| 主权项 |
1. A process for the reduction by hydrogenation, using molecular H2, of a C5-C20 substrate of formulawherein Ra represents a C4-C19 linear, branched or cyclic alkyl, alkenyl or alkadienyl group optionally comprising an aromatic ring and optionally comprising one, two or three functional groups selected among ketone, ether, carbon-carbon double or triple bond and carboxylic groups; into the corresponding alcohol or diol, wherein said process is carried out in the presence of
at least one catalyst or pre-catalyst of formula
[Ru(PP)(NN)(RCOO)2] (1)wherein NN represents a C2-C20 bidentate ligand of formula wherein a and a′, simultaneously or independently, represent 0 or 1 (when a′ is 0 then the nitrogen atom is part of an aromatic heterocycle);the R1, taken separately, represent, simultaneously or independently, a hydrogen atom or a C1-6 linear, branched or cyclic alkyl group or a benzyl group optionally substituted; two R1, taken together, may form a saturated heterocycle containing 5 to 7 atoms and including the atoms to which said R1 are bonded, said heterocycle being optionally substituted;R2 and R3, taken separately, represent, simultaneously or independently, a hydrogen atom, a C1-6 linear, branched alkyl group or a C6-10 aromatic group optionally substituted; a R1 and an adjacent R2, taken together, may form a saturated or aromatic heterocycle containing 5 to 8 atoms and including the atoms to which said R1 and R2 are bonded, and optionally containing one additional nitrogen or oxygen atom; two R2, taken together, may form a saturated or unsaturated ring having 5 to 8 atoms and including the carbon atoms to which said R2 or R3 groups are bonded, said ring optionally containing one additional nitrogen and/or oxygen atom; andQ represents a group of formula wherein m is 1 or 2, andR5 and R6 represent, simultaneously or independently, a hydrogen atom, a C1-6 linear, branched or cyclic alkyl or, a C6-10 aromatic group optionally substituted; two distinct R6 and/or R5 groups, taken together, may form a C3-8 saturated ring optionally substituted, including the atoms to which said R6 and/or R5, groups are bonded, and optionally containing one or two additional nitrogen or oxygen atoms;the optional substituents of R1, R2, R3, R5, R6 being one, two, three or four groups selected amongst i) halogens (in particular when said substituents are on aromatic moieties) iii) C1-6 alkoxy, alkyl, alkenyl, or iv) a benzyl group or a fused or non-fused phenyl group, said group being optionally substituted by one, two or three halogen, C1-8 alkyl, alkoxy, amino, nitro, ester, sulfonate or halo- or perhalo-hydrocarbon groups;PP represents a C6-C50 bidentate ligand of formula wherein R11 and R12, when taken separately, represent, simultaneously or independently, a C3-6 branched or cyclic alkyl group or a C6-10 aromatic group optionally substituted; andQ′ representsa group of formula wherein m′ is 1, 2, 3 or 4 and R5′ and R6′ represent, simultaneously or independently, a hydrogen atom, a C1-6 linear or branched alkyl group or a C6-10 aromatic group optionally substituted; two distinct R6′ and/or R5′ groups, taken together, may form a C3 to C8 saturated or unsaturated ring optionally substituted, including the atoms to which said R6′ and/or R5′ groups are bonded, and optionally containing one or two additional nitrogen or oxygen atoms; ora C10-C16 metallocenediyl, a 2,2′-diphenyl, a 1,1 ‘-binaphthalene-2,2’-diyl, a benzenediyl, a naphthalenediyl, 2,3-bicyclo[2:2:1]hept-5-enediyl, 4,6-phenoxazinediyl, 4,5-(9,9-dimethyl)-xanthenediyl, or bis(phen-2-yl)ether group optionally substituted;the optional substituents of R5′, R6′, R11 and R12 are one to five halogens (in particular when said substituents are on aromatic moieties), or one, two or three i) C1-6 linear or branched alkyl alkoxy, groups or halo- or perhalo-hydrocarbon, amine groups, ii) COORh wherein Rh is a C1-6 linear, branched or cyclic alkyl group, iii) NO2 group, or iv) a benzyl group or a fused or non-fused phenyl group, said group being optionally substituted by one, two or three halogen, C1-8 alkyl, alkoxy, amino, nitro, ester, sulfonate or halo- or perhalo-hydrocarbon groups; andeach R represents, simultaneously or independently, a C2-C12 hydrocarbon group branched or cyclic in the α and/or β position, and said hydrocarbon group is optionally comprising one to five heteroatom selected amongst halogen, oxygen and nitrogen atoms; and optionally of an acidic additive. |
