Cobalt–Tertiary Amine Mediated Peroxy-trifluoromethylation and -halodifluoromethylation of Alkenes with CF2XBr (X = F, Cl, Br) and tert-Butyl Hydroperoxide

Liangzhi Pang; Qilin Sun; Zhan Huang; Suhua Li; Qiankun Li

doi:10.1055/a-1702-4445

Synthesis, Table of Contents

Synthesis 2022; 54(09): 2193-2204
DOI: 10.1055/a-1702-4445

paper

Cobalt–Tertiary Amine Mediated Peroxy-trifluoromethylation and -halodifluoromethylation of Alkenes with CF₂XBr (X = F, Cl, Br) and tert-Butyl Hydroperoxide

Liangzhi Pang

^aDepartment of Applied Chemistry, Anhui Agricultural University, Hefei 230036, P. R. of China

,

Qilin Sun

^aDepartment of Applied Chemistry, Anhui Agricultural University, Hefei 230036, P. R. of China

,

Zhan Huang

^aDepartment of Applied Chemistry, Anhui Agricultural University, Hefei 230036, P. R. of China

,

Suhua Li∗

^bSchool of Chemistry, Sun Yat-Sen University, Guangzhou 510275, P. R. of China

^cKey Lab of Functional Molecular Engineering of Guangdong Province, South China University of Technology, Guangzhou 510641, P. R. of China

,

Qiankun Li ∗

^aDepartment of Applied Chemistry, Anhui Agricultural University, Hefei 230036, P. R. of China

› Author Affiliations

Abstract

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Abstract

An efficient cobalt-tertiary amine mediated peroxy-trifluoromethylation and -halodifluoromethylation of alkenes with simple and inexpensive CF₂XBr (X = F, Cl, Br) has been described. This method demonstrated broad substrate scope and good to high yields with the tolerance of mono-, di-, and trisubstituted alkenes with both electron-donating and electron-withdrawing groups. The protocol provides an efficient access to various β-peroxyl trifluoromethyl/halodifluoromethyl derivatives. Further transformation of these type of compounds into other useful molecules, such as a ketene aminal, an α-trifluoromethyl ketone, and a gem-difluoroalkene, demonstrated the utility of this methodology.

Key words

trifluoromethylation - chlorodifluoromethylation - bromodifluoromethylation - peroxyl - cobalt

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References

References

1a Fluorine in Medicinal Chemistry and Chemical Biology. Ojima I. Blackwell; Chichester: 2009
1b Kirsch P. Modern Fluoroorganic Chemistry: Synthesis, Reactivity, Applications, 2nd ed. Wiley-VCH; Weinheim: 2013
1c Smart BE. J. Fluorine Chem. 2001; 109: 3
1d Müller K, Faeh C, Diederich F. Science 2007; 317: 1881
1e Hird M. Chem. Soc. Rev. 2007; 36: 2070
1f Inoue M, Sumii Y, Shibata N. ACS Omega 2020; 5: 10633
1g Ogawa Y, Tokunaga E, Kobayashi O, Hirai K, Shibata N. iScience 2020; 23: 101467
1h Han J, Kiss L, Mei H, Remete AM, Ponikvar-Svet M, Sedgwick DM, Roman R, Fustero S, Moriwaki H, Soloshonok VA. Chem. Rev. 2021; 121: 4678

2a Simons JH, Lewis CJ. J. Am. Chem. Soc. 1938; 60: 492
2b Yagupolskii LM, Fedyuk DV, Petko KI, Troitskaya VI, Rudyk VI, Rudyuk VV. J. Fluorine Chem. 2000; 106: 181
2c Hasek WR, Smith WC, Engelhardt VA. J. Am. Chem. Soc. 1960; 82: 543

3a Tomashenko OA, Grushin VV. Chem. Rev. 2011; 111: 4475
3b Chu L, Qing F.-L. Acc. Chem. Res. 2014; 47: 1513
3c Charpentier J, Früh N, Togni A. Chem. Rev. 2015; 115: 650
3d Liu X, Xu C, Wang M, Liu Q. Chem. Rev. 2015; 115: 683
3e Yang X, Wu T, Phipps RJ, Toste FD. Chem. Rev. 2015; 115: 826
3f Alonso C, Martínez de Marigorta E, Rubiales G, Palacios F. Chem. Rev. 2015; 115: 1847
3g Koike T, Akita M. Acc. Chem. Res. 2016; 49: 1937

4a Rozen, S.; Hagooly, A. Bromotrifluoromethane, In e-EROS Encyclopedia of Reagents for Organic Synthesis [Online]; Wiley & Sons, Posted October 15, 2005.
4b Qi Q, Shen Q, Lu L. J. Fluorine Chem. 2012; 133: 115
4c He L, Natte K, Rabeah J, Taeschler C, Neumann H, Brückner A, Beller M. Angew. Chem. Int. Ed. 2015; 54: 4320
4d Natte K, Jagadeesh RV, He L, Rabeah J, Chen J, Taeschler C, Ellinger S, Zaragoza F, Neumann H, Brückner A, Beller M. Angew. Chem. Int. Ed. 2016; 55: 2782
4e Ren Y.-Y, Zheng X, Zhang X. Synlett 2018; 29: 1028
4f Zhang K.-F, Bian K.-J, Li C, Sheng J, Li Y, Wang X.-S. Angew. Chem. Int. Ed. 2019; 58: 5069
4g Li Q, Fan W, Peng D, Meng B, Wang S, Huang R, Liu S, Li S. ACS Catal. 2020; 10: 4012
4h Peng D, Fan W, Zhao X, Chen W, Wen Y, Zhang L, Li S. Org. Chem. Front. 2021; 8: 6356

5a Beckers H, Bürger H, Bursch P, Ruppert I. J. Organomet. Chem. 1986; 316: 41
5b Tordeux M, Langlois B, Wakselman C. J. Org. Chem. 1989; 54: 2452

6a Xu B, Mashuta MS, Hammond GB. Angew. Chem. Int. Ed. 2006; 45: 7265
6b Lin J.-H, Xiao J.-C. Eur. J. Org. Chem. 2011; 4536
6c Nguyen JD, Tucker JW, Konieczynska MD, Stephenson CR. J. J. Am. Chem. Soc. 2011; 133: 4160
6d Min Q.-Q, Yin Z, Feng Z, Guo W.-H, Zhang X. J. Am. Chem. Soc. 2014; 136: 1230
6e Yue X, Zhang X, Qing F.-L. Org. Lett. 2009; 11: 73
6f Surmont R, Verniest G, De Kimpe N. Org. Lett. 2009; 11: 2920

7a Farina A, Meille SV, Messina MT, Metrangolo P, Resnati G, Vecchio G. Angew. Chem. Int. Ed. 1999; 38: 2433
7b Zhu S, Xing C, Xu W, Jin G, Li Z. Cryst. Growth Des. 2004; 4: 53

8a Tarrant P, Lovelace AM. J. Am. Chem. Soc. 1955; 77: 768
8b Molines H, Wakselman C. J. Fluorine Chem. 1987; 37: 183
8c Yoshida M, Morinaga Y, Iyoda M. J. Fluorine Chem. 1994; 68: 33
8d Salomon P, Zard SZ. Org. Lett. 2014; 16: 2926
8e Daniel M, Dagousset G, Diter P, Klein P.-A, Tuccio B, Goncalves A.-M, Masson G, Magnier E. Angew. Chem. Int. Ed. 2017; 56: 3997
8f McAtee RC, Beatty JW, McAtee CC, Stephenson CR. J. Org. Lett. 2018; 20: 3491
8g Kawamura S, Henderson CJ, Aoki Y, Sekine D, Kobayashi S, Sodeoka M. Chem. Commun. 2018; 54: 11276
8h Zhang J, Xu X.-H, Qing F.-L. Tetrahedron Lett. 2016; 57: 2462
8i Yu J, Wang D, Xu Y, Wu Z, Zhu C. Adv. Synth. Catal. 2018; 360: 744
8j Lin Q.-Y, Xu X.-H, Qing F.-L. Org. Biomol. Chem. 2015; 13: 8740
8k Dmitriev IA, Supranovich VI, Levin VV, Dilman AD. Eur. J. Org. Chem. 2019; 4119
8l Wallentin C.-J, Nguyen JD, Finkbeiner P, Stephenson CR. J. J. Am. Chem. Soc. 2012; 134: 8875
8m Zhao Y, Gao B, Hu J. J. Am. Chem. Soc. 2012; 134: 5790

9a The Chemistry of Peroxides, Parts 1 and 2. Rappoport Z. Wiley; Chichester: 2006
9b Dembitsky VM. Eur. J. Med. Chem. 2008; 43: 223

10a Kornblum N, DeLaMare HE. J. Am. Chem. Soc. 1951; 73: 880
10b Staben ST, Linghu X, Toste FD. J. Am. Chem. Soc. 2006; 128: 12658
10c Liu W, Li Y, Liu K, Li Z. J. Am. Chem. Soc. 2011; 133: 10756
10d Lv L, Shen B, Li Z. Angew. Chem. Int. Ed. 2014; 53: 4164
10e Chen Y, Li L, Ma Y, Li Z. J. Org. Chem. 2019; 84: 5328
10f Chen Y, Ma Y, Li L, Cui M, Li Z. Org. Chem. Front. 2020; 7: 1837
10g Wang L, Ma Y, Jiang Y, Lv L, Li Z. Chem. Commun. 2021; 57: 7846
10h Chen Y, Li L, He X, Li Z. ACS Catal. 2019; 9: 9098
10i Ma Y, Chen Y, Lv L, Li Z. Adv. Synth. Catal. 2021; 363: 3233
10j Ma Y, Chen Y, Lou C, Li Z. Asian J. Org. Chem. 2020; 9: 1018

11a Kolb HC, VanNieuwenhze MS, Sharpless KB. Chem. Rev. 1994; 94: 2483
11b Minatti A, Muñiz K. Chem. Soc. Rev. 2007; 36: 1142
11c Jensen KH, Sigman MS. Org. Biomol. Chem. 2008; 6: 4083
11d McDonald RI, Liu G, Stahl SS. Chem. Rev. 2011; 111: 2981
11e Wolfe JP. Angew. Chem. Int. Ed. 2012; 51: 10224
11f Yin G, Mu X, Liu G. Acc. Chem. Res. 2016; 49: 2413
11g Cao MY, Ren X, Lu Z. Tetrahedron Lett. 2015; 56: 3732

12a Zhang H.-Y, Ge C, Zhao J, Zhang Y. Org. Lett. 2017; 19: 5260
12b Qi B, Zhang T, Li M, He C, Duan C. Catal. Sci. Technol. 2017; 7: 5872

13a Shi Y, Sitkoff D, Zhang J, Klei HE, Kish K, Liu EC.-K, Hartl KS, Seiler SM, Chang M, Huang C, Youssef S, Steinbacher TE, Schumacher WA, Grazier N, Pudzianowski A, Apedo A, Discenza L, Yanchunas JJr, Stein PD, Atwal KS. J. Med. Chem. 2008; 51: 7541
13b Chen N, Meng X, Zhu F, Cheng J, Shao X, Li Z. J. Agric. Food Chem. 2015; 63: 1360

14 Wang L, Qi C, Guo T, Jiang H. Org. Lett. 2019; 21: 2223

15a Spier E, Neuenschwander U, Hermans I. Angew. Chem. Int. Ed. 2013; 52: 1581
15b Turrà N, Neuenschwander U, Baiker A, Peeters J, Hermans I. Chem. Eur. J. 2010; 16: 13226

16 Su X, Huang H, Yuan Y, Li Y. Angew. Chem. Int. Ed. 2017; 56: 1338

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