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DOI: 10.1055/a-1671-6602
A Concise Copper-Catalyzed Oxytrifluoromethylation of Allyl Alcohols
We are grateful for the financial support from the Natural Science Foundation of Tianjin (19JCYBJC20200) and Tianjin University for support of this research.
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In deep memory of Dr. Ei-ichi Negishi.
Abstract
An efficient oxytrifluoromethylation of 1-aryl-substituted allyl alcohols has been developed using Togni’s reagent II as a trifluoromethylation reagent and copper(I) chloride as a catalyst. This reaction proceeded through a one-pot process of trifluoromethylation followed by nucleophilic attack of the vicinal hydroxyl group. This strategy features good diastereoselectivity and broad substrate scope, which provides a facile access to various 2-aryl-3-(2,2,2-trifluoroethyl)oxiranes.
Key words
oxytrifluoromethylation - allyl alcohols - CF3-substituted epoxides - Togni’s reagent - copper catalysis - 2-(2,2,2-trifluoroethyl)oxiranesSupporting Information
- Supporting information for this article is available online at https://doi.org/10.1055/a-1671-6602.
- Supporting Information
Publication History
Received: 18 September 2021
Accepted after revision: 18 October 2021
Accepted Manuscript online:
18 October 2021
Article published online:
30 November 2021
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References
- 1a Müller K, Faeh C, Diederich F. Science 2007; 317: 1881
- 1b Jeschke P. ChemBioChem 2004; 5: 570
- 1c Schlosser M. Angew. Chem. Int. Ed. 2006; 45: 5432
- 1d O’Hagan D. Chem. Soc. Rev. 2008; 37: 308
- 1e Purser S, Moore PR, Swallow S, Gouverneur V. Chem. Soc. Rev. 2008; 37: 320
- 2 Heidelberger C, Chaudhuri NK, Danneberg P, Mooren D, Griesbach L, Duschinsky R, Schnitzer RJ, Pleven E, Scheiner J. Nature 1957; 179: 663
- 3a Ma J.-A, Cahard D. Chem. Rev. 2004; 104: 6119
- 3b Shimizu M, Hiyama T. Angew. Chem. Int. Ed. 2005; 44: 214
- 3c Ma J.-A, Cahard D. J. Fluorine Chem. 2007; 128: 975
- 3d Feruya T, Kamlet AS, Ritter T. Nature 2011; 473: 470
- 3e Studer A. Angew. Chem. Int. Ed. 2012; 51: 8950
- 3f Liu H, Gu Z, Jiang X. Adv. Synth. Catal. 2013; 355: 617
-
4a
Eisenberger P,
Gischig S,
Togni A.
Chem. Eur. J. 2006; 12: 2579
- 4b Niedermann K, Welch JM, Koller R, Cvengroš J, Santschi N, Battaglia P, Togni A. Tetrahedron 2010; 66: 5753
- 4c Pair E, Monteriro N, Bouyssi D, Baudoin O. Angew. Chem. Int. Ed. 2013; 52: 5346
- 4d Matoušek V, Pietrasiak E, Schwenk R, Togni A. J. Org. Chem. 2013; 78: 6763
- 4e Andries-Ulmer A, Brunner C, Rehbein J, Gulder T. J. Am. Chem. Soc. 2018; 140: 13034
- 4f Li C, Xue L, Zhou J, Zhao Y, Han G, Hou J, Song Y, Liu Y. Org. Lett. 2020; 22: 3291
- 5a Chen P, Liu G. Synthesis 2013; 45: 2919
- 5b Wang F, Chen P, Liu G. Acc. Chem. Res. 2018; 51: 2036
- 5c Merino E, Nevado C. Chem. Soc. Rev. 2014; 43: 6598
- 5d Egami H, Sodeoka M. Angew. Chem. Int. Ed. 2014; 53: 8294
- 5e Kieltsch I, Eisenberger P, Togni A. Angew. Chem. Int. Ed. 2007; 46: 754
- 5f Koller R, Stanek K, Stolz D, Aardoom R, Niedermann K, Togni A. Angew. Chem. Int. Ed. 2009; 48: 4332
- 5g Niedermann K, Früh N, Vinogradova E, Wiehn MS, Moreno A, Togni A. Angew. Chem. Int. Ed. 2011; 50: 1059
- 5h Früh N, Togni A. Angew. Chem. Int. Ed. 2014; 53: 10813
- 5i Katayev D, Matoušek V, Koller R, Togni A. Org. Lett. 2015; 17: 5898
- 5j Kalim J, Duhail T, Le T.-N, Vanthuyne N, Anselmi E, Togni A, Magnier E. Chem. Sci. 2019; 10: 10516
- 6a Wang X, Zhao S, Liu J, Zhu D, Guo M, Tang X, Wang G. Org. Lett. 2017; 19: 4187
- 6b Li X.-T, Gu Q.-S, Dong X.-Y, Meng X, Liu X.-Y. Angew. Chem. Int. Ed. 2018; 57: 7668
- 6c He F.-S, Chen X, Yang S, Zhang J, Xia H, Wu J. Org. Chem. Front. 2018; 5: 2437
- 6d Shu C, Mega RS, Andreassen BJ, Noble A, Aggarwal VK. Angew. Chem. Int. Ed. 2018; 57: 15430
- 6e Gao C, Li B, Geng X, Zhou Q, Zhang X, Fan X. Green Chem. 2019; 21: 5113
- 6f Wang J, Sun K, Chen X, Chen T, Liu Y, Qu L, Zhao Y, Yu B. Org. Lett. 2019; 21: 1863
- 6g Mou X.-Q, Rong F.-M, Zhang H, Chen G, He G. Org. Lett. 2019; 21: 4657
- 6h Wang L, Qi C, Cheng R, Liu H, Xiong W, Jiang H. Org. Lett. 2019; 21: 7386
- 6i Li Z.-L, Fang G.-C, Gu Q.-S, Liu X.-Y. Chem. Soc. Rev. 2020; 49: 32
- 6j Meng F, Fang Q, Yuan W, Xu N, Cao S, Chun J, Li J, Zhang H, Zhu Y. Org. Chem. Front. 2020; 7: 1358
- 7a Shen Y, Liao Q, Qiu W. J. Chem. Soc., Chem. Commun. 1988; 1309
- 7b Shimizu M, Fujimoto T, Minezaki H, Hata T, Hiyama T. J. Am. Chem. Soc. 2001; 123: 6947
- 7c Shimizu M, Fujimoto T, Liu X, Minezaki H, Hata T, Hiyama T. Tetrahedron 2003; 59: 9811
- 7d Yamazaki T, Ichige T, Kitazume T. Org. Lett. 2004; 6: 4073
- 7e Obinata R, Kawasaki-Takasuka T, Yamazaki T. Org. Lett. 2010; 12: 4316
- 8 Fuchikami T, Shibata Y, Urata H. Chem. Lett. 1987; 16: 521
- 9 Kim E, Choi S, Kim H, Cho EJ. Chem. Eur. J. 2013; 19: 6209
- 10 Zhu R, Buchwald SL. J. Am. Chem. Soc. 2012; 134: 12462
- 11a Chen H, Wang X, Guo M, Zhao W, Tang X, Wang G. Org. Chem. Front. 2017; 4: 2403
- 11b Wang X, Li M, Guo M, Tang X, Wang G. Adv. Synth. Catal. 2018; 360: 2151
- 11c Wang X, Liu J, Yu Z, Guo M, Tang X, Wang G. Org. Lett. 2018; 20: 6516
- 11d Yuan F, Zhou S, Yang Y, Guo M, Tang X, Wang G. Org. Chem. Front. 2018; 5: 3306
- 11e Yang Y, Yuan F, Ren X, Wang G, Zhao W, Tang X, Guo M. J. Org. Chem. 2019; 84: 4507
- 11f Wang L, Chen H, Zhao W, Wang G. Synlett 2021; 32: 1029
- 12 The cis- and trans-diastereomers were determined by comparison with reported spectra in ref. 10.
- 13 Chen Z.-M, Bai W, Wang S.-H, Yang B.-M, Tu Y.-Q, Zhang F.-M. Angew. Chem. Int. Ed. 2013; 52: 9781
- 14a Smith DM, Golding BT, Radom L. J. Am. Chem. Soc. 2001; 123: 1664
- 14b Kinoshita K, Kawata M, Ogura K.-i, Yamasaki A, Watanabe T, Komoto N, Hieda N, Yamanishi M, Tobimatsu T, Toraya T. Biochemistry 2008; 47: 3162
- 15a Huang L, Qi J, Wu X, Wu W, Jiang H. Chem. Eur. J. 2013; 19: 15462
- 15b Vellakkaran M, Andappan MM. S, Kommu N. Green Chem. 2014; 16: 2788
- 15c Liao J, Zhang Z, Tang X, Wu W, Guo W, Jiang H. J. Org. Chem. 2015; 80: 8903
- 16 Hatcher LQ, Karlin KD. In Advances in Inorganic Chemistry, Vol. 58. van Eldik R, Reedijk J. Elsevier/Academic Press; Amsterdam: 2006: 131-184
- 17 Spoehrle SS. M. S, West TH, Taylor JE, Slawin AM. Z, Smith AD. J. Am. Chem. Soc. 2017; 139: 11895
- 18 Chu L, Qing F.-L. Acc. Chem. Res. 2014; 47: 1513
- 19 Sun K, Li G, Guo S, Zhang Z, Zhang G. Org. Biomol. Chem. 2021; 19: 375
- 20 Yi N, Zhang H, Xu C, Deng W, Wang R, Peng D, Zeng Z, Xiang J. Org. Lett. 2016; 18: 1780
For selected reviews, see:
For selected reviews, see:
For selected examples, see:
For selected reviews, see:
For selected examples, see:
For selected examples, see: