Hydrogenation of carbonyls with tetradentate pnnp ligand ruthenium complexes

A process for the reduction by hydrogenation, using molecular H2, of a C3-C70 substrate containing one or two ketones, aldehydes, esters, or lactones functional groups into the corresponding alcohol, or diol, wherein said process is carried out in the presence of a base and at least one catalyst or pre-catalyst containing Ruthenium and a tetradentate ligand of formula

• wherein one dotted line indicates a single bond and the other dotted line a single or a double bond, z is 1 when both dotted lines is a single bond or is 0 when one dotted line is a double bond and the other a single bond;
• m is 0 or 1;
• n is a integer between 0 and 4;
• q is 0 when the dotted line between N and C(R9)(R10) indicates a double bond or is 1 when the dotted line between N and C(R9)(R10) indicates a single bond;
• q′ is 0 when the dotted line between N and C(R11)(R12) indicates a double bond or is 1 when the dotted line between N and C(R2) indicates a single bond;
• R1 and R2, when taken separately, represent, simultaneously or independently, a linear C1 to C8 alkyl group optionally substituted, a linear C2 to C8 alkenyl group optionally substituted, a branched or cyclic C3 to C8 alkyl or alkenyl group optionally substituted, a C6 to C10 aromatic group optionally substituted, or an OR1′ or NR1′R2′ group, R1′ and R2 being a C1 to C8 alkyl group or a C2 to C8 alkenyl group;
• or R1 and R2, when taken together, form a saturated or unsaturated ring optionally substituted, having 4 to 10 atoms and including the phosphorus atom to which said R1 and R2 groups are bonded;
• R3, R4, R5, R6, R7, R8, R9, R10, R11 and R12, taken separately, represent, simultaneously or independently, a hydrogen atom, a C1-C10 linear alkyl group optionally substituted, a C2-C10 linear alkenyl group optionally substituted, a C3-C10 branched or cyclic alkyl or alkenyl group optionally substituted or a C6 to C10 aromatic group optionally substituted;
• or R3 and R4 and/or R4 and R5 and/or R5 and R6 and/or R6 and R7 and/or R7 and R8 and/or R8 and R9 and/or R9 and R10 and/or R9 and R11 and/or R11 and R12, when taken together, form a saturated or unsaturated ring optionally substituted, having 4 to 10 atoms;
• R13 and R14, when taken separately, represent, simultaneously or independently, a C6 to C10 aromatic group optionally substituted or an OR1′ or NR1′R2′ group wherein R1′ and R2′ is a C1 to C8 alkyl group or a C2 to C8 alkenyl group;
• and
• R15 when taken separately, represent, simultaneously or independently, a hydrogen atom, a halogen atom, a linear C1 to C8 alkyl group optionally substituted, a linear C2 to C8 alkenyl group optionally substituted, a branched or cyclic C3 to C8 alkyl or alkenyl group optionally substituted, or a halo- or perhalo-hydrocarbon, CN, SO3R3′, SO2R3′, NO2, OR3′, or CONR3′R4′ group, R3′ and R4′, independently from each other, being a hydrogen atom or a C1 to C8 alkyl group or a C2 to C8 alkenyl group;
• two adjacent R15 groups can be bonded together to form a C5 to C10 ring optionally substituted;
• the optional substituents of the R1 to R15 groups are one or two halogen atoms, C1 to C10 alkoxy, polyalkyleneglycols, halo- or perhalo-hydrocarbon, COOR, or R groups, wherein R is a C1 to C6 alkyl, or a C5 to C12 cycloalkyl, aralkyl or aromatic group, the latter being also optionally substituted by one, two, or three halogen atoms or C1-C8 alkyl, alkoxy, nitro, sulfonates, halo- or perhalo-hydrocarbon or ester groups.