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Synlett 2025; 36(02): 157-160
DOI: 10.1055/s-0043-1775367
DOI: 10.1055/s-0043-1775367
letter
Copper(II) Triflate Catalyzed Rearrangement of Amino 2,3-Epoxides to α-Amino Ketones
This research is funded by Kasetsart University through the Graduate School Fellowship Program and Kasetsart University Research and Development Institute (KURDI) (grant number FF(KU8.65)). An international travel grant from the International Affairs Division and the Faculty of Science Kasetsart University for SC to perform short-term research at Stockholm University is gratefully acknowledged.
Abstract
α-Amino ketones were synthesized by a Meinwald rearrangement of biomass-based amino epoxides using copper(II) triflate as a catalyst. The regioselectivity of the rearrangement can be rationalized in terms of the reaction proceeding via the most stable carbocationic intermediate to give various α-amino α′-aryl ketones in moderate to good yields. This is an attractive method to prepare α-amino ketones using a benign and inexpensive catalyst.
Key words
Meinwald rearrangement - amino ketones - amino epoxide - copper catalysis - copper triflateSupporting Information
- Supporting information for this article is available online at https://doi.org/10.1055/s-0043-1775367.
- Supporting Information
Publication History
Received: 23 April 2024
Accepted after revision: 08 May 2024
Article published online:
23 May 2024
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References and Notes
- 1a Nchinda AT, Chibale K, Redelinghuys P, Sturrock ED. Bioorg. Med. Chem. Lett. 2006; 16: 4612
- 1b Deddish PA, Marcic B, Jackman HL, Wang H.-Z, Skidgel RA, Erdös EG. Hypertension 1998; 31: 912
- 2 Pan X, Huang R, Zhang J, Ding L, Li W, Zhang Q, Liu F. Tetrahedron Lett. 2012; 53: 5364
- 3 Lin D, Qian W, Hilgenfeld R, Jiang H, Chen K, Liu H. Sci. China Chem. 2012; 55: 1101
- 4a Wu X, Hao L, Zhang Y, Rakesh M, Reddi RN, Yang S, Song B.-A, Chi YR. Angew. Chem. Int. Ed. 2017; 56: 4201
- 4b Groso EJ, Golonka AN, Harding RA, Alexander BW, Sodano TM, Schindler CS. ACS Catal. 2018; 8: 2006
- 4c Yoshikawa M, Saitoh M, Katoh T, Seki T, Bigi SV, Shimizu Y, Ishii T, Okai T, Kuno M, Hattori H, Watanabe E, Saikatendu KS, Zou H, Nakakariya M, Tatamiya T, Nakada Y, Yogo T. J. Med. Chem. 2018; 61: 2384
- 4d Donohoe TJ, Fishlock LP, Basutto JA, Bower JF, Procopiou PA, Thompson AL. Chem. Commun. 2009; 3008
- 4e Yoshida K, Kawagoe F, Hayashi K, Horiuchi S, Imamoto T, Yanagisawa A. Org. Lett. 2009; 11: 515
- 4f Soares AR. M, Taniguchi M, Chandrashaker V, Lindsey JS. New J. Chem. 2013; 37: 1073
- 4g Westermann J, Schneider M, Platzek J, Petrov O. Org. Process Res. Dev. 2007; 11: 200
- 5 Allen LA. T, Raclea R.-C, Natho P, Parsons PJ. Org. Biomol. Chem. 2021; 19: 498
- 6 Evans RW, Zbieg JR, Zhu S, Li W, MacMillan DW. C. J. Am. Chem. Soc. 2013; 135: 16074
- 7 Tran TV, Le HT. N, Ha HQ, Duong XN. T, Nguyen LH.-T, Doan TL. H, Nguyen HL, Truong T. Catal. Sci. Technol. 2017; 7: 3453
- 8 Jiang Q, Xu B, Zhao A, Jia J, Liu T, Guo C. J. Org. Chem. 2014; 79: 8750
- 9 Lv Y, Li Y, Xiong T, Lu Y, Liu Q, Zhang Q. Chem. Commun. 2014; 50: 2367
- 10 Li L.-y, Zeng Q.-l, Li G.-x, Tang Z. Synlett 2019; 30: 694
- 11 Yadagiri D, Anbarasan P. Chem. Commun. 2015; 51: 14203
- 12 Miura T, Biyajima T, Fujii T, Murakami M. J. Am. Chem. Soc. 2012; 134: 194
- 13 Raclea R.-C, Natho P, Allen LA. T, White AJ. P, Parsons PJ. J. Org. Chem. 2020; 85: 9375
- 14 Gudla V, Balamurugan R. Chem. Asian J. 2013; 8: 414
- 15 Tian Y, Jürgens E, Mill K, Jordan R, Maulbetsch T, Kunz D. ChemCatChem 2019; 11: 4028
- 16 Kita Y, Matsuda S, Inoguchi R, Ganesh JK, Fujioka H. J. Org. Chem. 2006; 71: 5191
- 17 Trillo P, Baeza A, Nájera C. Eur. J. Org. Chem. 2012; 2929
- 18 Rearrangement of α-Amino Epoxides 1; General Procedure A dried tube was charged with Cu(OTf)2 (1 mol%) then capped and flushed with argon. A solution of the appropriate α-amino epoxide 1 (1 mmol) in anh 1,4-dioxane (4 mL) was added, and the mixture was stirred at 80 °C for 2 h. Sat. aq NaHCO3 was added, and the mixture was extracted with EtOAc. The combined organic layers were dried (Na2SO4) and the solvent was evaporated under reduced pressure, then the mixture was then purified by column chromatography (silica gel, EtOAc–hexane gradient). N-Cyclohexyl-2-nitro-N-(2-oxo-3-phenylpropyl)benzenesulfonamide (2a) Yellow oil; yield: 250 mg (60%). 1H NMR (400 MHz, CDCl3): δ = 8.16–8.11 (m, 1 H), 7.72–7.60 (m, 3 H), 7.39–7.23 (m, 5 H), 4.21 (s, 2 H), 3.80 (s, 2 H), 3.71 (tt, J = 12.1, 3.5 Hz, 1 H), 1.74–1.52 (m, 5 H), 1.31–1.20 (m, 2 H), 1.09–0.81 (m, 3 H). 13C NMR (100 MHz, CDCl3): δ = 203.3, 148.0, 134.1, 133.5, 133.3, 131.7, 131.2, 129.5 (2C), 128.9 (2C), 127.3, 124.1, 58.2, 51.2, 46.7, 31.2 (2 C), 25.7 (2 C), 25.1. HRMS (ESI): m/z [M + Na]+ calcd for C21H24N2NaO5S: 439.1298; found: 439.1368.