Hydrogenation of esters with Ru/tetradentate ligands complexes
AssigneeFirmenich SA
InventorsLionel Saudan, Philippe Dupau, Jean-Jacques Riedhauser, Patrick Wyss
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Abstract
The present invention relates to the field of catalytic hydrogenation and, more particularly, to the use of Ru complexes with tetradentate ligands having at least one amino or imino coordinating group and at least one phosphino coordinating group in hydrogenation processes for the reduction of esters or lactones into the corresponding alcohol or diol respectively.
Claims14
A process for the reduction by molecular hydrogenation, of a substrate containing one or two ester or lactone functional groups into its corresponding alcohol or diol, the process comprising reducing said substrate with molecular hydrogen in the presence of a base and at least one catalyst or pre-catalyst in the form of a ruthenium complexes of formula 1 or 2
- [Ru(L4)Y2] (1)
- [Ru(L4)(X)n(Y)2-n](Z)n (2)
- wherein:
- L4 is a ligand of formula (4-A):
- R2 and R3, when taken separately, represent, simultaneously or independently, a linear, branched or cyclic C1 to C8 alkyl or alkenyl group optionally substituted, a C6 to C10 aromatic group optionally substituted, or an OR20′ or NR2′R3′ group, R2′ and R3′ being a C1 to C8 alkyl or alkenyl group;
- or the groups R2 and R3, when taken together, form a saturated or unsaturated ring optionally substituted, having 4 to 10 atoms and including the phosphorus atom to which the R2 and R3 groups are bonded ;
- R9, R10 and R11, taken separately, represent, simultaneously or independently, a hydrogen atom, a C1-C8 linear, branched or cyclic alkyl or alkenyl group optionally substituted or a C6 to C10 aromatic group optionally substituted;
- two adjacent or geminal R9, taken together, may form preferably C5 to C8, ring including the carbon atom to which the R9 groups are bonded;
- an R10 group and an R9 group, in α-position to the same N atom, can be bonded together to form a C4 - to C6 ring;
- two adjacent R11 groups can be bonded together to form a C6 to C10 aromatic ring optionally substituted or a C5 to C12 metallocediyl group optionally substituted and including the carbon atom to which the R11 groups are bonded;
- and
- k are, simultaneously or independently, equal to 0 or 1;
- each Y represents, simultaneously or independently, CO, a hydrogen or halogen atom, a hydroxyl group, or a C1-C6 alkoxy or carboxylic radical, or a BH4 or ALH4 group;
- X represents a C3-C30 mono-phosphine or a solvent;
- Z represents a non-coordinated anion;
- and
- n is 0, 1 or 2 and
- the substrate is a compound of formula (I)
- wherein Ra and Rb represent, simultaneously or independently, a linear, branched or cyclic C1-C30 aromatic, alkyl or alkenyl group optionally substituted;
- or
- Ra and Rb are bonded together and form a C4-C20 saturated or unsaturated group, optionally substituted;
- and
- wherein the substituents of Ra and Rb are a COORc, group, one, two or three halogen, ORc, NRc2 or Rc groups, in which Rc is a hydrogen atom, a halogenated C1- to C2 groups or a C1 to C10 cyclic, linear or branched alkyl, or alkenyl group.
The ligand N,N′-bis{[2-(diphenylphosphino) phenyl]methylene}-2,2-dimethyl-1,3-propanediamine.
A complex of formula (1) or (2)
- [Ru(L4)Y2] (1)
- [Ru(L4)(X)n(Y)2-n](Z)n (2)
- wherein each Y represents, simultaneously or independently, CO, a hydrogen or halogen atom, a hydroxyl group, or a C1-C6 alkoxy or carboxylic radical, or a BH4 or ALH4 group;
- X represents a C3- to C30 mono-phosphine or a solvent;
- Z represents a non-coordinated anion;
- and
- n is 0, 1 or 2, and
- L4 is N,N′-bis{[2-(diphenylphosphino)phenyl]methylene}-2,2-dimethyl-1,3-propanediamine.
Dependencies are inferred from the claim text.