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DOI: 10.1055/a-1747-2724
Chiral Urea-Catalyzed Asymmetric Mannich Reaction of 3-Fluorooxindoles with α-Amidosulfones: Synthesis of Optically Active α-Fluoro-β-amino-oxindoles
Autoren
We thank the financial support from the National Natural Science Foundation of China (Grant No. 51373067).
Abstract
The asymmetric Mannich reaction of 3-fluorooxindoles and α-amidosulfones catalyzed by a chiral urea catalyst derived from quinine in presence of K3PO4 was developed. Through the asymmetric reaction, a series of α-fluoro-β-amino-oxindoles, containing a tertiary carbon stereocenter, could be obtained in high yields (up to 95%) with high enantioselectivity (95%) and diastereoselectivity (>99:1). Such α-fluoro-β-amino-oxindole compounds are expected to become candidates in the field of medicine.
Key words
Mannich reaction - 3-fluorooxindoles - α-fluoro-β-amino-oxindoles - quinine-derived skeleton - urea-catalyzed catalystsSupporting Information
- Supporting information for this article is available online at https://doi.org/10.1055/a-1747-2724.
- Supporting Information (PDF) (opens in new window)
Publikationsverlauf
Eingereicht: 18. November 2021
Angenommen nach Revision: 20. Januar 2022
Accepted Manuscript online:
20. Januar 2022
Artikel online veröffentlicht:
09. Februar 2022
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References and Notes
- 1 Yang X, Wu T, Phipps RJ, Toste FD. Chem. Rev. 2015; 115: 826
- 2 Zheng B.-Q, Chen L.-Y, Zhao J.-B, Ji J, Qiu Z.-B, Ren X, Li Y. Org. Biomol. Chem. 2018; 16: 8989
- 3 Ma J.-A, Cahard D. Chem. Rev. 2004; 104: 6119
- 4 Wu Z.-J, Xu H.-C. Angew. Chem. Int. Ed. 2017; 56: 4734
- 5 Zhou Y, Wang J, Gu Z, Wang S, Zhu W, Aceña JL, Soloshonok VA, Izawa K, Liu H. Chem. Rev. 2016; 116: 422
- 6 Kaur M, Singh M, Chadha N, Silakari O. Eur. J. Med. Chem. 2016; 123: 858
- 7 Qiu Z.-B, Chen L.-Y, Ji J, Ren X, Li Y. J. Fluorine Chem. 2020; 236: 109594
- 8 Li B.-Y, Du D.-M. Adv. Synth. Catal. 2018; 360: 3164
- 9 Jin Y, Chen M, Ge S, Hartwig JF. Org. Lett. 2017; 19: 1390
- 10 Hewawasam P, Gribkoff VK, Pendri Y, Dworetzky SI, Meanwell NA, Martinez E, Boissard CG, Post-Munson DJ, Trojnacki JT, Yeleswaram K, Pajor LM, Knipe J, Gao Q, Perrone R, Starrett JE. Bioorg. Med. Chem. Lett. 2002; 12: 1023
- 11 Balaraman K, Ding R, Wolf C. Adv. Synth. Catal. 2017; 359: 4165
- 12 Li B.-Y, Lin Y, Du D.-M. J. Org. Chem. 2019; 84: 11752
- 13 Paladhi S, Park SY, Yang JW, Song CE. Org. Lett. 2017; 19: 5336
- 14 Jin Q, Zheng C, Zhao G, Zou G. Tetrahedron 2018; 74: 4134
- 15 Zhao J, Li Y, Chen L.-Y, Ren X. J. Org. Chem. 2019; 84: 5099
- 16 Marcantoni E, Palmieri A, Petrini M. Org. Chem. Front. 2019; 6: 2142
- 17 Liu Y, Wang J, Wei Z, Cao J, Liang D, Lin Y, Duan H. Org. Biomol. Chem. 2018; 16: 8927
- 18 Wang B, Xu T, Zhu L, Lan Y, Wang J, Lu N, Wei Z, Lin Y, Duan H. Org. Chem. Front. 2017; 4: 1266
- 19 Lu N, Li R, Wei Z, Cao J, Liang D, Lin Y, Duan H. J. Org. Chem. 2017; 82: 4668
- 20 To a stirred solution of isatin (1 mmol) in 5 mL methanol, hydrazine hydrate (1.5 mmol) was added over 6 h at 75 ℃. After concentrated under reduced pressure, it was next purified by flash chromatography using DCM to obtain the desired isatin hydrazone products. Next, LiOAc (5 mmol) and Selectfluor (2 mmol) were added into the isatin hydrazone (1 mmol) in DCE and stirred at 80 ℃ for 16 h. The reaction mixture was extracted with EtOAc (3 × 5 mL), dried over anhydrous Na2SO4, and concentrated under reduced pressure. The crude mixture was next purified by flash chromatography using hexane/EtOAc (8:1) to obtain product 1.