meyer TH, Tian C. J. Am. Chem. Soc. 2017; 139: 18452
• 28 Huang P.-F, Wang P, Tang S, Fu Z.-J, Lei A.-W. Angew. Chem. Int. Ed. 2018; 57: 8115; Angew. Chem. 2018, 130, 8247
• 29 Wang L, Ma Z.-G, Wei X.-J, Meng Q.-Y, Yang D.-T, Du S.-F, Chen Z.-F, Wu L.-Z, Liu Q. Green Chem. 2014; 16: 3752
• 30 Yoon SB, Chun EJ, Noh YR. Bull. Korean Chem. Soc. 2013; 34: 2819
• 31 Bruce WM. J. Am. Chem. Soc. 1904; 26: 449