# US 2020/0399299 A1 · Hydrogenation of carbonyls with tetradentate pnnp ligand ruthenium complexes

> Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt

- Number: US 2020/0399299 A1
- Document ID: US20200399299A1
- Status: Published application
- Kind: A1
- Application number: 16/766,543
- Filed: 2019-03-12
- Published: 2020-12-24
- Earliest claimed: 2018-03-16
- Assignees: Firmenich SA
- Applicants: Firmenich SA
- Inventors: Philippe DUPAU; Lucia BONOMO; Laurent KERMORVAN; Murielle HALDIMANN SANCHEZ
- Web page: https://patentgrep.com/patent/US20200399299A1

## CPC

- C07F 15/0053: {without a metal-carbon linkage}
- B01J 31/189: {containing both nitrogen and phosphorus as complexing atoms, including e.g. phosphino moieties, in one at least bidentate or bridging ligand}
- B01J 31/2409: {with more than one complexing phosphine-P atom}
- C07B 35/00: Reactions without formation or introduction of functional groups containing hetero atoms, involving a change in the type of bonding between two carbon atoms already directly linked
- C07D 307/92: Naphthofurans; Hydrogenated naphthofurans
- C07F 9/58: Pyridine rings
- B01J 2231/641: Hydrogenation of organic substrates, i.e. H2 or H-transfer hydrogenations, e.g. Fischer-Tropsch processes
- B01J 2531/004: Ligands
- B01J 2531/821: Ruthenium
- C07C 29/149: with hydrogen or hydrogen-containing gases
- C07F: ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM (metal-containing porphyrins C07D487/22)
- B01J: CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- C07B: GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR (preparation of carboxylic acid esters by telomerisation C07C67/47; telomerisation C08F)
- C07D: HETEROCYCLIC COMPOUNDS (macromolecular compounds C08)
- C07C: ACYCLIC OR CARBOCYCLIC COMPOUNDS

## Abstract

Described herein are catalytic hydrogenation processes, using Ru complexes with tetradentate ligands of formula L in hydrogenation processes for the reduction of ketone, aldehyde, ester, or lactone into the corresponding alcohol or diol respectively. These processes use a ruthenium complex of formula (1) as defined herein.

## Claims

### Claim 1

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.

### Claim 2 (depends on 1)

A process according to claim 1, wherein the ruthenium complex is of formula
[Ru(L)Y2] (1)
wherein L represents a tetradentate ligand as defined in claim 1; and
each Y represents, simultaneously or independently, CO, a hydrogen or halogen atom, a hydroxyl group, or a C1-C6 alkyl, alkenyl, alkoxy, or carboxylic radical, or a BH4 or ALH4 group.

### Claim 3 (depends on 1)

A process according to claim 1, wherein m is 1.

### Claim 4 (depends on 1)

A process according to claim 1, wherein L is a ligand of formula
wherein z, n, q, R1, R2, R3, R4, R5, R6, R9, R10, R11, R12, R13, R14, and R15 have the same meaning as defined in claim 1.

### Claim 5 (depends on 1)

A process according to claim 1, wherein R1 and R2 represent, simultaneously or independently, a linear C1 to C6 alkyl group optionally substituted, a branched or cyclic C3 to C6 alkyl group optionally substituted, a phenyl group optionally substituted; or R1 and R2, when taken together, form a saturated or unsaturated ring optionally substituted, having 4, 5, 6, or 7 carbon atoms and including the phosphorus atom to which said R1 and R2 groups are bonded.

### Claim 6 (depends on 5)

A process according to claim 5, wherein R1 and R2 represent a cyclohexyl, a phenyl, a tert-butyl, an iso-propyl, or an ethyl group.

### Claim 7 (depends on 1)

A process according to claim 1, wherein R13 and R14 represent a phenyl group optionally substituted.

### Claim 8 (depends on 1)

A process according to claim 1, wherein R3, R4, R5, R6, R7, R8, R9, R10, R11, and R12, taken separately, represent, simultaneously or independently, a hydrogen atom, a C1-C4 linear alkyl group optionally substituted, a C5-C6 branched or cyclic alkyl group optionally substituted or a phenyl group optionally substituted; R4 and R5 or R5 and R6 or R8 and R9, when taken together, form a saturated or unsaturated ring optionally substituted, having 4 to 7 carbon atoms.

### Claim 9 (depends on 1, 2, 3, 4, 5, 6, 7, 8)

A process according to claim 1, wherein L is a ligand of formula
wherein z, n, R1, R2, R9, R13, R14, and R15 have the same meaning as defined in claims 1 to 8.

### Claim 10 (depends on 1)

A process according to claim 1, wherein the base has a pKa above 14.

### Claim 11 (depends on 10)

A process according to claim 10, wherein the base is an alkaline or alkaline-earth metal carbonates, an alkaline or alkaline-earth metal hydroxides, C1-10 amidures, C10-26 phosphazene, or an alcoholate of formula (R17O)2M or R17OM′, wherein M is an alkaline-earth metal, M′ is an alkaline metal or an ammonium NR184+, wherein R17 stands for hydrogen or a C1 to C6 linear or branched alkyl radical and R18 stands for a C1 to C10 linear or branched alkyl radical.

### Claim 12 (depends on 1)

A process according to claim 1, wherein the substrate is a compound of formula (I)
wherein p is 0 or 1;
when p is 1, Ra and Rb represent, simultaneously or independently, a linear, branched or cyclic C1-C30 aromatic, alkyl, or alkenyl group, optionally substituted; or
when p is 0, Ra represents a linear, branched or cyclic C1-C30 aromatic, alkyl, or alkenyl group, optionally substituted and Rb represents a hydrogen atom, 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-C2 group, or a C1 to C10 cyclic, linear or branched alkyl, or alkenyl group.

### Claim 13 (depends on 12)

A process according to claim 12, wherein the substrate is a C5-C30 compound of formula (I) wherein Ra and Rb represent, simultaneously or independently, a linear C1-C30 alkyl group optionally substituted, a branched or cyclic C3-C30 alkyl or alkenyl group optionally substituted, or a C5-C30 aromatic group optionally substituted; or Ra and Rb are bonded together and form a C4-C20 saturated or unsaturated linear, branched, mono-, di-, or tri-cyclic group, optionally substituted.

### Claim 14 (depends on 1, 2, 3, 4, 5, 6, 7, 8, 9)

A ligand of formula
wherein m, n, q, z, R2, R3, R4, R5, R6, R7, R8, R9, R10, R11, R12, R13, R14 and R15 have the same meaning as in any one of claims 1 to 9.

### Claim 15 (depends on 2)

A complex of formula (1), as defined in claim 2.