I₂/CH₃ONa-Promoted Ring-Opening Alkylation of Benzothiazoles with Dialkyl Carbonates

Abstract

Dialkyl carbonates were used as the green alkylating reagents in the I₂-promoted ring-opening alkylation of benzothiazoles. A variety of benzo[d]thiazole derivatives underwent the alkylation smoothly to provide the diverse N-alkyl-N-(o-alkylthio)phenylformamides in moderate to excellent yields. The synthetic utility of this protocol was verified by gram-scale reaction and further derivatization of the products. The mechanism of the involvement of two molecules of dialkyl carbonates in the formation of sulfur-alkyl and nitrogen-alkyl groups, respectively, was also demonstrated.

Key words

alkylation - benzothiazole - dialkyl carbonate - ring-opening - iodine

Publication History

Received: 15 April 2022

Accepted after revision: 28 September 2022

Article published online:
03 November 2022

• References

• 1a Tundo P, Musolino M, Aricò F. Front. Chem. 2019; 7: 300
• 1b Musolino M, Aricò F. Synthesis 2019; 51: 1770
• 1c Huang S, Yan B, Wang S, Ma X. Chem. Soc. Rev. 2015; 44: 3079
• 1d Tabanelli T, Bonincontro D, Albonetti S, Cavani F. Stud. Surf. Sci. Catal. 2019; 178: 125
• 2a Tundo P, Selva M. Acc. Chem. Res. 2002; 35: 706
• 2b Peng W, Zhao N, Xiao F, Wei W, Sun Y. Pure Appl. Chem. 2011; 84: 603
• 2c Saada R, Kellici S, Heil T, Morganc D, Saha B. Appl. Catal., B. 2015; 168: 353
• 2d Tundo P, Musolino M, Aricò F. Green Chem. 2018; 20: 28
• 3a Sun S, Fu J. Bioorg. Med. Chem. Lett. 2018; 28: 3283
• 3b Cernak T, Dykstra KD, Tyagarajan S, Vachal P, Krska SW. Chem. Soc. Rev. 2016; 45: 546
• 3c Leung CS, Leung SS. F, Tirado-Rives J, Jorgensen WL. J. Med. Chem. 2012; 55: 4489
• 3d Chatterjee J, Gilon C, Hoffman A, Kessler H. Acc. Chem. Res. 2008; 41: 1331
• 3e Kuntz KW, Campbell JE, Keilhack H, Pollock RM, Knutson SK, Porter-Scott M, Richon VM, Sneeringer CJ, Wigle TJ, Allain CJ, Majer CR, Moyer MP, Copeland RA, Chesworth R. J. Med. Chem. 2016; 59: 1556
• 4a Ohno K, Nishiyama H, Nagase H. Tetrahedron Lett. 1979; 20: 4405
• 4b Ogawa H, Ichimura Y, Chihara T, Teratani S, Bull KT. Bull. Chem. Soc. Jpn. 1986; 59: 2481
• 4c Chang J.-S, Lee Y.-D, Chou LC.-S, Ling T.-R, Chou T.-C. Ind. Eng. Chem. Res. 2012; 51: 655
• 4d Sutter M, Dayoub W, Metay E, Raoul Y, Lemaire M. ChemCatChem 2013; 5: 2893
• 4e Yi J.-C, Liu C, Dai L.-X, You S.-L. Chem. Asian J. 2017; 12: 2975
• 4f Wang X, Dong J, Li Y, Liu Y, Wang Q. J. Org. Chem. 2020; 85: 7459
• 4g Chen B, Cao P, Liao Y, Wang M, Liao J. Org. Lett. 2018; 20: 1346
• 4h Zhang S.-Y, Li Q, He G, Nack WA, Chen G. J. Am. Chem. Soc. 2013; 135: 12135
• 5a Liu Z, Yang Z, Yu X, Zhang H, Yu B, Zhao Y, Liu Z. Org. Lett. 2017; 19: 5228
• 5b Tsukamoto Y, Itoh S, Kobayashi M, Obora Y. Org. Lett. 2019; 21: 3299
• 5c Lv W, Wen S, Liu J, Cheng G. J. Org. Chem. 2019; 84: 9786
• 5d Xia Q, Liu X, Zhang Y, Chen C, Chen W. Org. Lett. 2013; 15: 3326
• 5e Li Y, Xue D, Lu W, Wang C, Liu ZT, Xiao J. Org. Lett. 2014; 16: 66
• 5f Xia H.-M, Zhang F.-L, Ye T, Wang Y.-F. Angew. Chem. Int. Ed. 2018; 57: 11770
• 5g Hara Y, Matsuda M. Bull. Chem. Soc. Jpn. 1976; 49: 1126
• 5h Mouselmani R, Silva ED, Lemaire M. Tetrahedron 2015; 71: 8905
• 6 Wang B, Zhang Q, Guo Z, Ablajan K. Synthesis 2020; 52: 3058
• 7 Gao Q, Wu X, Jia F, Liu M, Zhu Y, Cai Q, Wu A. J. Org. Chem. 2013; 78: 2792
• 8 Xu W.-X, Ye F.-X, Liu X.-H, Weng J.-Q. Tetrahedron Lett. 2020; 61: 151807
• 9 Gao Y, Song Q, Cheng G, Cui X. Org. Biomol. Chem. 2014; 12: 1044
• 10 Qiu J.-W, Hu B.-L, Zhang X.-G, Tang R.-Y, Zhong P, Li J.-H. Org. Biomol. Chem. 2015; 13: 3122
• 11 Mitra S, Chakraborty A, Mishra S, Majee A, Hajra A. Org. Lett. 2014; 16: 5652
• 12 Feng Y.-S, Qi H.-X, Wang W.-C, Liang Y.-F, Xu H.-J. Tetrahedron Lett. 2012; 53: 2914
• 13 Yao L, Zhou Q, Han W, Wei S. Eur. J. Org. Chem. 2012; 6856
• 14 Li X, Liu P, He J, Li W, Yang Z, Wei Y, Wei Y, Gu Y. Green Synth. Catal. 2021; 2: 381
• 15 Li X, He J, Du M, Zhang J, Gu Y, Vaccaro L, Liu P. Mol. Catal. 2022; 517: 112051
• 16 Guo Y.-Q, Chen F, Deng C.-L, Zhang X.-G. Chem. Commun. 2021; 57: 1923
• 17a Selva M, Perosa A. Green Chem. 2008; 10: 457
• 17b Selva M, Tundo P. J. Org. Chem. 2006; 71: 1464
• 17c Selva M, Tundo P. J. Org. Chem. 2006; 71: 5570
• 18a Yang Z, He J, Wei Y, Li W, Liu P. Org. Biomol. Chem. 2020; 18: 3360
• 18b Yang Z, He J, Wei Y, Li W, Liu P, Zhao J, Wei Y. Org. Biomol. Chem. 2020; 18: 9088
• 18c Chen L.-J, Hang J, Wei Z.-T, Yang Z, Liu P, Zhang J, Dai B. Tetrahedron 2019; 75: 130664
• 18d Wei Y.-T, He J, Liu Y.-L, Xu L, Vaccaro L, Liu P, Gu Y.-L. ACS Omega 2020; 5: 18515
• 18e Wei Y.-T, Liu Y.-L, He J, Li X.-Z, Liu P, Zhang J. Tetrahedron 2020; 76: 131646
• 18f Wei Y, Liu P, Liu Y, He J, Li X, Li S, Zhao J. Org. Biomol. Chem. 2021; 19: 3932
• 18g He J, Yang Z, Li W, Wei Y, Dai B, Zhao J, Liu P. ChemCatChem 2021; 13: 2641
• 18h He J, Yang Z, Li W.-W, Wei Y.-T, Dai B, Zhao J.-X, Liu P. Tetrahedron Lett. 2021; 66: 152824
• 18i Feng Y, He J, Li W, Yang Z, Wei Y, Liu P, Zhao J, Gu C, Wang W. Tetrahedron 2021; 78: 131803
• 18j Liu Y, Wei Y, Yang Z, Li Y, Liu Y, Liu P. Org. Biomol. Chem. 2021; 19: 5191
• 18k Liu Y.-L, Yang Z, Li Y, Yang Y, Liu P. Chin. J. Org. Chem. 2021; 41: 4789
• 18l Feng Y.-J, He J, Wei Y.-T, Tang T, Li C.-T, Liu P. Chin. J. Org. Chem. 2021; 42: 226
• 18m He J, Wei Y.-T, Feng Y.-J, Li C.-T, Dai B, Liu P. Synthesis 2022; 54: 1793
• 18n Hao D, Yang Z, Liu Y.-L, Li Y, Li C.-T, Gu Y.-L, Vaccaro LG, Liu J.-C, Liu P. Org. Biomol. Chem. 2022; 20: 847
• 18o He J, Wei Y.-T, Li X.-Z, Dai B, Liu P. Synthesis 2022; 54: 490
• 19 CCDC 2151802 (3e) and 2151801 (3n) 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