The cationic Ru−H complex [(C6H6)(PCy3)(CO)RuH]+BF4− (1) with 3,4,5,6-tetrachloro-1,2-benzoquinone (L1) was found to be a highly effective catalytic system for the deaminative coupling reaction of enones with simple amines. The coupling reaction led to a regioselective cleavage of unstrained Cα−Cβ bond of enones without employing any reactive reagents or forming wasteful byproducts. The analogous coupling reaction of enones with anilines led to the selective Cα−Cβ cleavage of the enone substrates in forming the N-alkylated anilines. The coupling reaction of benzyl-α,α-d2-amine and 2-octen-4-one resulted in 55% of deuterium on benzylic position and 18-21% of deuterium on α-CH2 of the coupling product. The Hammett plot from the coupling of 2-octen-4-one with para-substituted benzylamines p-X-C6H4CH2NH2 (X = OMe, Me, H, F, Cl, CF3) showed a strong promotional effect by the electron releasing group (ρ = -0.74 ± 0.1). The carbon kinetic isotope effect from the coupling reaction of 4-methoxybenzylamine with 2-octen-4-one was observed on the benzylic carbon of the coupling product (Cα = 1.018). The substrate scope and mechanism of the catalytic reaction will be presented.

Ruthenium-catalyzed coupling reactions of enones with amines via regioselective C–C bond activation

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