The Synthesis and Application of 2-Cyano and -Ester Containing Anilines: Selective Copper-Catalyzed Reductive Amination, N-Benz­ylation, and Cyclization Reactions

Abstract

A convenient and practical pathway to 2-cyano and 2-ester anilines is described via efficient and selective copper(II)-catalyzed reductive amination via hydrosilylation process. Both 2-cyano and 2-ester anilines were successfully synthesized with good functional group tolerance and high selectivity. The application of the 2-cyano and -iodine containing anilines was developed in the synthesis of indoloindole derivatives via CuSO₄-catalyzed N-benzylation and cyclization reaction in ‘one pot’. More interestingly, the photophysical property investigations of these 2-cyano and 2-ester containing anilines exhibit excellent fluorescent properties, which have great potential application in the development of interesting near-ultraviolet optical devices in the near future.

Key words

copper catalysis - hydrosilane - reductive amination - amines - indoloindole

Publication History

Received: 25 April 2022

Accepted after revision: 02 May 2022

Accepted Manuscript online:
02 May 2022

Article published online:
14 June 2022

• References

• 1a Vitaku E, Smith DT, Njardarson JT. J. Med. Chem. 2014; 57: 10257
• 1b Froidevaux V, Negrell C, Caillol S, Pascault JP, Boutevin B. Chem. Rev. 2016; 116: 14181
• 1c Mayol-Llinàs J, Nelson A, Farnaby W, Ayscough A. Drug Discov. Today 2017; 22: 965
• 1d Jagadeesh Rajenahally V, Murugesan K, Alshammari Ahmad S, Neumann H, Pohl M.-M, Radnik J, Beller M. Science 2017; 358: 326
• 1e Afanasyev OI, Kuchuk E, Usanov DL, Chusov D. Chem. Rev. 2019; 119: 11857
• 1f Ferjancic Z, Saicic RN. Eur. J. Org. Chem. 2021; 22: 3241
• 2a Cao L, Zhao H, Guan R, Jiang H, Dixneuf PH, Zhang M. Nat. Commun. 2021; 12: 4206
• 2b Yang J, Zhao H, Tan Z, Cao L, Jiang H, Ci C, Dixneuf PH, Zhang M. ACS Catal. 2021; 11: 9271
• 2c Xie R, Mao W, Jia H, Sun J, Lu G, Jiang H, Zhang M. Chem. Sci. 2021; 12: 13802
• 2d Tan Z, Ci C, Yang J, Wu Y, Cao L, Jiang H, Zhang M. ACS Catal. 2020;  10: 5243
• 2e Feng J.-B, Wu X.-F. Adv. Synth. Catal. 2016; 358: 2179
• 3a Ruiz-Castillo P, Buchwald SL. Chem. Rev. 2016; 116: 12564
• 3b Zhang D, Liu R, Zhou X. Catal. Sci. Technol. 2018; 8: 5573
• 3c Chamakuri S, Shah MM, Yang DC. H, Santini C, Young DW. Org. Biomol. Chem. 2020; 18: 8844
• 3d Wiklund P, Bergman J. Org. Biomol. Chem. 2003; 1: 367
• 4 Chen C.-Y, He F, Tang G, Yuan H, Li N, Wang J, Faessler R. J. Org. Chem. 2018; 83: 2395
• 5 Li L, Chua WK. S. Tetrahedron Lett. 2011; 52: 1574
• 6 Shan X.-H, Yang B, Qu J.-P, Kang Y.-B. Chem. Commun. 2020; 56: 4063
• 7a Cho BT, Kang SK. Tetrahedron 2005; 61: 5725
• 7b Kalbasi RJ, Mazaheri O. Catal. Commun. 2015; 69: 86
• 7c Kalbasi RJ, Mazaheri O. New. J. Chem. 2016; 40: 9627
• 7d Fiore AM, Romanazzi G, Dell’Anna MM, Latronico M, Leonelli CM, Rizzuti A, Mastrorilli P. Mol. Catal. 2019; 476: 110507
• 7e Huang M.-Y, Yang J.-M, Zhao Y.-T, Zhu S.-F. ACS Catal. 2019; 9: 5353
• 7f Kitamura M, Chiba S, Narasaka K. Bull. Chem. Soc. Jpn. 2003; 76: 1063
• 8a Wei D, Darcel C. Chem. Rev. 2019; 119: 2550
• 8b Wu J, Tongdee S, Ammaiyappan Y, Darcel C. Adv. Synth. Catal. 2021; 363: 3859
• 8c Maya RJ, Poulose S, John J, Luxmi R. V. Adv. Synth. Catal. 2017; 359: 1177
• 9a Lokhande R, Sonawane J, Roy A, Ravishankar L. Green Chem. Lett. Rev. 2011; 4: 69
• 9b Zhu X, Zhou X, Zhang W. J. Chem. Res. 2015; 39: 390
• 10a Enthaler S. Catal. Lett. 2011; 141: 55
• 10b Werkmeister S, Fleischer S, Zhou S, Junge K, Beller M. ChemSusChem 2012; 5: 777
• 10c Yang L, Lin J, Kang L, Zhou W, Ma D.-Y. Adv. Synth. Catal. 2018; 360: 485
• 10d Stoll EL, Tongue T, Andrews KG, Valette D, Hirst DJ, Denton RM. Chem. Sci. 2020; 11: 9494
• 11a Enthaler S. ChemCatChem 2010; 2: 1411
• 11b Thai TT, Merel DS, Poater A, Gaillard S, Renaud JL. Chem. Eur. J. 2015; 21: 7066
• 11c Facchini SV, Cettolin M, Bai XS, Casamassima G, Pignataro L, Gennari C, Piarulli U. Adv. Synth. Catal. 2018; 360: 1054
• 11d Petricci E, Santillo N, Castagnolo D, Cini E, Taddei M. Adv. Synth. Catal. 2018; 360: 2560
• 12a Li B, Sortais J.-B, Darcel C. Chem. Commun. 2013; 49: 3691
• 12b Li B, Zheng J, Zeng W, Li Y, Chen L. Synthesis 2017; 49: 1349
• 12c Zhang B, Liu L, Guo D, Wang J. ChemistrySelect 2019; 4: 1195
• 12d Makarova M, Afanasyev OI, Kliuev F, Nelyubina YV, Godovikova M, Chusov DJ. J. Organomet. Chem. 2021; 941: 121806
• 13 Pletz J, Berg B, Breinbauer R. Synthesis 2016; 48: 1301
• 14a Kukushkin VY, Pombeiro AJ. L. Chem. Rev. 2002; 5: 1771
• 14b Gushchin PV, Kuznetsov ML, Haukka M, Wang M.-J, Gribanov AV, Kukushkin VY. Inorg. Chem. 2009; 48: 2583
• 14c Li B, Sortais J.-B, Darcel C, Dixneuf PH. ChemSusChem 2012; 5: 396
• 15 Shen H, Gao Q, Zhang Y, Lin Y, Lin Q, Li Z, Chen L, Zeng Z, Li X, Jia Y, Wang S, Du Z, Li LS, Zhang Z. Nat. Photonics 2019; 13: 192
• 16 Zhang F, Silver SH, Noel NK, Ullrich F, Rand BP, Kahn A. Adv. Energy Mater. 2020; 1903252
• 17 Barlev A, Sen D. Acc. Chem. Res. 2018; 51: 526
• 18 Chen S, Hu H. Chem. Soc. Rev. 2021; 50: 8639
• 19 Zhu S, Song Y, Shao J, Zhao X, Yang B. Angew. Chem. Int. Ed. 2015; 54: 14626
• 20 Qiu Z, Tan J, Cai N, Wang K, Ji S, Huo Y. Chin. J. Org. Chem. 2019; 39: 679
• 21 Frederik F, Torsten I, Rhett K. J. Am. Chem. Soc. 2019; 141: 11677
• 22 Hidemasa H, Toshitaka K, Kyoko I, Shoko K, Isao A. Adv. Synth. Catal. 2016; 358: 784
• 23 Akira M, Takami S, Etsuo O, Takeo H. Heterocycles 1994; 37: 823
• 24 Patil NT, Wu H, Kadota I, Yamamoto Y. J. Org. Chem. 2004; 69: 8745
• 25 Rahul N, Gregor J, Chitra S, Jeet K. Org. Biomol. Chem. 2018; 16: 4304
• 26 Linsenmeier AM, Williams CM, Braese S. J. Org. Chem. 2011; 76: 9127
• 27 CCDC 2118550 contains 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