Divergent Synthesis of Substituted Amino-1,2,4-triazole Derivatives

Fenghai Zhao; Thishana Singh; Yumei Xiao; Wangcang Su; Dongyan Yang; Changqing Jia; Jia-Qi Li; Zhaohai Qin

doi:10.1055/a-1477-4630

Synthesis, Table of Contents

Synthesis 2021; 53(11): 1901-1910
DOI: 10.1055/a-1477-4630

paper

Divergent Synthesis of Substituted Amino-1,2,4-triazole Derivatives

Authors

Fenghai Zhao

^aInnovation Center of Pesticide Research, Department of Chemistry, College of Science, China Agricultural University, Beijing 100193, P. R. of China
Thishana Singh

^bCollege of Agriculture, Engineering and Science, School of Chemistry and Physics, University of KwaZulu-Natal, Durban 4000, South Africa
Yumei Xiao

^aInnovation Center of Pesticide Research, Department of Chemistry, College of Science, China Agricultural University, Beijing 100193, P. R. of China
Wangcang Su

^aInnovation Center of Pesticide Research, Department of Chemistry, College of Science, China Agricultural University, Beijing 100193, P. R. of China

^cInstitute of Plant Protection, Henan Academy of Agricultural Sciences, Zhengzhou 450002, P. R. of China
Dongyan Yang

^aInnovation Center of Pesticide Research, Department of Chemistry, College of Science, China Agricultural University, Beijing 100193, P. R. of China

^dCollege of Chemistry and Chemical Engineering, Zhongkai University of Agriculture and Engineering, Guangzhou, Guangdong 510225, P. R. of China
Changqing Jia

^aInnovation Center of Pesticide Research, Department of Chemistry, College of Science, China Agricultural University, Beijing 100193, P. R. of China

^eNational Engineering Research Center, Tongren Polytechnic College, Guizhou 554300, P. R. of China
Jia-Qi Li∗

^aInnovation Center of Pesticide Research, Department of Chemistry, College of Science, China Agricultural University, Beijing 100193, P. R. of China
Zhaohai Qin∗

^aInnovation Center of Pesticide Research, Department of Chemistry, College of Science, China Agricultural University, Beijing 100193, P. R. of China

Abstract

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Abstract

A divergent efficient assembly of disubstituted 1,2,4-triazoles was established by cyclization of readily accessible N′-nitro-2-hydrocarbylidene-hydrazinecarboximidamides with moderate to excellent yields under mild reaction conditions. This divergent synthetic strategy was achieved simply by varying the reaction conditions. Under acidic conditions, amino-1,2,4-triazoles were obtained by an intramolecular redox reaction involving the NO₂ group. Control experiments and DFT studies revealed that this transformation proceeds via an intramolecular 1,3-hydride transfer pathway leading to HNO₂ elimination. Under neutral conditions with water as the solvent, nitroimino-1,2,4-triazoles were obtained by oxidative intramolecular annulation under air.

Key words

1,2,4-triazoles - divergent synthesis - redox chemistry - cyclization - heterocycles

Full Text

References

References

1a Smith CA, Narouz MR, Lummis PA, Singh I, Nazemi A, Li C.-H, Crudden CM. Chem. Rev. 2019; 119: 4986
1b Ghareeb H, Metanis N. Chem. Eur. J. 2020; 26: 10175

2a Li Y.-Q, He Y, Shao T, Pei H.-X, Guo W.-K, Mi D.-Z, Krimm I, Zhang Y.-J, Wang P.-L, Wang X, Liu M.-Y, Yi Z.-F, Chen Y.-H. J. Med. Chem. 2019; 62: 4949
2b Ajmal M, Yunus U, Graham RM, Leblanc RM. ACS Omega 2019; 4: 22280
2c Gao H.-X, Shreeve JM. Chem. Rev. 2011; 111: 7377

3a Romagnoli R, Baraldi PG, Salvador MK, Prencipe F, Bertolasi V, Cancellieri M, Brancale A, Hamel E, Castagliuolo I, Consolaro F, Porcu E, Basso G, Viola G. J. Med. Chem. 2014; 57: 6795
3b El-Sherief HA. M, Youssif BG. M, Bukhari SN. A, Abdelazeem AH, Abdel-Aziz M, Abdel-Rahman HM. Eur. J. Med. Chem. 2018; 156: 774
3c Seth S, McDonald KA, Matzger AJ. Inorg. Chem. 2017; 56: 10151

4 Battaglia U, Moody CJ. J. Nat. Prod. 2010; 73: 1938
5 Ashton TD, Devine SM, Möhrle JJ, Laleu B, Burrows JN, Charman SA, Creek DJ, Sleebs BE. J. Med. Chem. 2019; 62: 10526
6 Li X, Zhang Z, Chen Y, Wan H, Sun J, Wang B, Feng B, Hu B, Shi X, Feng J, Zhang L, He F, Bai C, Zhang L, Tao W. ACS Med. Chem. Lett. 2019; 10: 996
7 Lou K, Yao Y, Hoye AT, James MJ, Cornec AS, Hyde E, Gay B, Lee VM, Trojanowski JQ, Smith AB. III, Brunden KR, Ballatore C. J. Med. Chem. 2014; 57: 6116
8 Zhao XX, Zhang JC, Li SH, Yang QP, Li YC, Pang SP. Org. Process Res. Dev. 2014; 18: 886
9 Yen W.-P, Kung F.-C, Wong FF. Eur. J. Org. Chem. 2016; 2328
10 Yin P, Ma W.-B, Chen Y, Huang W.-C, Deng Y, He L. Org. Lett. 2009; 11: 5482
11 Dolzhenko AV, Pastorin G, Dolzhenko AV, Chui WK. Tetrahedron Lett. 2009; 50: 2124
12 Yin P, Parrish DA, Shreeve JM. Angew. Chem. Int. Ed. 2014; 53: 12889
13 Jia C.-Q, Su W.-C, Xu Y.-J, Liu J.-P, Qin Z.-H. Chin. J. Org. Chem. 2016; 36: 830
14 Su W.-C, Zhou Y.-H, Ma Y.-Q, Wang L, Zhang Z, Rui C.-H, Duan H.-X, Qin Z.-H. J. Agric. Food Chem. 2012; 60: 5028
15 CCDC 1995578 (3a) and 1995580 (8a) 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
16 Wang J, Brower KR, Naud DL. J. Org. Chem. 1997; 62: 9055
17 Intermediate 7 is unstable in air and was partially oxidized to compound 8a during the purification. Hence, the isolated yield of intermediate 7 is lower than that of compound 8a if compound 1a is the starting material.
18 The cyclization of 1a with PTSA in methanol was studied by using an in situ ReactIR spectrophotometer to further understand the reaction mechanism. However, besides starting material 1a and product 3a, no intermediates were detected. This result might be the result of the highly reactivities of the reaction intermediates leading to insufficient concentrations.

Supplementary Material

Supporting Information (PDF)