Catalytic ability of a cationic Ru(II) monochloro complex for the asymmetric hydrogenation of dimethyl itaconate and enamides

Isabel Serrano, Montserrat Rodríguez, Isabel Romero, Antoni Llobet, Teodor Parella, Juan M. Campelo, Diego Luna, José M. Marinas, Jordi Benet-Buchholz

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21 Citations (Scopus)

Abstract

The synthesis of two Ru chloro complexes, RuIIICl 3(bpea), 1, and cis-fac-Δ-[RuIICl{(R)-(bpea)}{(S) (BINAP)}]-(BF4), cis-fac-Δ-(R)-(S)-2, (bpea = N,N-bis(2-pyridylmethyl)ethylamine; (S)-BINAP = 2,2′- bis(diphenylphosphino)-1,1′-binaphthyl), is described. Complex 2 is characterized in solution through UV-vis, cyclic voltammetry (CV), and 1D and 2D NMR spectroscopy. X-ray diffraction analysis indicates that in the solid state it possesses the same structure as in solution, as expected for a low-spin d6 Ru(II)-type complex. The molecular structure of cis-fac-Δ-(R)-(S)-2, consists of a nonsymmetric complex, where the Ru metal center has a significantly distorted octahedraltype coordination because of the bulkiness of the (S)-BINAP ligand. cis-fac-Δ-(R)-(S)-2 has a remarkable catalytic performance at P = 6.8 atm of H2 and T = 70°C toward the hydrogenation of prochiral double bonds both from efficiency and from stereoselectivity viewpoints. As an example, prochiral olefins of technological interest such as dimethyl itaconate, methyl 2-acetamidoacrylate or methyl 2-acetamidocinnamate are catalytically hydrogenated by cis-fac-Δ-(R)-(S)-2, with conversions higher than 99.9% and ee > 99. Furthermore, cis-fac-Δ-(R)-(S)-2, also catalyzes the selective hydrogenation of β-keto esters, although the reaction rates are lower than those found with the former substrates. © 2006 American Chemical Society.
Original languageEnglish
Pages (from-to)2644-2651
JournalInorganic Chemistry
Volume45
Issue number6
DOIs
Publication statusPublished - 20 Mar 2006

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