Hydrogenation of carbonyls with tetradentate PNNP ligand ruthenium complexes

Patent metadata

Field	Value
Publication number	US-11858948-B2
Application number	US-201916766543-A
Country	US
Kind code	B2
Filing date	Mar 12, 2019
Priority date	Mar 16, 2018
Publication date	Jan 2, 2024
Grant date	Jan 2, 2024

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.

First claim

The invention claimed is:

1. A process for the reduction by hydrogenation, using molecular H 2 , of a C 3 -C 70 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(R 9 )(R 10 ) indicates a double bond or is 1 when the dotted line between N and C(R 9 )(R 10 ) indicates a single bond;
q′ is 0 when the dotted line between N and C(R 11 )(R 12 ) indicates a double bond or is 1 when the dotted line between N and C(R 11 )(R 12 ) indicates a single bond;
R 1 and R 2 , when taken separately, represent, simultaneously or independently, a linear C 1 to C 8 alkyl group optionally substituted, a linear C 2 to C 8 alkenyl group optionally substituted, a branched or cyclic C 3 to C 8 alkyl or alkenyl group optionally substituted, a C 6 to C 10 aromatic group optionally substituted, or an OR 1′ or NR 1′ R 2′ group, R 1′ and R 2′ being a C 1 to C 8 alkyl group or a C 2 to C 8 alkenyl group; or R 1 and R 2 , when taken together, form a saturated or unsaturated ring optionally substituted, having 4 to 10 atoms and including the phosphorus atom to which said R 1 and R 2 groups are bonded;
R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 and R 12 , taken separately, represent, simultaneously or independently, a hydrogen atom, a C 1 -C 10 linear alkyl group optionally substituted, a C 2 -C 10 linear alkenyl group optionally substituted, a C 3 -C 10 branched or cyclic alkyl or alkenyl group optionally substituted or a C 6 to C 10 aromatic group optionally substituted; or R 3 and R 4 and/or R 4 and R 5 and/or R 5 and R 6 and/or R 6 and R 7 and/or R 7 and R 8 and/or R 8 and R 9 and/or R 9 and R 10 and/or R 9 and R 11 and/or R 11 and R 12 , when taken together, form a saturated or unsaturated ring optionally substituted, having 4 to 10 atoms;
R 13 and R 14 , when taken separately, represent, simultaneously or independently, a C 6 to C 10 aromatic group optionally substituted or an OR 1′ or NR 1′ R 2′ group wherein R 1′ and R 2′ is a C 1 to C 8 alkyl group or a C 2 to C 8 alkenyl group; and
R 15 when taken separately, represent, simultaneously or independently, a hydrogen atom, a halogen atom, a linear C 1 to C 8 alkyl group optionally substituted, a linear C 2 to C 8 alkenyl group optionally substituted, a branched or cyclic C 3 to C 8 alkyl or alkenyl group optionally substituted, or a halo- or perhalo-hydrocarbon, CN, SO 3 R 3′ , SO 2 R 3′ , NO 2 , OR 3′ , or CONR 3′ R 4′ group, R 3′ and R 4′ , independently from each other, being a hydrogen atom or a C 1 to C 8 alkyl group or a C 2 to C 8 alkenyl group; two adjacent R 15 groups can be bonded together to form a C 5 to C 10 ring optionally substituted;
the optional substituents of the R 1 to R 15 groups are one or two halogen atoms, C 1 to C 10 alkoxy, polyalkyleneglycols, halo- or perhalo-hydrocarbon, COOR, or R groups, wherein R is a C 1 to C 6 alkyl, or a C 5 to C 12 cycloalkyl, aralkyl or aromatic group, the latter being also optionally substituted by one, two, or three halogen atoms or C 1 -C 8 alkyl, alkoxy, nitro, sulfonates, halo- or perhalo-hydrocarbon or ester groups.

2. A process according to claim 1 , wherein the ruthenium complex is of formula
[Ru(L)Y 2 ]   (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 C 1 -C 6 alkyl, alkenyl, alkoxy, or carboxylic radical, or a BH 4 or ALH 4 group.

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

4. A process according to claim 1 , wherein L is a ligand of formula

wherein z, n, q, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , and R 15 have the same meaning as defined in claim 1 .

5. A process according to claim 1 , wherein R 1 and R 2 represent, simultaneously or independently, a linear C 1 to C 6 alkyl group optionally substituted, a branched or cyclic C 3 to C 6 alkyl group optionally substituted, a phenyl group optionally substituted; or R 1 and R 2 , 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 R 1 and R 2 groups are bonded.

6. A process according to claim 5 , wherein R 1 and R 2 represent a cyclohexyl, a phenyl, a tert-butyl, an iso-propyl, or an ethyl group.

7. A process according to claim 1 , wherein R 13 and R 14 represent a phenyl group optionally substituted.

8. A process according to claim 1 , wherein R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , and R 12 , taken separately, represent, simultaneously or independently, a hydrogen atom, a C 1 -C 4 linear alkyl group optionally substituted, a C 5 -C 6 branched or cyclic alkyl group optionally substituted or a phenyl group optionally substituted; R 4 and R 5 or R 5 and R 6 or R 8 and R 9 , when taken together, form a saturated or unsaturated ring optionally substituted, having 4 to 7 carbon atoms.

9. A process according to claim 1 , wherein L is a ligand of formula

wherein z, n, R 1 , R 2 , R 9 , R 13 , R 14 , and R 15 have the same meaning as defined in claims 1 to 8 .

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

11. A process according to claim 10 , wherein the base is an alkaline or alkaline-earth metal carbonates, an alkaline or alkaline-earth metal hydroxides, C 1-10 amidures, C 10-26 phosphazene, or an alcoholate of formula (R 17 O) 2 M or R 17 OM′, wherein M is an alkaline-earth metal, M′ is an alkaline metal or an ammonium NR 18 4 + , wherein R 17 stands for hydrogen or a C 1 to C 6 linear or branched alkyl radical and R 18 stands for a C 1 to C 10 linear or branched alkyl radical.

12. 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, R a and R b represent, simultaneously or independently, a linear, branched or cyclic C 1 -C 30 aromatic, alkyl, or alkenyl group, optionally substituted; or
when p is 0, R a represents a linear, branched or cyclic C 1 -C 30 aromatic, alkyl, or alkenyl group, optionally substituted and R b represents a hydrogen atom, a linear, branched or cyclic C 1 -C 30 aromatic, alkyl, or alkenyl group, optionally substituted; or
R a and R b are bonded together and form a C 4 -C 20 saturated or unsaturated group, optionally substituted; and
wherein the substituents of R a and R b are a COOR c , group, one, two, or three halogen, OR c , NR c 2 or R c groups, in which R c is a hydrogen atom, a halogenated C

Assignees

• Firmenich & Cie

Inventors

• Dupau Philippe
• Bonomo Lucia
• Kermorvan Laurent
• Haldimann Sanchez Murielle

Classifications

• C07F15/0053 Primary

  without a metal-carbon linkage · CPC title

• B01J31/189

  containing both nitrogen and phosphorus as complexing atoms, including e.g. phosphino moieties, in one at least bidentate or bridging ligand · CPC title

• B01J31/2409

  with more than one complexing phosphine-P atom · CPC title

• C07B35/00

  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 · CPC title

• C07D307/92

  Naphthofurans; Hydrogenated naphthofurans · CPC title