Pd-Catalyzed Homo Cross-Dehydrogenative Coupling of 2-Arylpyridines by Using I₂ as the Sole Oxidant

Abstract

A palladium-catalyzed homo cross-dehydrogenative coupling (CDC) of 2-arylpyridines via C–H activation is described. This reaction employs I₂ as the sole oxidant without any other additives, which complements the hypervalent iodine chemistry, such as of phenyliodonium diacetate (PIDA) or IOAc, in C–H activation research field. A tentative mechanism involving a Pd(II)–Pd(IV) catalytic cycle is proposed to rationalize this homo CDC reaction.

Key words

palladium - biaryl - iodine - C–H activation - cross-dehydrogenative coupling

• References

• 1a Kotha S, Lahiri K, Kashinath D. Tetrahedron 2002; 58: 9633
• 1b Hassan J, Sévignon M, Gozzi C, Schulz E, Lemaire M. Chem. Rev. 2002; 102: 1359
• 1c Tohma H, Morioka H, Takizawa S, Arisawa M, Kita Y. Tetrahedron 2001; 57: 345
• 2a Littke AF, Dai C, Fu GC. J. Am. Chem. Soc. 2000; 122: 4020
• 2b Dai C, Fu GC. J. Am. Chem. Soc. 2001; 123: 2719
• 2c Milne JE, Buchwald SL. J. Am. Chem. Soc. 2004; 126: 13028
• 3a Murai S, Kakiuchi F, Sekine S, Tanaka Y, Kamatani A, Sonoda M, Chatani N. Nature (London) 1993; 366: 529
• 3b Ritleng V, Sirlin C, Pfeffer M. Chem. Rev. 2002; 102: 1731
• 3c Dyker G. Angew. Chem. Int. Ed. 1999; 38: 1699
• 3d Alberico D, Scott ME, Lautens M. Chem. Rev. 2007; 107: 174
• 4a Li C.-J. Acc. Chem. Res. 2009; 42: 335
• 4b Li Z, Li C.-J. J. Am. Chem. Soc. 2004; 126: 11810
• 4c Girard SA, Knauber T, Li C.-J. Angew. Chem. Int. Ed. 2014; 53: 74
• 5a Cai Z.-J, Wang S.-Y, Ji S.-J. Org. Lett. 2013; 15: 5226
• 5b Kanth JV. B, Periasamy M. J. Org. Chem. 1991; 56: 5964
• 6 Wang X.-C, Hu Y, Bonacorsi S, Hong Y, Burrell R, Yu J.-Q. J. Am. Chem. Soc. 2013; 135: 10326
• 7a Dick AR, Hull KL, Sanford MS. J. Am. Chem. Soc. 2004; 126: 2300
• 7b Dudnik AS, Chernyak N, Huang C, Gevorgyan V. Angew. Chem. Int. Ed. 2010; 49: 8729
• 8 Schröder N, Wencel-Delord J, Glorius F. J. Am. Chem. Soc. 2012; 134: 8298
• 9 Giri R, Chen X, Yu JQ. Angew. Chem. Int. Ed. 2005; 44: 2112
• 10 Lyons TW, Sanford MS. Chem. Rev. 2010; 110: 1147
• 11 Dick AR, Sanford MS. Tetrahedron 2006; 62: 2439
• 12 Hull KL, Lanni EL, Sanford MS. J. Am. Chem. Soc. 2006; 128: 14047
• 13 Desai LV, Malik HA, Sanford MS. Org. Lett. 2006; 8: 1141
• 14 Chen X, Dobereiner G, Hao X.-S, Giri R, Maugel N, Yu J.-Q. Tetrahedron 2009; 65: 3085
• 15 Guo X, Deng G, Li C.-J. Adv. Synth. Catal. 2009; 351: 2071
• 16a Liu W, Li L, Li C.-J. Nat. Commun. 2015; 6: 6526
• 16b Liu W, Li L, Chen Z, Li C.-J. Org. Biomol. Chem. 2015; 13: 6170
• 16c Li L, Liu W, Zeng H, Mu X, Cosa G, Mi Z, Li C.-J. J. Am. Chem. Soc. 2015; 137: 8328
• 16d Liu W, Chen Z, Li L, Wang H, Li C.-J. Chem. Eur. J. 2016; in press; DOI: 10.1002/chem.201600219
• 17 Based on our research, higher temperature, longer reaction time and higher concentration produced a higher reaction yield. However, to make a comprimse on these three parameters, we decided to use 110 °C, 0.4 M, and 24 h to optimize the solvent and additive effects.
• 18 Teskey CJ, Lui AY. W, Greaney MF. Angew. Chem. Int. Ed. 2015; 54: 11677
• 19 Park J, Chang S. Angew. Chem. Int. Ed. 2015; 54: 14103