Palladium-catalyzed C(sp²)-C(sp³) cross-couplings are particularly valuable tools in synthetic chemistry and hence a great deal of interest has emerged in this area.^[1] Recently, our group has developed a new cross-coupling strategy based on the migration of an organopalladium species along an alkyl chain.^[2] Through experimental and theoretical mechanistic studies, we have shown that this migration occurs through a beta-H elimination/rotation/insertion sequence.^[3]

In this work, we have extended this migrative-coupling to simple and commercially available alkyl bromides. Under practical Barbier-type conditions involving magnesium insertion and transmetallation with ZnCl₂, a series of linear arylated products could be obtained in a regioconvergent manner with good to excellent linear/branched selectivities, thanks to the use of a suitable phosphine ligand. Moreover, this strategy could be coupled to a non-selective radical bromination process, which allowed the terminal-selective functionalization of simple alkanes in just two steps.^[4]

[1] a) Ranjan Jana, Tejas P. Pathak, Matthew S. Sigman, Chem. Rev. 2011, 111, 1417-1492; b) Olivier Baudoin, Chem. Soc. Rev. 2011, 40, 4902-4911. 
[2] a) Alice Renaudat, Ludivine Jean-Gérard, Rodolphe Jazzar, Christos E. Kefalidis, Eric Clot, Olivier Baudoin, Angew. Chem. Int. Ed. 2010, 49, 7261-7265; b) Sam Aspin, Anne-Sophie Goutierre, Paolo Larini, Rodolphe Jazzar, Olivier Baudoin, Angew. Chem. Int. Ed. 2012, 51, 10808-10811; c) Anthony Millet, Paolo Larini, Eric Clot, Olivier Baudoin, Chem. Sci. 2013, 4, 2241-2247; d) Anthony Millet, David Dailler, Paolo Larini, Olivier Baudoin, Angew. Chem. Int. Ed. 2014, 53, 2678-2682. 
[3] Paolo Larini, Christos E. Kefalidis, Rodolphe Jazzar, Alice Renaudat, Eric Clot, Olivier Baudoin, Chem. Eur. J. 2012, 18, 1932-1944. 
[4] Stéphanie Dupuy, Ke-Feng Zhang, Anne-Sophie Goutierre, Olivier Baudoin, Angew. Chem. Int. Ed. 2016, 55, 14793-14797.