Hydrodefluorination of Perfluoroarenes Meets Visible Light Photocatalysis

Abstract

Partially fluorinated arenes are increasingly found in pharmaceuticals, agrochemicals and materials. While interest in these molecules is high, the number of available methods for their syntheses is severely limited. While installation of a single fluorine is achievable, installation of several fluorines represents a significant challenge. Approaching this synthetic problem from the opposite direction has been more fruitful. Specifically, by subjecting perfluorinated arenes to selective hydrodefluorination the desired molecules can be obtained. Herein, the advancement of this approach is discussed.

Key words

fluorine - reduction - partially fluorinated arenes - photochemistry - hydrodefluorination

• References

• 1 Gray GW, Jones B. J. Chem. Soc. 1954; 2556
• 2 Rowley M, Hallett DJ, Goodacre S, Moyes C, Crawforth J, Sparey TJ, Patel S, Marwood R, Patel S, Thomas S, Hitzel L, O’Connor D, Szeto N, Castro JL, Hutson PH, MacLeod AM. J. Med. Chem. 2001; 44: 1603
• 3 Smart BE. J. Fluorine Chem. 2001; 109: 3
• 4 Purser S, Moore PR, Swallow S, Gouverneur V. Chem. Soc. Rev. 2008; 37: 320
• 5 In New FDA approved drugs in 2013 http://www.fda.gov/downloads/Drugs/DevelopmentApprovalProcess/Drug-Innovation/UCM381803.pdf.
• 6 Chambers RD. Fluorine in Organic Chemistry. CRC Press LLC; Boca Raton: 2004
• 7 Prakash GK. S, Mathew T, Hoole D, Esteves PM, Wang Q, Rasul G, Olah GA. J. Am. Chem. Soc. 2004; 126: 15770
• 8 Lafrance M, Shore D, Fagnou K. Org. Lett. 2006; 8: 5097
• 9 Wei Y, Kan J, Wang M, Su W, Hong M. Org. Lett. 2009; 11: 3346
• 10 Li H, Liu J, Sun C.-L, Li B.-J, Shi Z.-J. Org. Lett. 2010; 13: 276
• 11 Chu L, Qing F.-L. J. Am. Chem. Soc. 2011; 134: 1298
• 12 Adonin NY, Bardin VV, Frohn H.-J. Collect. Czech. Chem. Commun. 2008; 73: 1681
• 13 Nield E, Stephens R, Tatlow JC. J. Chem. Soc. 1959; 166
• 14 Blanksby SJ, Ellison GB. Acc. Chem. Res. 2003; 36: 255
• 15 Luo Y.-R. Comprehensive Handbook of Chemical Bond Energies. CRC Press; Boca Raton: 2007
• 16 Aizenberg M, Milstein D. Science 1994; 265: 359
• 17 Arndt P, Spannenberg A, Baumann W, Burlakov VV, Rosenthal U, Becke S, Weiss T. Organometallics 2004; 23: 4792
• 18 Lentz D, Braun T, Kuehnel MF. Angew. Chem. Int. Ed. 2013; 52: 3328
• 19a Kraft BM, Lachicotte RJ, Jones WD. J. Am. Chem. Soc. 2001; 123: 10973
• 19b For a recent example utilizing gold hydrides, see: Lv H, Zhan J.-H, Cai Y.-B, Yu Y, Wang B, Zhang J.-L. J. Am. Chem. Soc. 2012; 134: 16216
• 20 Aizenberg M, Milstein D. J. Am. Chem. Soc. 1995; 117: 8674
• 21 Laev SS, Shteingarts VD, Bilkis II. Tetrahedron Lett. 1995; 36: 4655
• 22 Ischay MA, Anzovino ME, Du J, Yoon TP. J. Am. Chem. Soc. 2008; 130: 12886
• 23 Nicewicz DA, MacMillan DW. C. Science 2008; 322: 77
• 24 Narayanam JM. R, Tucker JW, Stephenson CR. J. J. Am. Chem. Soc. 2009; 131: 8756
• 25 Narayanam JM. R, Stephenson CR. J. Chem. Soc. Rev. 2011; 40: 102
• 26 Yoon TP, Ischay MA, Du J. Nature Chem. 2010; 2: 527
• 27 Schultz DM, Yoon TP. Science 2014; 343
• 28 Nguyen JD, D’Amato EM, Narayanam JM. R, Stephenson CR. J. Nature Chem. 2012; 4: 854
• 29 Senaweera SM, Singh A, Weaver JD. J. Am. Chem. Soc. 2014; 136: 3002
• 30 Freeman DB, Furst L, Condie AG, Stephenson CR. J. Org. Lett. 2011; 14: 94
• 31 Campagna S, Puntoriero F, Nastasi F, Bergamini G, Balzani V. Top. Curr. Chem. 2007; 280: 117
• 32 Shchegoleva LN, Bilkis II, Schastnev PV. Chem. Phys. 1983; 82: 343
• 33 Jäger-Fiedler U, Klahn M, Arndt P, Baumann W, Spannenberg A, Burlakov VV, Rosenthal U. J. Mol. Catal. A: Chem. 2007; 261: 184
• 34 Zhan J.-H, Lv H, Yu Y, Zhang J.-L. Adv. Synth. Catal. 2012; 354: 1529
• 35 Andrews RS, Becker JJ, Gagné MR. Angew. Chem. Int. Ed. 2012; 51: 4140