The development of new catalytic methodologies for carbon-carbon bond formation continues to be a major challenge in organic synthesis. Cross-coupling reactions, in particular palladium-catalyzed processes, are among the most important current methods for C-C bond formation.1-2 A tremendous effort has been dedicated in the last 40 years to expand the scope of these methodologies and many organometallic reagents as Grignard, zinc, boron, tin and silicon reagents were identified as suitable partner in this reactions. Organolithium reagents in contrast have been scarcely considered due to the difficult control of their reactivity. Considering the importance of organolithium compounds, a procedure to directly employ this reagent in coupling reactions is desirable. Herein we report a general methodology for the cross-coupling of aryllithium with aryl halides that proceeds under mild conditions and in short times.3-4 The observed high efficiency of organolithium in cross-coupling also prompted us to exploit them in the challenging synthesis of highly hindered tri- and tetra-ortho-substituted biaryls.5 References1) E. Negishi, Angew. Chem. Int. Ed. 2011  , 50, 6738.2) J. Magano, J. R. Dunetz, Chem. Rev. 2011  , 111, 2177.3) M. Giannerini, M. Fa�an�s-Mastral, B. L. Feringa, Nat. Chem. 2013  , 5, 667.4) V. Hornillos, M. Giannerini, C. Vila, M. Fa�an�s-Mastral, B. L. Feringa, Org lett. 2013  , 15, 5114.5) M. Giannerini, V. Hornillos, C. Vila, M. Fa�an�s-Mastral, B. L. Feringa, Angew. Chem. Int. Ed. 2013  , 52, 13329.

Direct catalytic cross-coupling of organolithium compounds

248th National Meeting (2014)

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