The catalytic sequential activation and functionalization of inert C-H bonds can now be easily promoted by Ruthenium(II) catalysts and contrasts with the previous use of the Ru(0) systems. We shall now show that ruthenium(II) catalysts, associated with carboxylate or phosphate partners, easily lead to the deprotonation of the sp2 C-H bonds, and that water as solvent increases the activity of ruthenium-carboxylate catalysts. Examples of C-C bond cross-couplings involving functional arene C-H bonds will be presented, via direct controlled mono or diarylations, for the synthesis of polydentate nitrogen containing ligands, and via dehydrogenative alkenylations. Whereas Pd-catalyzed dehydrogenation of functional saturated sulfonamides can be achieved via sp3 C-H bond activation, the later appeared more difficult to achieved with ruthenium catalysts. However, it will be shown that selected ruthenium(II) catalysts are able to promote the alkylation, with alkenes, of unsaturated coordinating ketones in the presence of alcohol. Moreover, the dehydrogenation of cyclic saturated heterocycles, followed by regioselective alkylation at the heteroatom beta position, can now be controlled with functional -ruthenium(II) catalysts and innovate in the synthesis of heterocycles. 1. P. B. Arockiam, C. Bruneau, P. H. Dixneuf, Chem. Rev. 112 (2012) 5879. 2. E. Ferrer-Flegeau, C. Bruneau, P. H. Dixneuf, A. Jutand, J. Am. Chem. Soc. 133 (2011) 10161. 3. P. B. Arockiam, C. Fischmeister, C. Bruneau, P. H. Dixneuf, Angew. Chem. Int. Ed. 49 (2010) 6629 4. B. Li, C. Darcel, P. H. Dixneuf, Chem. Commun.,50 ( 2014) 5970.

Unique C-H bond activations and functionalizations with ruthenium(II) catalysts

249th National Meeting (2015)

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