WO2024099911A1 - Complexes de carbonyle de fer avec ligands de biphosphine bidentates chiraux - Google Patents

Complexes de carbonyle de fer avec ligands de biphosphine bidentates chiraux Download PDF

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WO2024099911A1
WO2024099911A1 PCT/EP2023/080730 EP2023080730W WO2024099911A1 WO 2024099911 A1 WO2024099911 A1 WO 2024099911A1 EP 2023080730 W EP2023080730 W EP 2023080730W WO 2024099911 A1 WO2024099911 A1 WO 2024099911A1
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iron carbonyl
hydrogen
carbonyl complex
compound
hydrogenation
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Mathias SCHELWIES
Rocco Paciello
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Basf Se
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
    • C07F15/02—Iron compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/20—Carbonyls
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
    • B01J31/2404—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring
    • B01J31/2409—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring with more than one complexing phosphine-P atom
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
    • C07C5/02—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation
    • C07C5/03—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation of non-aromatic carbon-to-carbon double bonds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/60—Reduction reactions, e.g. hydrogenation
    • B01J2231/64—Reductions in general of organic substrates, e.g. hydride reductions or hydrogenations
    • B01J2231/641—Hydrogenation of organic substrates, i.e. H2 or H-transfer hydrogenations, e.g. Fischer-Tropsch processes
    • B01J2231/645—Hydrogenation of organic substrates, i.e. H2 or H-transfer hydrogenations, e.g. Fischer-Tropsch processes of C=C or C-C triple bonds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
    • B01J2531/84—Metals of the iron group
    • B01J2531/842—Iron
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2531/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • C07C2531/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • C07C2531/24—Phosphines
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
    • C07C2601/14—The ring being saturated

Definitions

  • the present invention relates to iron carbonyl complexes of the general formula LFe(CO) 3 (I) with chiral, bidentate biphosphine ligands, processes for their preparation and their use as catalysts for the hydrogenation of olefins, such as, for example, alkyl-substituted olefins or prochiral ⁇ , ⁇ -unsaturated aldehydes or ketones, with hydrogen.
  • olefins such as, for example, alkyl-substituted olefins or prochiral ⁇ , ⁇ -unsaturated aldehydes or ketones
  • Olefins can be hydrogenated using a variety of homogeneous catalysts using hydrogen.
  • Rhodium, iridium or ruthenium-based transition metal complexes are usually used as noble metal catalysts (see, for example, Blaser et al. in Applied Homogeneous Catalysis with Organometallic Compounds, editors B. Cornils, W. A. Herrmann, M. Beller, R. Paciello, Wiley-VCH, New York, Vol. 3, 2018, 621-690).
  • iron carbonyl complexes of the general formula (I) which have chiral, bidentate biphosphine ligands can be used as hydrogenation catalysts and can represent a cost-effective alternative to noble metal catalysts.
  • the iron carbonyl complexes of the general formula (I) can be characterized by high activity, high product selectivity and/or high conversion rates. When using prochiral substrates, the iron carbonyl complexes of the general formula (I) can deliver high enantioselectivities.
  • a further advantage of the iron carbonyl complexes of the general formula (I) is the cost-effective disposal of catalyst residues.
  • the present invention relates to iron carbonyl complexes of the general formula LFe(CO) 3 (I), where
  • L represents a chiral, bidentate bisphosphine ligand, which is preferably selected from compounds of the formula their enantiomers, where
  • R 1 and R 2 each independently represent an unbranched, branched or cyclic hydrocarbon radical having 1 to 20 carbon atoms, which is saturated or can have one or more, usually 1 to about 4, non-conjugated, ethylenic double bonds and which is unsubstituted or carries one or more, usually 1 to 4, identical or different substituents selected from OR 9 , NR 10 R 11 , halogen, C 6 -C 10 aryl and C 3 -C 9 hetaryl, or
  • R 1 and R 2 together can also represent a 2 to 10-membered alkylene group or a 3 to 10-membered cycloalkylene group, in which 1, 2, 3 or 4 non-adjacent CH 2 groups can be replaced by O or NR 9c , where the alkylene group and the cycloalkylene group are saturated or have one or two non-conjugated ethylenic double bonds, and where the alkylene group and the cycloalkylene group are unsubstituted or carry one or more identical or different substituents selected from C 1 -C 4 alkyl;
  • R 3 and R 4 each independently represent hydrogen or straight-chain or branched C 1 -C 4 alkyl
  • R 5 , R 6 , R 7 and R 8 are the same or different and represent C 6 -C 10 aryl which is unsubstituted or carries one or more substituents selected from C 1 -C 6 alkyl, C 3 - C 6 cycloalkyl, C 6 -C 10 aryl, C 1 -C 6 alkoxy and amino;
  • R 9c represents hydrogen, C 1 -C 6 alkyl, C 6 -C 10 aryl, C 7 -C 12 aralkyl or C 7 -C 12 alkylaryl
  • R 9 , R 10 and R 11 each independently represent hydrogen, C 1 -C 4 alkyl, C 6 -C 10 aryl, C 7 - C 12 aralkyl or C 7 -C 12 alkylaryl, where
  • R 10 and R 11 together may also represent an alkylene chain having 2 to 5 carbon atoms, which may be interrupted by N or O.
  • the iron carbonyl complex of the general formula (I) or the iron carbonyl complex formed therefrom, containing a fragment of the formula LFeCO (I') or LFeCO 2 (I") is used to prepare an optically active compound by asymmetric hydrogenation of a prochiral, unsaturated compound with hydrogen.
  • Suitable chiral bidentate bisphosphine ligands for the purposes of the present invention are compounds such as those described, for example, in: I. Ojima (ed.), Catalytic Asymmetry Synthesis, Wiley-VCh, 2nd edition, 2000 or in EN Jacobsen, A. Pfaltz, H. Yamamoto (ed.), Comprehensive Asymmetry Catalysis, 2000, Springer or in W. Tang, X. Zhang, Chem. Rev. 2003, 103, 3029-3069.
  • the following compounds are cited as examples of chiral ligands (1) to (91) that can preferably be used according to the invention, as well as their enantiomers:
  • Particularly preferred chiral, bidentate bisphosphine ligands are those of the general formulas or
  • R 1 and R 2 each independently represent an unbranched, branched or cyclic hydrocarbon radical having 1 to 20 carbon atoms, which is saturated or can have one or more, usually 1 to about 4, non-conjugated, ethylenic double bonds and which is unsubstituted or carries one or more, usually 1 to 4, identical or different substituents selected from OR 9 , NR 10 R 11 , halogen, C 6 -C 10 aryl and C 3 -C 9 hetaryl, or
  • R 1 and R 2 together may also represent a 2 to 10-membered alkylene group or a 3 to 10-membered cycloalkylene group, in which 1, 2, 3 or 4 non-adjacent CH 2 groups may be replaced by O or NR 9c , where the alkylene group and the Cycloalkylene group are saturated or have one or two non-conjugated ethylenic double bonds, and wherein the alkylene group and the cycloalkylene group are unsubstituted or carry one or more identical or different substituents selected from C 1 -C 4 alkyl;
  • R 3 and R 4 each independently represent hydrogen or straight-chain or branched C 1 -C 4 alkyl and R 5 , R 6 , R 7 and R 8 are identical or different and represent C 6 -C 10 aryl which is unsubstituted or carries one or more substituents selected from C 1 -C 6 alkyl, C 3 - C 6 cycloalkyl, C 6 -C 10
  • R 1 and R 2 each independently represent an unbranched, branched or C 1 -C 4 alkyl radical or R 1 and R 2 together or represent a C 3 -C 7 alkanediyl radical, C 3 -C 7 alkenediyl radical, C 5 - C 7 cycloalkanediyl radical or a C 5 -C 7 cycloalkenediyl radical, where the four aforementioned radicals are unsubstituted or carry one or more identical or different substituents selected from C 1 -C 4 alkyl; R 3 and R 4 each independently represent hydrogen or straight-chain or branched C 1 -C 4 alkyl and R 5 , R 6 , R 7 and R 8 represent phenyl.
  • particularly preferred chiral, bidentate bisphosphine ligands are those of the general formula (II), in particular the compound of the formula (1) or the formulas (IIa) or (IIb), referred to below as “Chiraphos”, and the compound of formulas (IId) or (IIc) designated as "Norphos”, and the compound designated as DIOP of formula (4) or formulas (IIe) or (IIf), and the compound of formula (91) or formulas (IIg) or (IIh), where Ph is phenyl and Bn is benzyl.
  • the chiral bidentate bisphosphine ligand is either a compound of the formula or the formula ( ) where Ph stands for phenyl.
  • the selected chiral ligands are each used in the form of one of their two enantiomers.
  • the chiral ligands typically have an enantiomeric excess (ee) of at least 80% ee, in particular at least 90% ee and especially at least 95% ee.
  • collective terms are used which are generally representative of the respective substituents.
  • C n -C m - indicates the possible number of carbon atoms in the respective substituent or substituent part.
  • alkyl includes unbranched or branched alkyl groups having 1 to 4, 6, 12 or 25 C atoms. These include, for example, C 1 -C 6 -alkyl, such as methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec.-butyl, tert.-butyl, n-pentyl, 2-pentyl, 2-methylbutyl, 3-methylbutyl, 1,2-dimethylpropyl, 1,1-dimethylpropyl, 2,2-dimethylpropyl, 1-ethylpropyl, n-hexyl, 2-hexyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl, 2,3-dimethylbutyl, 1,1-dimethylbutyl, 2,2-dimethylbutyl, 3,
  • Alkyl preferably refers to unbranched or branched C 1 - C 6 alkyl groups.
  • cycloalkyl encompasses cyclic, saturated hydrocarbon groups having 3 to 6, 12 or 25 carbon ring members, e.g. C 3 - C 8 cycloalkyl such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl and cyclooctyl, or C 7 -C 12 bicycloalkyl.
  • alkoxy stands for an alkyl group bonded via an oxygen and having 1 to 6 C atoms, e.g.
  • C 1 -C 6 -alkoxy such as methoxy, ethoxy, n-propoxy, 1-methylethoxy, butoxy, 1-methylpropoxy, 2-methylpropoxy, 1,1-dimethylethoxy, pentoxy, 1-methylbutoxy, 2-methylbutoxy, 3-methylbutoxy, 1,1-dimethylpropoxy, 1,2-dimethylpropoxy, 2,2-dimethylpropoxy, 1-ethylpropoxy, hexoxy, 1-methylpentoxy, 2-methylpentoxy, 3-methylpentoxy, 4-methylpentoxy, 1,1-dimethylbutoxy, 1,2-dimethylbutoxy, 1,3-dimethylbutoxy, 2,2-dimethylbutoxy, 2,3-dimethylbutoxy, 3,3-dimethylbutoxy, 1-ethylbutoxy, 2-ethylbutoxy, 1,1,2-trimethylpropoxy, 1,2,2-trimethylpropoxy, 1-ethyl-1-methylpropoxy or 1-ethyl-2-methylpropoxy.
  • Alkoxy is preferably C 1 -C 4 -alkoxy.
  • alkenyl includes unbranched or branched hydrocarbon radicals having 2 to 4, 6, 12 or 25 C atoms which contain at least one double bond, for example 1, 2, 3 or 4 double bonds.
  • C 2 -C 6 -alkenyl such as ethenyl, 1-propenyl, 2-propenyl, 1-methylethenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-methyl-1-propenyl, 2-methyl-1-propenyl, 1-methyl-2-propenyl, 2-methyl-2-propenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 1-methyl-1-butenyl, 2-methyl-1-butenyl, 3-methyl-1-butenyl, 1-methyl-2-butenyl, 2-methyl-2-butenyl, 3-methyl-2-butenyl, 1-methyl-3-butenyl, 2-methyl-3-butenyl, 3-Methyl-3-butenyl, 1,1-Dimethyl-2-propenyl, 1,2-Dimethyl-1-propenyl, 1,2-Dimethyl-2-propenyl, 1-Ethyl-1propenyl, 1,1-
  • Alkenyl preferably refers to unbranched C 2 -C 12 alkenyl groups or branched C 3 -C 12 alkenyl groups each having 1 to 3 double bonds, particularly preferably unbranched C 2 -C 6 alkenyl groups or branched C 3 -C 6 alkenyl groups each having one double bond.
  • alkylene refers to divalent hydrocarbon radicals having 2 to 25 carbon atoms. The divalent hydrocarbon radicals can be unbranched or branched.
  • C 2 -C 16 alkylene groups such as 1,4-butylene, 1,5-pentylene, 2-methyl-1,4-butylene, 1,6-hexylene, 2-methyl-1,5-pentylene, 3-methyl-1,5-pentylene, 1,7-heptylene, 2-methyl-1,6-hexylene, 3-methyl-1,6-hexylene, 2-ethyl-1,5-pentylene, 3-ethyl-1,5-pentylene, 2,3-dimethyl-1,5-pentylene, 2,4-dimethyl-1,5-pentylene, 1,8-octylene, 2-methyl-1,7-heptylene, 3-methyl-1,7-heptylene, 4-methyl-1,7-heptylene, 2-ethyl-1,6-hexylene, 3-ethyl-1,6-hexylene, 2,3-dimethyl-1,6- hexylene, 2,4-dimethyl-1,
  • Alkylene is preferably unbranched C 2 -C 12 alkylene groups or branched C 3 -C 12 alkylene groups, in particular unbranched C 2 -C 6 alkylene groups or branched C 3 -C 6 alkylene groups.
  • the carbon atom at the branching point or the carbon atoms at the respective branching points can, independently of one another, have an R or an S configuration or both configurations in equal or different proportions.
  • alkenylene refers to divalent hydrocarbon radicals having 2 to 25 carbon atoms, which may be unbranched or branched, wherein the main chain has one or more double bonds, for example 1, 2 or 3 double bonds.
  • C 2 -C 1 8- alkenylene groups such as ethylene, propylene, 1-, 2-butylene, 1-, 2-pentylene, 1-, 2-, 3-hexylene, 1,3-hexadienylene, 1,4-hexadienylene, 1-, 2-, 3-heptylene, 1,3-heptadienylene, 1,4-heptadienylene, 2,4-heptadienylene, 1-, 2-, 3-octenylene, 1,3-octadienylene, 1,4-octadienylene, 2,4-octadienylene, 1-, 2-, 3-nonenylene, 1-, 2-, 3-, 4-, 5-decenylene, 1-, 2-, 3-, 4-, 5- Undecenylene, 2-, 3-, 4-, 5-, 6-Dodecenylene, 2,4-Dodecadienylene, 2,5-Dodecadienylene, 2,6- Dodecadienylene
  • alkenylene is unbranched C 3 -C 12 alkenylene groups or branched C 4 -C 12 alkenylene groups each having one or two Double bonds, in particular unbranched C 3 - C 8 alkenylene groups with one double bond.
  • the double bonds in the alkenylene groups can be present independently of one another in the E and Z configurations or as a mixture of both configurations.
  • halogen includes fluorine, chlorine, bromine and iodine, preferably fluorine, chlorine or bromine.
  • aryl includes one to three-nuclear aromatic ring system containing 6 to 14 carbon ring members.
  • aryl includes one to three-nuclear aromatic ring system containing 6 to 14 carbon ring members, where one or more, for example 1, 2, 3, 4, 5 or 6, carbon atoms are substituted by a nitrogen, oxygen and/or sulfur atom.
  • C 3 -C 9 - hetaryl groups such as 2-furyl, 3-furyl, 2-thienyl, 3-thienyl, 2-pyrrolyl, 3-pyrrolyl, 3-isoxazolyl, 4-isoxazolyl, 5-isoxazolyl, 3-isothiazolyl, 4-isothiazolyl, 5-isothiazolyl, 3-pyrazolyl, 4-pyrazolyl, 5-pyrazolyl, 2-oxazolyl, 4-oxazolyl, 5-oxazolyl, 2-thiazolyl, 4-thiazolyl, 5-thiazolyl, 2-imidazolyl, 4-imidazolyl, 1,2,4-oxadiazol-3-yl, 1,2,4-oxadiazol-5-yl, 1,2,4-thiadiazol-3-yl, 1,2,4-thiadiazol-5-yl, 1,2,4-triazol-3-yl, 1,3,4-oxadiazol-2-yl, 1,3,4-oxadiazol-2-
  • Hetaryl is preferably C 5 - C 6 -hetaryl.
  • aralkyl includes a mono- to di-nuclear aromatic ring system bonded via an unbranched or branched C 1 -C 6 -alkyl group, containing 6 to 10 carbon ring members. These include, for example, C 7 -C 12 -aralkyl, such as phenylmethyl, 1-phenylethyl, 2-phenylethyl, 1-phenylpropyl, 2-phenylpropyl, 3-phenylpropyl and the like.
  • aralkyl includes a mono- to di-nuclear aromatic ring system containing 6 to 10 carbon ring members, which is substituted by one or more, for example 1, 2 or 3, unbranched or branched C 1 -C 6 -alkyl radicals.
  • C 7 -C 12 -alkylaryl such as 1-methylphenyl, 2-methylphenyl, 3-methylphenyl, 1-ethylphenyl, 2-ethylphenyl, 3-ethylphenyl, 1-propylphenyl, 2-propylphenyl, 3-propylphenyl, 1-iso-propylphenyl, 2-iso-propylphenyl, 3-iso-propylphenyl, 1-butylphenyl, 2-butylphenyl, 3-butylphenyl, 1-iso-butylphenyl, 2-iso-butylphenyl, 3-iso-butylphenyl, 1-sec-butylphenyl, 2-sec-butylphenyl, 3- sec-butylphenyl, 1-tert-butylphenyl, 2-tert-butylphenyl, 3-tert-butylphenyl, 1-(1- phenyl, 2-(1-phenyl, 2-
  • the present invention relates to iron carbonyl complexes of the general formula LFe(CO) 3 (I), where
  • L represents a chiral bidentate bisphosphine ligand selected from
  • R 1 and R 2 each independently represent an unbranched, branched or C 1 -C 4 alkyl radical or
  • R 1 and R 2 together or represent a C 3 -C 7 -alkanediyl radical, C 3 -C 7 -alkenediyl radical, C 5 - C 7 -cycloalkanediyl radical or a C 5 -C 7 -cycloalkenediyl radical, where the four aforementioned radicals are unsubstituted or carry one or more identical or different substituents selected from C 1 -C 4 - alkyl;
  • R 3 and R 4 each independently represent hydrogen or straight-chain or branched C 1 -C 4 alkyl
  • R 5 , R 6 , R 7 and R 8 stand for phenyl.
  • the chiral bidentate bisphosphine ligand L is particularly preferably a compound of the general formula (II).
  • Particularly preferred iron complexes of the general formula LFe(CO) 3 (I) are listed in the following table: The most preferred iron complexes are A-1 and A-2.
  • Fig.1 shows the asymmetric unit of the crystal structure of Fe(CO) 3 (R,R-Chiraphos).
  • Fig.2 shows the crystal structure of Fe(CO) 3 (R,R-chiraphos).
  • the iron complex has an axial-equatorial coordination of R,R-chiraphos to the central atom.
  • the present invention also relates to the use of the above-described iron carbonyl complexes of the general formula (I) as a catalyst, in particular the use of the iron carbonyl complexes of the general formula (I) for preparing an organic compound by hydrogenating an unsaturated organic compound, such as an unsaturated carbonyl compound, an alkene or imine, with hydrogen.
  • the iron carbonyl complex can advantageously be used to prepare an optically active compound by asymmetric hydrogenation of a prochiral, unsaturated compound with hydrogen.
  • the present invention is also directed to processes for preparing a compound by hydrogenating an unsaturated compound with hydrogen in the presence of at least one iron carbonyl complex of the general formula (I).
  • the process according to the invention has at least one or all of the following features a - h: a) carrying out the hydrogenation at a hydrogen pressure of 5 to 200 bar, in particular at a hydrogen pressure of 10 to 100 bar; b) carrying out the process batchwise or continuously; c) in-situ generation of the iron carbonyl complex before or during the hydrogenation by reacting an achiral iron precursor compound with a chiral, bidentate bisphosphine ligand L and optionally CO; d) pretreatment of the catalyst before the hydrogenation with a gas mixture containing carbon monoxide or carbon monoxide/hydrogen; e) carrying out the hydrogenation in the presence of carbon monoxide additionally added to the reaction mixture; f) carrying out the hydrogenation with hydrogen which has a carbon monoxide content in the range from 50 to
  • the unsaturated organic compound is preferably a doubly or trisubstituted, prochiral or non-prochiral, unsaturated organic compound, in particular a prochiral or non-prochiral, unsaturated carbonyl compound, in particular a prochiral or non-prochiral, ⁇ , ⁇ -unsaturated ketone or a prochiral or non-prochiral ⁇ , ⁇ -unsaturated aldehyde.
  • Examples of preferred unsaturated organic compounds are compounds of the general formula , in which R 12 and R 13 are the same or different and each represent hydrogen, C 6 -C 10 -aryl, C 3 -C 9 -hetaryl, an unbranched, branched or cyclic hydrocarbon radical having 1 to 25 carbon atoms, which is saturated or has one or more, e.g. 1, 2, 3, 4 or 5, preferably non-conjugated ethylenic double bonds, and which is unsubstituted or carries one or more, e.g.
  • R 14 represents hydrogen, C 1 -C 6 -alkoxy or a straight-chain, branched or cyclic hydrocarbon radical having 1 to 25 carbon atoms which is saturated or has one or more, e.g.
  • R 14 together with one of the radicals R 12 or R 13 can also represent a 3 to 25-membered alkylene group, in which 1, 2, 3 or 4 non-adjacent CH 2 groups can be replaced by O or NR 16c , where the alkylene group is saturated or has one or more, eg 1, 2, 3, 4 or 5, preferably non-conjugated ethylenic double bonds, and where the alkylene group is unsubstituted or carries one or more, eg 1, 2, 3 or 4, identical or different substituents selected from OR 17 , NR 16a R 16b , halogen, C 1
  • the prochiral ⁇ , ⁇ -unsaturated carbonyl compound is preferably a prochiral, ⁇ , ⁇ -unsaturated ketone or, in particular, a prochiral, ⁇ , ⁇ -unsaturated aldehyde.
  • the process according to the invention is preferably suitable for the preparation of optically active aldehydes or ketones by asymmetric hydrogenation of prochiral ⁇ , ⁇ -unsaturated aldehydes or ketones.
  • the process according to the invention is particularly preferably suitable for the preparation of optically active aldehydes by asymmetric hydrogenation of prochiral ⁇ , ⁇ -unsaturated aldehydes.
  • the prochiral ⁇ , ⁇ -unsaturated carbonyl compound is selected from compounds of the general formula , wherein R 12 and R 13 are different from one another and each represents an unbranched, branched or cyclic hydrocarbon radical having 1 to 25 carbon atoms, which is saturated or has one or more, eg 1, 2, 3, 4 or 5, preferably non-conjugated ethylenic double bonds, and which is unsubstituted or carries one or more, eg 1, 2, 3 or 4, identical or different substituents selected from OR 17 , NR 16a R 16b , halogen, C 6 -C 10 aryl and C 3 -C 9 hetaryl;
  • R 14 represents hydrogen or an unbranched, branched or cyclic hydrocarbon radical having 1 to 25 carbon atoms which is saturated or has one or more, eg 1, 2, 3, 4 or 5, preferably non-conjugated ethylenic double bonds, and which is unsubstit
  • the unbranched, branched or cyclic hydrocarbon radicals having 1 to 25 carbon atoms mentioned in the definitions of the radicals R 12 , R 13 and R 14 are generally unbranched C 1 -C 25 alkyl groups, unbranched C 2 -C 25 alkenyl groups, unbranched C 4 -C 25 alkadienyl groups, branched C 3 -C 25 alkyl groups, branched C 3 -C 25 alkenyl groups, branched C 5 -C 25 alkadienyl groups and C 3 -C 25 cycloalkyl groups or C 3 -C 24 cycloalkyl groups which are substituted by one or more, e.g.
  • the cyclic hydrocarbon radicals also include those cyclic hydrocarbon radicals which have a phenyl ring which optionally carries one or more, for example 1, 2, 3, 4, 5 or 6 C 1 -C 4 -alkyl groups, where the phenyl ring is bonded directly to the ethylenically unsaturated double bond or the carbonyl group in formula (II) or is bonded via a C 1 -C 6 -alkylene group.
  • An alkenyl group is understood to be a linear or branched aliphatic hydrocarbon radical which is monounsaturated.
  • An alkdienyl group is understood to be a linear or branched aliphatic hydrocarbon radical which is diunsaturated.
  • the 3- to 25-membered alkylene groups which are saturated and which are mentioned in the definition of the radical R 14 are generally unbranched or branched C 3 -C 25 -alkylene groups, as defined above.
  • the 3- to 25-membered alkylene groups mentioned in the definition of the radical R 14 which have one or more, eg 1, 2, 3 or 4, non-conjugated ethylenic double bonds, are generally unbranched or branched C 3 -C 25 alkenylene groups, as defined above.
  • one of the radicals R 12 and R 13 is methyl or ethyl, in particular methyl
  • the other radical is an unbranched, branched or cyclic hydrocarbon radical having 3 to 25 carbon atoms, which is saturated or has one or more, eg 1, 2, 3, 4 or 5, preferably non-conjugated ethylenic double bonds, and which is unsubstituted or has one or more, eg 1, 2, 3 or 4, identical or different substituents selected from OR 17 , NR 16a R 16b , halogen, C 6 - to C 10 -aryl and C 3 - to C 9 -hetaryl.
  • one of the radicals R 12 and R 13 is methyl or ethyl, in particular methyl
  • the other radical is an unbranched, branched or cyclic hydrocarbon radical having 3 to 25 carbon atoms, which is saturated or has one or more, e.g. 1, 2 or 3, preferably non-conjugated ethylenic double bonds.
  • R 14 is in particular hydrogen.
  • the prochiral ⁇ , ⁇ -unsaturated carbonyl compound is selected from compounds of the general formula , in which R 12 and R 13 each represent an unbranched or branched hydrocarbon radical having 2 to 25, in particular 3 to 20 carbon atoms, which is saturated or has 1, 2, 3, 4 or 5 non-conjugated ethylenic double bonds, such as, for example, neral/geranial.
  • the process according to the invention can be used to asymmetrically hydrogenate prochiral ⁇ , ⁇ -unsaturated aldehydes or ketones of the formula (VIII), such as, for example, citronellal, in optically active form, the carbon atom which carries the radicals R 12 and R 13 representing the asymmetry center generated by the hydrogenation.
  • formula R 12 , R 13 and 14 d R has the meanings given for formula (VIII), in particular the meanings given for formulas (VIIIa) and (VIIIb).
  • the corresponding ⁇ , ⁇ -saturated aldehydes are accessible through the inventive asymmetric, i.e.
  • the E or Z double bond isomers used are preferably one of the enantiomers of the optically active aldehyde. The same applies to the substrates or
  • mixtures of the two double bond isomers can also be reacted in the manner according to the invention. In this way, mixtures of the two enantiomers of the desired target compound are obtained.
  • the preparation process according to the invention is carried out in the presence of an optically active iron carbonyl complex of the general formula (I) which is soluble in the reaction mixture or of an iron carbonyl complex formed therefrom and containing a fragment of the formula LFeCO (I') or LFeCO (I").
  • the present invention also relates to a process for the preparation of an iron carbonyl complex of the general formula (I) comprising the reaction of a chiral, bidentate bisphosphine ligand L, which is preferably selected from compounds
  • the iron precursor compound is preferably a compound of the formula Fe(COT)(CO) 3 (Va) or Fe(CO) 5 (Vb), where COT is cyclooctatetraene.
  • Fe(COT)(CO) 3 (Va) is preferably reacted with the chiral, bidentate bisphosphine ligand L at a temperature of 20 to 120 °C.
  • Fe(CO) 5 (Vb) can also be reacted directly with the bidentate bisphosphine ligand L.
  • an Fe(II) source can also be used under reductive conditions.
  • FeBr 2 or FeCl 2 can be treated with the bidentate bisphosphine ligand L and then reacted with CO, H 2 /CO or CO and a reducing agent.
  • the iron carbonyl complex can be generated in situ by reacting an achiral iron precursor compound with a chiral, bidentate bisphosphine ligand L and optionally CO before or during hydrogenation.
  • the term “in situ” means that the iron carbonyl complex is generated directly before or at the beginning of the hydrogenation.
  • the catalyst is generated before the hydrogenation.
  • This means that the iron carbonyl complex used is either pretreated with a gas mixture containing carbon monoxide and hydrogen before hydrogenation (i.e. a so-called preformation is carried out) or the hydrogenation is carried out in the presence of carbon monoxide additionally added to the reaction mixture or a preformation is carried out and then the hydrogenation is carried out in the presence of carbon monoxide additionally added to the reaction mixture.
  • the iron carbonyl complex is pretreated with a gas mixture containing carbon monoxide and hydrogen and the hydrogenation is carried out in the presence of carbon monoxide additionally added to the reaction mixture.
  • the above-mentioned pretreatment of the iron carbonyl complex is carried out with a gas mixture comprising 20 to 90 vol.% carbon monoxide, 10 to 80 vol.% hydrogen and 0 to 5 vol.% other gases, the above-mentioned volume fractions adding up to 100 vol.%, at a pressure of 5 to 100 bar.
  • excess carbon monoxide is separated from the catalyst thus obtained before use in the hydrogenation.
  • excess carbon monoxide is understood to mean carbon monoxide that is contained in the resulting reaction mixture in gaseous or dissolved form and is not bound to the iron carbonyl complex. Accordingly, the excess carbon monoxide that is not bound to the iron carbonyl complex is removed at least to a large extent, i.e. to an extent that any residual amounts of dissolved carbon monoxide do not have a disruptive effect on the subsequent hydrogenation. This is usually ensured if about 90%, preferably about 95% or more of the carbon monoxide used for preforming is separated. The excess carbon monoxide is preferably completely removed from the iron carbonyl complex obtained by preforming. The excess carbon monoxide can be separated from the reaction mixture containing the iron carbonyl complex in various ways.
  • the iron carbonyl complex or the mixture containing the iron carbonyl complex obtained by preforming is preferably depressurized to a pressure of up to about 5 bar (absolute), preferably, especially when carrying out the preforming in the pressure range from 5 to 10 bar, to a pressure of less than 5 bar (absolute), preferably to a pressure in the range from about 1 bar to about 5 bar, preferably 1 to less than 5 bar, particularly preferably to a pressure in the range from 1 to 3 bar, very particularly preferably to a pressure in the range from about 1 to about 2 bar, particularly preferably to normal pressure, so that gaseous, unbound carbon monoxide escapes from the preforming product.
  • the above-mentioned relaxation of the preformed catalyst can be carried out, for example, using a high-pressure separator, as is known to those skilled in the art.
  • a high-pressure separator in which the liquid is in the continuous phase, are described, for example, in: Perry's Chemical Engineers' Handbook, 1997, 7th edition, McGraw-Hill, pp. 14.95 and 14.96; the prevention of possible droplet entrainment is described on pages 14.87 to 14.90.
  • the relaxation of the preformed iron carbonyl complex can be carried out in one or two stages until the desired pressure in the range from 1 bar to about 5 bar is reached, the temperature usually falling to 10 to 40°C.
  • the separation of excess carbon monoxide can be achieved by so-called stripping of the iron carbonyl complex or the mixture containing the iron carbonyl complex with a gas, advantageously with a gas that is inert under the reaction conditions.
  • stripping is understood by the person skilled in the art to mean the introduction of a gas into the iron carbonyl complex or the reaction mixture containing the iron carbonyl complex, as described, for example, in WRA Vauck, HA Müller, Grundoperationenchemischer Maschinenmaschinestechnik, Deutscher Verlag für Grundstoffchemie Leipzig, Stuttgart, 10th edition, 1984, page 800.
  • suitable inert gases are: hydrogen, helium, neon, argon, xenon, nitrogen and/or CO 2 , preferably hydrogen, nitrogen, argon.
  • the hydrogenation is then preferably carried out using hydrogen which has a carbon monoxide content in the range from 50 to 3000 ppm, in particular in the range from 100 to 2000 ppm, especially in the range from 200 to 1000 ppm and very particularly in the range from 400 to 800 ppm.
  • the hydrogenation is advantageously carried out at a pressure of about 5 to about 200 bar, in particular from about 10 to about 100 bar, especially at about 60 to about 100 bar and a temperature of generally about 0°C to about 120°C, preferably about 20°C to about 110°C, in particular at about 50°C to about 100°C.
  • the choice of solvent to be used to carry out the hydrogenation is not critical.
  • Suitable solvents that are inert under the reaction conditions are, for example, ethers, alcohols (such as ethanol, methanol, iPrOH, nPrOH, n-BuOH and cyclohexanol), tetrahydrofuran, methyltetrahydrofuran, toluene, xylenes, chlorobenzene, octadecanol, biphenyl ether, Texanol, Marlotherm, Oxo-oil 9N (hydroformylation products from isomeric octenes, BASF SE) and the like.
  • alcohols such as ethanol, methanol, iPrOH, nPrOH, n-BuOH and cyclohexanol
  • tetrahydrofuran methyltetrahydrofuran
  • toluene toluene
  • xylenes chlorobenzene
  • octadecanol biphen
  • suitable reaction vessels for carrying out the hydrogenation according to the invention are all those which allow reactions under the conditions mentioned, in particular pressure and temperature, and are suitable for hydrogenation reactions, such as autoclaves, tubular reactors, bubble columns, etc.
  • the hydrogenation is carried out using high-boiling, generally viscous solvents, such as those described above (such as the solvents octadecanol, biphenyl ether, Texanol, Marlotherm ® , oxo oil 9N mentioned), or if the hydrogenation is carried out without additional use of solvent but with a leveling of the high boilers which are formed to a small extent as by-products (such as dimers or trimers which are formed by reactions of the reactants or products and subsequent reactions), it can be advantageous to ensure good gas input and good mixing of the gas phase and condensed phase. This can be achieved, for example, by carrying out the hydrogenation step of the process according to the invention in a gas circulation reactor.
  • Gas circulation reactors are known to the person skilled in the art and are described, for example, in P. Trambouze, J.-P. Euzen, Chemical Reactors, Ed. Technip, 2004, pp. 280-283 and P. Zehner, R. Benfer, Chem. Eng. Sci.1996, 51, 1735-1744 and, for example, in EP 1140349.
  • gas or gas mixture to be used the hydrogen containing carbon monoxide
  • the two-fluid nozzle is characterized in that the liquid and gas to be introduced into the reactor pass through two separate, nested tubes under pressure to the nozzle mouth and are combined there.
  • the process according to the invention can be carried out successfully with and without the addition of tertiary amines. Instead of tertiary amines, alkoxides, carbonates or hydrogen carbonates can also be added.
  • the process according to the invention is preferably carried out in the absence, ie without the addition of additional tertiary amines or in the presence of only catalytic amounts of additional tertiary amines.
  • the amount of amine used can be between 0.5 and 500 mol equivalents based on the amount of metal used, but preferably 1 to 100 mol equivalents based on the amount of metal used.
  • the choice of tertiary amine is not critical.
  • short-chain alkylamines such as triethylamine
  • long-chain alkylamines such as tridodecylamine
  • the hydrogenation process according to the invention is carried out in the presence of a tertiary amine, preferably tridodecylamine, in an amount of about 2 to 30 mol equivalents, preferably about 5 to 20 mol equivalents and particularly preferably 5 to 15 mol equivalents, based on the amount of transition metal used.
  • the reaction is advantageously stopped when the target compound is present in the reaction mixture in the desired yield and, if appropriate, the desired optical activity, ie with the desired enantiomeric excess (ee), as can be determined by the person skilled in the art by routine investigations, for example by means of chromatographic methods.
  • the hydrogenation is usually complete after about 1 to about 150 hours, often after about 2 to about 24 hours.
  • the process according to the invention makes it possible to provide hydrogenated olefins, optically active carbonyl compounds, in particular optically active aldehydes in high yields and enantiomeric excesses.
  • the desired asymmetrically hydrogenated compounds are usually obtained in an enantiomeric excess of at least 80% ee, often with an enantiomeric excess of about 85 to about 99% ee.
  • the maximum achievable enantiomeric excess can depend on the purity of the substrate used, in particular with regard to the isomer purity of the double bond to be hydrogenated.
  • suitable starting substances are particularly those which have an isomer ratio of at least about 90:10, preferably at least about 95:5 with respect to the E/Z double bond isomers.
  • the homogeneous catalysts used can be stabilized by preforming and/or by the carbon monoxide additionally introduced into the reaction system, which on the one hand significantly increases the service life of the catalysts and on the other hand enables the homogeneous catalysts to be reused.
  • the reaction product obtained can be removed from the reaction mixture by methods known to those skilled in the art, such as distillation, and the remaining catalyst can be used in further reactions, if necessary after further preforming.
  • the process according to the invention can accordingly be operated both discontinuously (batchwise) or semi-continuously and continuously and is particularly suitable for reactions on an industrial scale.
  • the organic, unsaturated compound is converted to the desired organic compound in the presence of an iron precursor compound which is soluble in the reaction mixture, such as, for example, Fe(COT)(CO) 3 (Va) or Fe(COT)(CO) 3 (Va).
  • an iron precursor compound which is soluble in the reaction mixture
  • the catalyst is preferably preformed under the conditions mentioned above and the asymmetric hydrogenation is then carried out in the presence of hydrogen which contains in particular 50 to 3000 ppm of carbon monoxide.
  • the addition of solvents is advantageously dispensed with and the mentioned reactions in the substrate to be reacted or the product and optionally in high-boiling by-products as a solvent medium.
  • Example 1 Preparation of Fe(CO) 3 (R,R-Chiraphos) Under a protective gas atmosphere, Fe(COT)(CO) 3 (885 mg, 3.63 mmol) is dissolved in absolute toluene (20 mL) at room temperature and R,R-Chiraphos (1.65 g, 3.87 mmol) is added. The dark red solution is stirred for 96 h at 105°C. The solution is filtered through silica gel and washed with toluene (20 mL).
  • the iron carbonyl complex A-1 (Fe(CO) 3 (R,R-Chiraphos), crystallizes in an orthorhombic unit cell, space group P212121 (see Fig.1 and 2).
  • the structure of Fe(CO) 3 (R,R-Chiraphos) was determined by single crystal X-ray diffraction: details can be found in Tables 1, 2 and 3.
  • Table 1 Crystal structure data of Error! Reference source not found..
  • the temperature is increased to the values given in the table below. After reaching the desired reaction temperature, a hydrogen pressure of 80 bar is set. After 20 h, the mixture is cooled to room temperature and depressurized. The reaction product is analyzed by GC. VF-Wax column (30 mx 0.25 mm / 0.5 ⁇ m; 5 min at 60°C then at 20°C/min to 250°C; flow rate: 2.0 mL/min; H 2 as carrier gas). Conversion determined using GC-Fl.%.

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Abstract

La présente invention concerne des complexes de carbonyle de fer de formule générale LFe(CO)3 (I), dans laquelle L est un ligand biphosphine bidenté chiral, des procédés pour les préparer et leur utilisation en tant que catalyseurs pour hydrogéner des oléfines, par exemple des oléfines substituées par alkyle, ou des aldéhydes ou cétones α,β-insaturés prochiraux, avec de l'hydrogène.
PCT/EP2023/080730 2022-11-08 2023-11-03 Complexes de carbonyle de fer avec ligands de biphosphine bidentates chiraux WO2024099911A1 (fr)

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Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1140349A1 (fr) 1998-11-26 2001-10-10 Basf Aktiengesellschaft Reacteur pour effectuer en continu des reactions gaz-liquide, liquide-liquide ou gaz-liquide-solide

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1140349A1 (fr) 1998-11-26 2001-10-10 Basf Aktiengesellschaft Reacteur pour effectuer en continu des reactions gaz-liquide, liquide-liquide ou gaz-liquide-solide

Non-Patent Citations (13)

* Cited by examiner, † Cited by third party
Title
"Perry's Chemical Engineers' Handbook", 1997, MCGRAW-HILL, pages: 95 - 96
BLASER ET AL.: "Applied Homogeneous Catalysis with Organometallic Compounds", vol. 3, 2018, WILEY-VCH, pages: 621 - 690
C. ELSCHENBROICHA. SALZER, ORGANOMETALLCHEMIE, TEUBNER TASCHENBÜCHER CHEMIE, WIESBADEN, 1990
CASEY C P ET AL: "THE NATURAL BITE ANGLE OF CHELATING DIPHOSPHINES", ISRAEL JOURNAL OF CHEMISTRY, LASER PAGES PUBL, IL, vol. 30, 1 January 1990 (1990-01-01), pages 299 - 304, XP000564865, ISSN: 0021-2148 *
I. OJIMA: "Catalytic Asymmetrie Synthesis", 2000, WILEY-VCH
J. ANGELICI ET AL., J. AM. CHEM. SOC., vol. 114, 1992, pages 160 - 165
LANGER ET AL.: "Homogeneous Hydrogenation with Non-Precious Catalysts", 2020, WILEY-VCH, pages: 15 - 38
P. CASEY ET AL., ISRAEL JOURNAL OFCHEMISTRY, vol. 30, 1990, pages 299 - 304
P. TRAMBOUZEJ.-P. EUZEN, CHEMICAL REACTORS, 2004, pages 280 - 283
P. ZEHNERR. BENFER, CHEM. ENG. SCI., vol. 51, 1996, pages 1735 - 1744
P.-J. CHIRIK ET AL., ORGANOMETALLICS, vol. 33, 2014, pages 5781 - 5790
W. R. A. VAUCKH. A. MÜLLER: "Grundoperationen chemischer Verfahrenstechnik", 1984, DEUTSCHER VERLAG FÜR GRUNDSTOFFCHEMIE LEIPZIG, pages: 800
W. TANGX. ZHANG, CHEM. REV., vol. 103, 2003, pages 3029 - 3069

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