C., Li, Y., and Hu, J. (2006). J. Org. Chem. 71: 6829–6833.(c) Li, Y., Liu, J., Zhang, L. et al. (2007). J. Org. Chem. 72: 5824.(d) Zhang, W., Zhu, J., and Hu, J. (2008). Tetrahedron Lett. 49: 5006–5008.6 6 (a) Zhang, W., Huang, W., and Hu, J. (2009). Angew. Chem. Int. Ed. 48: 9858–9861.(b) Zhang, W., Wang, F., and Hu, J. (2009). Org. Lett. 11: 2109–2112.(c) Shen, X., Zhang, W., Ni, C. et al. (2012). J. Am. Chem. Soc. 134: 16999–17002.(d) Shen, X., Zhang, W., Zhang, L. et al. (2012). Angew. Chem. Int. Ed. 51: 6966–6970.(e) Shen, X., Miao, W., Ni, C., and Hu, J. (2014). Angew. Chem. Int. Ed. 53: 775–779.(f) Liu, Q., Shen, X., Ni, C., and Hu, J. (2017). Angew. Chem. Int. Ed. 56: 619–623.
7 7 (a) Zhao, Y., Huang, W., Zhu, L., and Hu, J. (2010). Org. Lett. 122: 1444–1447.(b) Zhao, Y., Gao, B., Ni, C., and Hu, J. (2012). Org. Lett. 14: 6080–6083.(c) Zhao, Y., Jiang, F., and Hu, J. (2015). J. Am. Chem. Soc. 137: 5199–5203.(d) Rong, J., Deng, L., Tan, P. et al. (2016). Angew. Chem. Int. Ed. 55: 2743–2747.
8 8 (a) Zhang, L., Zheng, J., and Hu, J. (2006). J. Org. Chem. 71: 9845–9848.(b) Zheng, J., Li, Y., Zhang, L. et al. (2007). Chem. Commun.: 5149–5151.(c) Wang, F., Huang, W., and Hu, J. (2011). Chin. J. Chem. 29: 2717–2721.(d) Wang, F., Luo, T., Hu, J. et al. (2011). Angew. Chem. Int. Ed. 50: 7153–7157.(e) Wang, F., Zhang, W., Zhu, J. et al. (2011). Chem. Commun. 47: 2411–2413.(f) Li, L., Wang, F., Ni, C., and Hu, J. (2013). Angew. Chem. Int. Ed. 52: 12390–12394.
9 9 He, Z., Tan, P., Ni, C., and Hu, J. (2015). Org. Lett. 17: 1838–1841.
10 10 Zhou, M., Ni, C., Zeng, Y., and Hu, J. (2018). J. Am. Chem. Soc. 140: 6801–6805.
11 11 Li, L., Ni, C., Wang, F., and Hu, J. (2016). Nat. Commun. 7: 13320–13330.
12 12 Guo, J., Kuang, C., Rong, J. et al. (2019). Chem. Eur. J. 25: 7259–7264.
13 13 Lipshutz, B.H. and Sengupta, S. (1992). Organocopper reagents: substitution, conjugate addition, carbo/metallocupration, and other reactions. In: Organic Reactions, vol. 41 (ed. L.A. Paquette), 135–631. Wiley.
14 14 Hu, M., Ni, C., and Hu, J. (2012). J. Am. Chem. Soc. 134: 15257–15260.
15 15 Hu, M., He, Z., Gao, B. et al. (2013). J. Am. Chem. Soc. 135: 17302–17305.
16 16 Hu, M., Ni, C., Li, L. et al. (2015). J. Am. Chem. Soc. 137: 14496–14501.
17 17 Nakao, Y., Takeda, M., Matsumoto, T., and Hiyama, T. (2010). Angew. Chem. Int. Ed. 49: 4447.
18 18 Prakash, G.K.S., Krishnamuri, R., and Olah, G.A. (1989). J. Am. Chem. Soc. 111: 393–395.
19 19 (a) Liu, X., Xu, C., Wang, M., and Liu, Q. (2015). Chem. Rev. 115: 683–730.(b) Singh, R.P. and Shreeve, J.M. (2000). Tetrahedron 56: 7613–7632.
20 20 Li, L., Ni, C., Xie, Q. et al. (2017). Angew. Chem. Int. Ed. 56: 9971–9975.
21 21 Xie, Q., Li, L., Zhu, Z. et al. (2018). Angew. Chem. Int. Ed. 57: 13211–13215.
22 22 Xie, Q., Zhu, Z., Li, L. et al. (2020). Chem. Sci. 11: 276–280.
23 23 (a) Xie, Q., Ni, C., Zhang, R. et al. (2017). Angew. Chem. Int. Ed. 56: 3206–3210.(b) Xie, Q., Zhu, Z., Li, L. et al. (2019). Angew. Chem. Int. Ed. 58: 6405–6410.
24 24 Dilman, A.D. and Levin, V.V. (2018). Acc. Chem. Res. 51: 1272–1280.
25 25 Seppelt, K. (1977). Angew. Chem. Int. Ed. 16: 322–323.
26 26 (a) Prakash, G.K.S., Hu, J., Wang, Y., and Olah, G.A. (2004). Angew. Chem. Int. Ed. 43: 5203–5206.(b) Prakash, G.K.S., Hu, J., Wang, Y., and Olah, G.A. (2004). Org. Lett. 6: 4315–4317.(c) Prakash, G.K.S., Hu, J., Mathew, T., and Olah, G.A. (2003). Angew. Chem. Int. Ed. 42: 5216–5219.(d) Stahly, G.P. (1989). J. Fluorine Chem. 43: 53–66.(e) Hine, J. and Porter, J.J. (1960). J. Am. Chem. Soc. 82: 6178–6181.
27 27 (a) Li, Y. and Hu, J. (2005). Angew. Chem. Int. Ed. 44: 5882–5886.(b) Liu, J., Li, Y., and Hu, J. (2007). J. Org. Chem. 72: 3119–3121.(c) Ni, C., Liu, J., Zhang, L., and Hu, J. (2007). Angew. Chem. Int. Ed. 46: 786–789.
28 28 Aïssa, C. (2009). Eur. J. Org. Chem.: 1831–1844.
29 29 Zhao, Y., Gao, B., and Hu, J. (2012). J. Am. Chem. Soc. 134: 5790–5793.
30 30 Miao, W., Ni, C., Zhao, Y., and Hu, J. (2016). Org. Lett. 18: 2766–2769.
31 31 Miao, W., Zhao, Y., Ni, C. et al. (2018). J. Am. Chem. Soc. 140: 880–883.
32 32 Gao, B., Zhao, Y., and Hu, J. (2015). Angew. Chem. Int. Ed. 54: 638–642.
33 33 (a) Kelly, B.D. and Lambert, T.H. (2009). J. Am. Chem. Soc. 131: 13930–13931.(b) Hardee, D.J., Kovalchuke, L., and Lambert, T.H. (2010). J. Am. Chem. Soc. 132: 5002–5003.(c) Vanos, C.M. and Lambert, T.H. (2011). Angew. Chem. Int. Ed. 50: 12222–12226.
34 34 (a) Nielsen, M.K., Ugaz, C.R., Li, W., and Doyle, A.G. (2015). J. Am. Chem. Soc. 137: 9571–9574.(b) Nielsen, M.K., Ahneman, D.T., Riera, O., and Doyle, A.G. (2018). J. Am. Chem. Soc. 140: 5004–5008.
2 Perfluoroalkylation Using Perfluorocarboxylic Acids and Anhydrides
Shintaro Kawamuraand Mikiko Sodeoka
1Catalysis and Integrated Research Group, RIKEN Center for Sustainable Resource Science, 2‐1 Hirosawa, Wako, Saitama, 351‐0198 Japan
2Synthetic Organic Chemistry Laboratory, RIKEN Cluster for Pioneering Research, 2‐1 Hirosawa, Wako, Saitama, 351‐0198 Japan
2.1 Introduction
In recent years, increasing numbers of perfluoroalkyl group‐containing medicines, agrochemicals, and functional materials have been reported [1], in large part due to the development of sophisticated perfluoroalkylating reagents, such as the Ruppert–Prakash, Togni, Umemoto, and Langlois reagents, as reviewed elsewhere in this book. Although synthetic routes to many perfluoroalkylated molecules can now be designed based on reported perfluoroalkylations using these reagents, it remains preferable to employ readily available, inexpensive, multipurpose perfluoroalkyl compounds that can be conveniently stored in the laboratory. In particular, perfluoroalkyl group‐containing building blocks that can be prepared by means of scalable perfluoroalkylation reactions are needed. In this context, we focus here on perfluoroalkylation reactions utilizing perfluorocarboxylic acids and anhydrides as user‐friendly perfluoroalkyl sources. Although several excellent secondary reagents, including the corresponding esters prepared from perfluorocarboxylic acids and anhydrides, are known [2], we will review only methods directly using the carboxylic acids and anhydrides themselves.
2.2 Perfluoroalkylation with Perfluorocarboxylic Acids
The history of perfluoroalkylation reactions of organic compounds using perfluorocarboxylic acids began in the 1970s, and since then various methods for the generation of perfluoroalkyl radicals or perfluoroalkyl metals as reactive species for perfluoroalkylations have been developed. In this section, we describe perfluoroalkylation reactions with perfluorocarboxylic acids, classified according to the following reaction modes: electrochemical reactions (2.1), reactions using XeF2 (2.2), reactions using copper and silver salts (2.3), photochemical reactions (2.4), and other methods (2.5).
