- METHOD FOR PRODUCING A RUTHENIUM COMPLEX
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Provided is a method for producing a ruthenium complex comprises the step of reacting a ruthenium compound represented by general formula (1): [in-line-formulae][RuX(L)(PP)]X ??(1),[/in-line-formulae] wherein Ru represents a ruthenium atom; X represents a halogen atom; L represents an arene; and PP represents an optically active bisphosphine, with a carboxylate salt represented by general formula (2): [in-line-formulae]R1CO2M ??(2),[/in-line-formulae] wherein M represents a monovalent cation; and R1 represents a group selected from the group consisting of alkyl groups, haloalkyl groups, phenyl groups optionally having a substituent(s), 1-aminoalkyl groups and 1-amino-1-phenylalkyl groups, to produce a ruthenium complex represented by general formula (3): [in-line-formulae]Ru(OCOR1)2(PP) ??(3),[/in-line-formulae] wherein R1 represents the group selected from the group consisting of alkyl groups, haloalkyl groups, phenyl groups optionally having a substituent(s), 1-aminoalkyl groups and 1-amino-1-phenylalkyl groups; and PP represents the optically active bisphosphine.
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Page/Page column 6
(2010/04/23)
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- BINAP-ruthenium(II) dicarboxylate complexes: New, highly efficient catalysts for asymmetric hydrogenations
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The BINAP-ruthenium(II) complexes Ru(OCOR)2[(R)- or (S)2,2′-bis(diarylphosphino)-1,1′-binaphthyl] [aryl = phenyl, p-tolyl; R = CH3, C(CH3)3] have been prepared. The crystal structure of Ru[OCOC(CH3)3] 2[(S)-2,2′-bis(diphenylphosphino)-1,1′-binaphthyl], determined by X-ray crystallography [diffraction data collected at -60°C, formula C54H50O4P2Ru, monoclinic, space group P21, Z = 2, a = 13.272 (2) A?, b = 16.224 (3) A?, c = 12.701 (2) A?, β = 124.34 (1)°, R = 0.037, Rw = 0.043], indicates that the monomeric ruthenium(II) complex has a distorted octahedron coordination geometry involving two phosphorus atoms of BINAP and four oxygen atoms of pivalate ligands. The complex has a Λ structure, while the BINAP-containing seven-membered chelate ring is fixed in a δ conformation. The molecular structure has been compared with that of Rh[(R)-BINAP](norbornadiene)ClO4. These BINAP-ruthenium complexes serve as highly efficient catalysts for asymmetric hydrogenations of various enamides, α-(acylamino)acrylic acids, α,β- and β,γ-unsaturated carboxylic acids, allylic and homoallylic alcohols, α-amino ketones, etc.
- Ohta, Tetsuo,Takaya, Hidemasa,Noyori, Ryoji
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p. 566 - 569
(2008/10/08)
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