EP1807437A1 - Ligands destines a l'hydroformulation asymetrique - Google Patents

Ligands destines a l'hydroformulation asymetrique

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Publication number
EP1807437A1
EP1807437A1 EP05799685A EP05799685A EP1807437A1 EP 1807437 A1 EP1807437 A1 EP 1807437A1 EP 05799685 A EP05799685 A EP 05799685A EP 05799685 A EP05799685 A EP 05799685A EP 1807437 A1 EP1807437 A1 EP 1807437A1
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EP
European Patent Office
Prior art keywords
alkyl
aryl
cycloalkyl
hydrogen
chiral
Prior art date
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Application number
EP05799685A
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German (de)
English (en)
Inventor
Wolfgang Ahlers
Martina Egen
Martin Volland
Christoph JÄKEL
Frank Hettche
Rocco Paciello
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BASF SE
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BASF SE
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Publication date
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Publication of EP1807437A1 publication Critical patent/EP1807437A1/fr
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    • 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
    • B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
    • B01J31/1845—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing phosphorus
    • B01J31/185—Phosphites ((RO)3P), their isomeric phosphonates (R(RO)2P=O) and RO-substitution derivatives thereof
    • B01J31/1855—Triamide derivatives thereof
    • 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
    • B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
    • B01J31/1845—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing phosphorus
    • B01J31/185—Phosphites ((RO)3P), their isomeric phosphonates (R(RO)2P=O) and RO-substitution derivatives thereof
    • B01J31/186—Mono- or diamide derivatives thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • 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
    • B01J31/2495—Ligands comprising a phosphine-P atom and one or more further complexing phosphorus atoms covered by groups B01J31/1845 - B01J31/1885, e.g. phosphine/phosphinate or phospholyl/phosphonate ligands
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/49—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reaction with carbon monoxide
    • C07C45/50—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reaction with carbon monoxide by oxo-reactions
    • C07C45/505—Asymmetric hydroformylation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/28—Preparation of carboxylic acid esters by modifying the hydroxylic moiety of the ester, such modification not being an introduction of an ester group
    • C07C67/293—Preparation of carboxylic acid esters by modifying the hydroxylic moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton
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    • C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
    • C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table compounds of the platinum group
    • C07F15/0073—Rhodium compounds
    • C07F15/008—Rhodium compounds without a metal-carbon linkage
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    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
    • C07F9/553—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having one nitrogen atom as the only ring hetero atom
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    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
    • C07F9/553—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having one nitrogen atom as the only ring hetero atom
    • C07F9/572—Five-membered rings
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    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
    • C07F9/553—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having one nitrogen atom as the only ring hetero atom
    • C07F9/572—Five-membered rings
    • C07F9/5728—Five-membered rings condensed with carbocyclic rings or carbocyclic ring systems
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    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
    • C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
    • C07F9/6581—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and nitrogen atoms with or without oxygen or sulfur atoms, as ring hetero atoms
    • C07F9/6584—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and nitrogen atoms with or without oxygen or sulfur atoms, as ring hetero atoms having one phosphorus atom as ring hetero atom
    • C07F9/65848—Cyclic amide derivatives of acids of phosphorus, in which two nitrogen atoms belong to the ring
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    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/30—Addition reactions at carbon centres, i.e. to either C-C or C-X multiple bonds
    • B01J2231/32—Addition reactions to C=C or C-C triple bonds
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B01J2231/30—Addition reactions at carbon centres, i.e. to either C-C or C-X multiple bonds
    • B01J2231/32—Addition reactions to C=C or C-C triple bonds
    • B01J2231/321—Hydroformylation, metalformylation, carbonylation or hydroaminomethylation
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    • B01J2231/30—Addition reactions at carbon centres, i.e. to either C-C or C-X multiple bonds
    • B01J2231/32—Addition reactions to C=C or C-C triple bonds
    • B01J2231/323—Hydrometalation, e.g. bor-, alumin-, silyl-, zirconation or analoguous reactions like carbometalation, hydrocarbation
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    • B01J2231/30—Addition reactions at carbon centres, i.e. to either C-C or C-X multiple bonds
    • B01J2231/32—Addition reactions to C=C or C-C triple bonds
    • B01J2231/324—Cyclisations via conversion of C-C multiple to single or less multiple bonds, e.g. cycloadditions
    • B01J2231/325—Cyclopropanations
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    • B01J2231/30—Addition reactions at carbon centres, i.e. to either C-C or C-X multiple bonds
    • B01J2231/32—Addition reactions to C=C or C-C triple bonds
    • B01J2231/324—Cyclisations via conversion of C-C multiple to single or less multiple bonds, e.g. cycloadditions
    • B01J2231/326—Diels-Alder or other [4+2] cycloadditions, e.g. hetero-analogues
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    • B01J2231/30—Addition reactions at carbon centres, i.e. to either C-C or C-X multiple bonds
    • B01J2231/34—Other additions, e.g. Monsanto-type carbonylations, addition to 1,2-C=X or 1,2-C-X triplebonds, additions to 1,4-C=C-C=X or 1,4-C=-C-X triple bonds with X, e.g. O, S, NH/N
    • B01J2231/341—1,2-additions, e.g. aldol or Knoevenagel condensations
    • B01J2231/342—Aldol type reactions, i.e. nucleophilic addition of C-H acidic compounds, their R3Si- or metal complex analogues, to aldehydes or ketones
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    • B01J2231/40—Substitution reactions at carbon centres, e.g. C-C or C-X, i.e. carbon-hetero atom, cross-coupling, C-H activation or ring-opening reactions
    • B01J2231/44—Allylic alkylation, amination, alkoxylation or analogues
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    • B01J2231/52—Isomerisation reactions
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    • B01J2231/54—Metathesis reactions, e.g. olefin metathesis
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    • B01J2231/641—Hydrogenation of organic substrates, i.e. H2 or H-transfer hydrogenations, e.g. Fischer-Tropsch processes
    • B01J2231/643—Hydrogenation of organic substrates, i.e. H2 or H-transfer hydrogenations, e.g. Fischer-Tropsch processes of R2C=O or R2C=NR (R= C, H)
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    • B01J2231/64—Reductions in general of organic substrates, e.g. hydride reductions or hydrogenations
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    • B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
    • B01J2531/0261—Complexes comprising ligands with non-tetrahedral chirality
    • B01J2531/0266—Axially chiral or atropisomeric ligands, e.g. bulky biaryls such as donor-substituted binaphthalenes, e.g. "BINAP" or "BINOL"
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Definitions

  • the present invention relates to chiral phosphorochelate compounds, catalysts containing such a compound as ligands and to asymmetric synthesis in the presence of such a catalyst.
  • Asymmetric synthesis is the term for reactions in which a chiral moiety is generated from a chiral moiety, resulting in unequal amounts of stereoisomeric products (enantiomers or diastereomers).
  • the asymmetric synthesis has gained immense importance, above all in the pharmaceutical industry, since frequently only a certain optically active isomer is therapeutically active.
  • the synthesis should lead to the desired isomer in high optical purity and in high chemical yield.
  • Hydroformylation or oxo synthesis is an important industrial process and serves to prepare aldehydes from olefins, carbon monoxide and hydrogen. These aldehydes may optionally be hydrogenated in the same operation with hydrogen to the corresponding oxo alcohols.
  • the asymmetric hydroformylation is an important method for the synthesis of chiral aldehydes and is of interest as access to chiral building blocks for the preparation of flavorings, cosmetics, plant protection agents and pharmaceuticals.
  • the hydroformylation reaction itself is highly exothermic and generally runs under elevated pressure and at elevated temperatures in the presence of catalysts.
  • the catalysts used are Co, Rh, Ir, Ru, Pd or Pt compounds or complexes which modify the activity and / or selectivity of N, P, As or Sb-containing ligands - can be decorated.
  • olefins having more than two carbon atoms it may come to the formation of mixtures of isomeric aldehydes due to the possible CO addition to each of the two carbon atoms of a double bond.
  • the use of olefins having at least four carbon atoms by double bond isomerization may lead to the formation of mixtures of isomeric olefins and optionally also of isomeric aldehydes.
  • phosphorus-containing ligands in the rhodium-low-pressure hydroformylation for stabilizing and / or activating the catalyst metal.
  • Suitable phosphorus ligands are z.
  • phosphines, phosphinites, phosphonites, phosphites, phosphoramidites, phospholes and phosphabenzenes are z.
  • the currently most widely used ligands are triarylphosphines, such as.
  • triphenylphosphine and sulfonated triphenylphosphine since they have sufficient stability under the reaction conditions.
  • WO 00/56451 describes hydroformylation catalysts based on phosphinamidite ligands, in which the phosphorus atom, together with an oxygen atom to which it is bonded, represents a 5- to 8-membered heterocycle.
  • WO 02/083695 describes pnicogen chelate compounds in which at least one pyrrole group is bonded to each of the pnicogen atoms via the pyrrole nitrogen atom. These pnicogen chelate compounds are useful as ligands for hydroformylation catalysts.
  • WO 03/018192 describes, inter alia, pyrrole phosphorus compounds in which at least one substituted and / or pyrrole group integrated into a fused ring system is covalently linked via its pyrrolic nitrogen atom to the phosphorus atom, which has very good stability when used as ligands in hydroformylation catalysts distinguished.
  • DE-A-103 42 760 describes pnicogen compounds which have two pnicogen atoms, pyrrole groups being able to be bound to both pnicogen atoms via a pyrrolic nitrogen atom and both pnicogen atoms being bound to a bridging group via a methylene group. These pnicogen compounds are useful as ligands for hydroformylation catalysts.
  • EP-AO 503 884 describes an optically active 2'-substituted 2'-diphenylphosphine-1, 1 '-binaphthyl compound, catalysts based on Koch ⁇ transition metal complexes having such a compound as ligands and a method for enantioselective Silylation using such a catalyst.
  • EP-A-0 614 870 describes a process for the preparation of optically active aldehydes by hydroformylation of prochiral 1-olefins in the presence of a rhodium complex as hydroformylation catalyst which has an asymmetrical phosphorus-containing ligand with 1, 1 ' -binaphthylene backbone.
  • the preparation of the unbalanced phosphorus atom-containing ligands is associated with high synthetic effort.
  • EP-A-0 614 901, EP-A-0 614 902, EP-A-0 614 903, EP-A-0 684 249 and DE-A-198 53 748 describe unbalanced phosphorus atom-containing ligands of comparable structure.
  • WO 93/03839 (EP-B-0 600 020) describes an optically active metal-ligand complex catalyst comprising an optically active pnicogen compound as ligand and processes for asymmetric synthesis in the presence of such a catalyst.
  • the unpublished German patent application P 103 55 066.6 relates to a process for asymmetric synthesis in the presence of a chiral catalyst, comprising at least one complex of a metal of VIII. Subgroup with ligands capable of dimerization via non-covalent bonds, such catalysts and their use.
  • the object of the present invention is to provide chiral compounds and catalysts based thereon which are suitable for the preparation of chiral compounds with high stereoselectivity and high reactivity. These catalysts should be particularly suitable for the hydroformylation of olefins with good stereoselectivity and high reactivity.
  • R a and R 8 independently of one another represent 5- to 7-membered heterocyclic groups which are bonded to the phosphorus atom via a ring nitrogen atom or
  • R ⁇ and R ⁇ together with the phosphorus atom to which they are attached, stand for a 5- to 7-membered heterocycle which additionally has an optionally substituted nitrogen atom and a further heteroatom selected from oxygen and optionally substituted nitrogen, both bound directly to the phosphorus atom,
  • R Y and R ⁇ independently of one another are alkyl, cycloalkyl, heterocycloalkyl, aryl or hetaryl, where the alkyl radicals have 1, 2, 3, 4 or 5 substituents selected from cycloalkyl, heterocycloalkyl, aryl, hetaryl, alkoxy, cycloalkoxy, heterocycloalkoxy , Aryloxy, hetaryloxy, hydroxy, thiol, polyalkylene oxide, polyalkyleneimine,
  • E 1 , E 2 and E 3 are each the same or different radicals selected under hydrogen, alkyl, cycloalkyl, or aryl and X 'is an anion equivalent,
  • cycloalkyl, heterocycloalkyl, aryl and hetaryl radicals R v and R ⁇ may have 1, 2, 3, 4 or 5 substituents which are selected from alkyl and the substituents previously mentioned for the alkyl radicals R Y and R ⁇ , or
  • X ⁇ is O, S, SiR ⁇ R or NR ⁇ , where R ⁇ , R ⁇ and ⁇ R is independently hydrogen, are alkyl, Cycioalkyl, heterocycloalkyl aryl or hetaryl, and Y stands for a chiral divalent bridging group.
  • Chiral compounds in the context of the present invention are compounds having at least one chiral center (that is to say at least one asymmetric atom, in particular at least one asymmetric C atom or P atom), with chirality axis, chirality plane or helical turn.
  • chiral catalyst is widely understood in the context of the present invention. It comprises both catalysts which have at least one chiral ligand and also catalysts with intrinsically achiral ligands which, owing to the arrangement of the ligands as a result of noncovalent interactions and / or the arrangement of the ligands in complexed form, have center chirality, axial chirality , planar chirality or helicity.
  • a “prochiral compound” is understood to mean a compound having at least one prochiral center.
  • “Asymmetric synthesis” refers to a reaction in which a compound having at least one prochiral center is formed from a compound having at least one center of chirality, a chirality axis, a plane of chirality, or a helical coil, whereby the stereoisomeric products are formed in uneven amounts.
  • Steps are compounds of the same constitution but with different atomic arrangements in three-dimensional space.
  • Enantiomers are stereoisomers which behave in mirror-image relationship to one another.
  • R and S are the descriptors of the CIP system for the two
  • Enantiomers and represent the absolute configuration of the asymmetric atom.
  • the process of the invention results in products that are enriched in a particular stereoisomer.
  • the achieved "enantiomeric excess” (ee) is generally at least 20%, preferably at least 50%, in particular at least 80%.
  • alkyl includes straight-chain and branched alkyl groups. Preferably, it is straight-chain or branched C 1 -C 20 -alkyl, preferably CrCl 2 -AIkVl-, particularly preferably C 1 -C 8 -AIkVl- and most preferably C r C 4 alkyl groups.
  • alkyl groups are in particular methyl, ethyl, propyl, isopropyl, n-butyl, 2-butyl, 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, 3,3-dimethylbutyl, 1, 1, 2-trimethylpropyl,
  • alkyl also includes substituted alkyl groups which are generally 1, 2, 3, 4 or 5, preferably 1, 2 or 3 and particularly preferably 1 substituent aus ⁇ selected from the groups cycloalkyl, aryl, hetaryl, halogen, NE 1 E 2 , NE 1 E 2 E 3+ , COOH, carboxylate, -SO 3 H and sulfonate.
  • alkylene in the context of the present invention stands for straight-chain or branched alkanediyl groups having 1 to 4 carbon atoms.
  • cycloalkyl in the context of the present invention comprises unsubstituted as well as substituted cycloalkyl groups, preferably C 5 -C 7 -cycloalkyl groups, such as cyclopentyl, cyclohexyl or cycloheptyl, which in the case of a substitution, in general 1, 2, 3, 4 or 5, preferably 1, 2 or 3 and particularly preferably 1 substituent selected from the groups alkyl, alkoxy and halogen, can carry.
  • substituted cycloalkyl groups preferably C 5 -C 7 -cycloalkyl groups, such as cyclopentyl, cyclohexyl or cycloheptyl, which in the case of a substitution, in general 1, 2, 3, 4 or 5, preferably 1, 2 or 3 and particularly preferably 1 substituent selected from the groups alkyl, alkoxy and halogen, can carry.
  • heterocycloalkyl in the context of the present invention comprises saturated, cycloaliphatic groups having generally 4 to 7, preferably 5 or 6, ring atoms in which 1 or 2 of the ring carbon atoms are selected by heteroatoms, preferably selected from the elements oxygen, nitrogen and sulfur, are substituted and which may optionally be substituted, wherein in the case of a substitution, these heterocycloaliphatic groups 1, 2 or 3, preferably 1 or 2, particularly preferably 1 substituent selected from alkyl, aryl, COOR f , COO " M + and NE 1 e 2, preferably alkyl, can carry.
  • heterocycloaliphatic Grup ⁇ examples are groups pyrrolidinyl, piperidinyl, 2,2,6,6-tetramethyl piperidinyl, imidazolidinyl, pyramidal zolidinyl, oxazolidinyl, Morpholidinyl, thiazolidinyl, isothiazolidinyl, isoxazolidinyl, Piperazinyl, tetrahydrothiophenyl, tetrahydrofuranyl, tetrahydropyranyl, dioxanyl.
  • aryl for the purposes of the present invention includes unsubstituted as well as substituted aryl groups, and is preferably phenyl, ToIyI, XyIyI, mesityl, naphthyl, fluorenyl, anthracenyl, phenanthrenyl or naphthacenyl, more preferably phenyl or naphthyl, said Aryl groups in the case of a substitution in general 1, 2, 3, 4 or 5, preferably 1, 2 or 3 and particularly preferably 1 substituent selected from the groups alkyl, alkoxy, carboxyl, carboxylate, trifluoromethyl, -SO 3 H, sulfonate, NE 1 E 2 , alkylene-NE 1 E 2 , nitro, cyano or halogen.
  • heterocycloaromatic groups preferably the groups pyridyl, quinolinyl, acridinyl, pyridazinyl, pyrimidinyl, pyrazinyl, and the subgroup of the "pyrrole group", these heterocycloaromatic groups in the case of Substitu tion generally 1, 2 or 3 substituents selected from the groups alkyl, alkoxy, carboxyl, carboxylate, -SO 3 H, sulfonate, NE 1 E 2 , alkylene-NE 1 E 2 , trifluoromethyl or halogen, can carry.
  • pyrrole group in the context of the present invention is a series of unsubstituted or substituted heterocycloaromatic groups which are structurally derived from the pyrrole skeleton and contain a pyrrole nitrogen atom in the heterocycle which is covalently linked to other atoms, for example a pnicogen atom can be.
  • pyrrole group thus includes the unsubstituted or substituted groups pyrrolyl, imidazolyl, pyrazolyl, indolyl, purinyl, indazolyl, benzotriazolyl, 1, 2,3-triazolyl, 1, 3,4-triazolyl and carbazolyl, which in the case of Substitution in general 1, 2 or 3, preferably 1 or 2, particularly preferably 1 substituent selected from the groups alkyl, alkoxy, acyl, carboxyl, carboxylate, -SO 3 H, sulfonate, NE 1 E 2 , alkylene-NE 1 E 2 , trifluoromethyl or halogen, tra ⁇ gene can.
  • a preferred substituted indolyl group is the 3-methylindolyl group.
  • bispyrrole group for the purposes of the present invention includes divalent groups of the formula
  • the bispyrrole groups may also be unsubstituted or substituted and in the case of a substitution per pyrrole group unit generally 1, 2 or 3, preferably 1 or 2, in particular 1 substituent selected from alkyl, alkoxy, carboxyl, carboxylate, -SO 3 H, sulfonate, NE 1 E 2 , alkylene-NE 1 E 2 , trifluoromethyl or halogen carry, wherein in these statements to the number of possible substituents linking the Pyrrol weaknessein- units by direct chemical bonding or by means of the genann ⁇ th groups mentioned above mediated linking is not considered a substitution.
  • Carboxylate and sulfonate in the context of this invention preferably represent a derivative of a carboxylic acid function or a sulfonic acid function, in particular a metal carboxylate or sulfonate, a carboxylic acid or sulfonic acid ester function or a carboxylic acid or sulfonic acid amide function.
  • these include z.
  • esters with CrC 4 alkanols such as methanol, ethanol, n-propanol, isopropanol, n-butanol, sec-butanol and tert-butanol. These include the primary amides and their N-alkyl and NN-dialkyl derivatives.
  • acyl in the context of the present invention represents alkanoyl or aroyl groups having generally 2 to 11, preferably 2 to 8, carbon atoms, for example, the acetyl, propanoyl, butanoyl, pentanoyl, hexanoyl, heptanoyl, 2-ethylhexanoyl, 2-propylheptanoyl, benzoyl or naphthoyl group.
  • the groups NE 1 E 2 , NE 4 E 5 , NE 7 E 8 , NE 10 E 11 , NE 13 E 14 , NE 16 E 17 and NE 19 E 20 are preferably N, N-dimethylamino, N, N-diethylamino , N, N-dipropylamino, N, N-diisopropylamino, N, N-di-n-butylamino, N, N-di-t-butylamino, N, N-dicyclohexylamino or N, N-diphenylamino.
  • Halogen is fluorine, chlorine, bromine and iodine, preferably fluorine, chlorine and bromine.
  • M + represents a cation equivalent, ie a monovalent cation or the proportion of a polyvalent cation corresponding to a positive single charge.
  • the cation M + serves only as a counterion to the neutralization of negatively charged substituent groups, such as the COO or the sulfonate group, and can in principle be chosen arbitrarily. Preference is therefore given to alkali metal, in particular Na + , K + , Li + ions or onium ions, such as ammonium, mono-, di-, tri-, tetraalkylammonium, phosphonium, tetraalkylphosphonium or tetraarylphosphonium ions used.
  • anion equivalent X ' which serves merely as a counterion of positively charged substituent groups, such as the ammonium groups, and can be chosen arbitrarily from monovalent anions and the portions of a polyvalent anion corresponding to a negative single charge.
  • Suitable anions are z.
  • halide ion X ' such as chloride and bromide.
  • Preferred anions are sulfate and sulfonate, e.g. As SO 4 2 " , tosylate, trifluoromethanesulfonate and methyl sulfonate.
  • the values of x represent an integer of 1 to 240, preferably an integer of 3 to 120.
  • Condensed ring systems may be fused (fused) aromatic, hydroaromatic and cyclic compounds.
  • Condensed ring systems consist of two, three or more than three rings.
  • ortho-fusing d. H. each ring has one edge or two atoms in common with each adjacent ring, and a peri-annulation in which one carbon atom belongs to more than two rings.
  • Preferred among the fused ring systems are ortho-fused ring systems.
  • the substituents R ⁇ and R ⁇ are heteroatom-containing groups which are bonded to the phosphorus atom via an optionally substituted nitrogen atom are where R ⁇ and R p are not connected to each other.
  • R ⁇ and R p are not connected to each other.
  • Aik is a C r C 4 alkyl group
  • R a, R b, R c and R d are independently hydrogen, CrC 4 alkyl, Ci-C 4 alkoxy, acyl, halogen, trifluoromethyl, dC 4 alkoxycarbonyl or carboxyl.
  • At least one of the radicals R ⁇ and R ⁇ is an unsubstituted or substituted indolyl group which is in particular selected from groups II. E to II. I.
  • the radicals R a and R b are preferably independently of one another selected from hydrogen, C 1 -C 4 -alkyl, C 1 -C 4 -alkoxy and halogen. If at least one of the radicals R a and R b is C 1 -C 4 -alkyl, then especially methyl, ethyl, n-propyl, isopropyl or tert-butyl. If at least one of the radicals R a and R b is C 1 -C 4 -alkoxy, then especially methoxy, ethoxy, n-propyloxy, isopropyloxy or tert-butyloxy. If at least one of R a and R b is halogen, then especially chlorine.
  • the radicals R a and R b are both hydrogen.
  • one of the radicals R a and R b is hydrogen and the other is a radical other than hydrogen, especially methyl, methoxy or chlorine.
  • the radical other than hydrogen is then preferably in the 4-, 5- or 6-position of the indole skeleton.
  • both radicals R ⁇ and R ⁇ stand for such an unsubstituted or substituted indolyl group.
  • R ⁇ and R ⁇ stand for such an unsubstituted or substituted indolyl group.
  • some advantageous pyrrol groups are listed below:
  • the 3-methylindolyl group (skatolyl group) of the formula II.f1 is particularly advantageous.
  • Hydroformylation catalysts based on ligands which have one or more 3-methylindolyl group (s) attached to the phosphorus atom are distinguished by particularly high stability and thus particularly long catalyst residence times.
  • phosphorus chelate compounds in which the radicals R ⁇ and R ⁇ are selected independently of one another below:
  • FT and R ß together with the phosphorus atom to which they are attached for a 5- to 7-membered heterocycle having two bonded to the phosphorus ring heteroatom me, wherein it is at least one of these ring heteroatoms is an optionally substituted nitrogen atom.
  • the second ring heteroatom bonded to the phosphorus atom is preferably also an optionally substituted nitrogen atom.
  • the substituent R ⁇ together with the substituent R ⁇ then particularly preferably forms a bispyrrole group bonded via the pyrrole nitrogen atoms to the phosphorus atom.
  • bispyrrole group corresponds to the definition given at the outset.
  • R ⁇ and R ⁇ together are a 5- to 7-membered heterocycle which is optionally additionally fi-, 2-, 3- or tetra-fused with cycloalkyl, heterocyclo- lauricyl, aryl or hetaryl, wherein the heterocycle and, if present, the fused groups independently of each other one, two, three or four substituents ten, which are selected from alkyl, cycloalkyl, heterocycloalkyl, aryl, hetaryl, hydroxy, thiol, polyalkylene oxide, polyalkyleneimine, alkoxy, halogen, COOH, carboxylate , SO 3 H, sulfonate, NE 4 E 5 , NE 4 E 5 E 6 X " , nitro, alkoxycarbonyl, acyl and cyano, wherein E 4 , E 5 and E 6 each represent identical or different radicals selected from hydrogen, alkyl, cycloalkyl and aryl
  • the substituent R ⁇ together with the substituent R ß is a divalent group of the formula ## STR5 ## which is bonded via the pyrrole nitrogen atom to the phosphorus atom
  • Py is a pyrrole group
  • I represents a chemical bond or represents O, S, SiR 1 R 2 , NR 3 or optionally substituted C 1 -C 10 -alkylene, preferably CR 4 R 5 ,
  • W is cycloalkyloxy or amino, aryloxy or amino, hetaryloxy or amino
  • R 1 , R 2 , R 3 , R 4 and R 5 independently of one another are hydrogen, alkyl, cycloalkyl, heterocycloalkyl, aryl or hetaryl,
  • Phosphor chelate compounds in which R ⁇ and R ⁇ together with the phosphorus atom to which they are bonded are preferred for a group of the formulas 11.1 to II.3
  • R 6 and R 7 independently of one another are hydrogen, alkyl, cycloalkyl, aryl, hetaryl, mesylate, tosylate or trifluoromethanesulfonate,
  • R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 , R 18 , R 19 , R 20 , R 21 , R 22 , R 23 , R 24 , R 25 , R 26 and R 27 independently of one another represent hydrogen, alkyl, cycloalkyl, heterocycloalkyl, aryl, hetaryl, W'COOR ', W 1 COO-M + , W (SO 3 ) R *, W' (SO 3 ) -M + , W'PO 3 (R f ) (R 9 ),
  • W ' represents a single bond, a heteroatom, a heteroatom-containing group or a divalent bridging group having 1 to 20 bridging atoms
  • R f , E 13 , E 14 , E 15 are each the same or different radicals selected from hydrogen, alkyl, cycloalkyl or aryl,
  • R g is hydrogen, methyl or ethyl
  • M + is a cation equivalent
  • x is an integer from 1 to 240
  • the radicals R 6 and R 7 are independently selected from hydrogen, C 1 -C 4 -AlkVl, in particular methyl, ethyl, n-propyl, isopropyl, n-butyl and tert-butyl , Cs-C ⁇ -cycloalkyl, in particular cyclohexyl and aryl, in particular phenyl.
  • the radicals R 8 , R 9 , R 10 and R 11 are hydrogen.
  • Pnicogen chelate compounds of the formula I in which R ⁇ and R ⁇ together with the phosphorus atom represent a chiral group of the formula II.1 are particularly preferred.
  • the radicals R 12 , R 13 , R 14 , R 15 , R 16 and R 17 are hydrogen.
  • the further rings are fused aromatic rings.
  • the fused aromatic rings are preferably benzene or naphthalene.
  • Anellissus benzene rings are preferably unsubstituted or have 1, 2 or 3, in particular 1 or 2 substituents, which are preferably selected from alkyl, alkoxy, halogen, SO 3 H, sulfonate, NE 7 E 8 , alkylene NE 7 E 8 , Trifluoromethyl, nitro, carboxyl, alkoxycarbonyl, acyl and cyano.
  • Anellated naphthalenes are preferably unsubstituted or have in the non-fused ring and / or in the fused ring in each case 1, 2 or 3, in particular 1 or 2 of those previously mentioned in the fused benzene rings Substituents on.
  • alkyl is preferably C 1 -C 4 -alkyl and in particular methyl, isopropyl and tert-butyl.
  • Alkoxy is preferably C 1 -C 4 -alkoxy and especially methoxy.
  • Alkoxycarbonyl is preferably C r C 4 alkoxycarbonyl.
  • Halogen is especially fluorine and chlorine.
  • radicals R 18 , R 19 , R 20 , R 21 , R 22 , R 23 , R 24 , R 25 , R 26 and R 27 are preferably hydrogen.
  • the further rings are preferably fused aromatic rings.
  • the fused aromatic rings are preferably benzene or naphthalene. If desired, these may be substituted as described above for groups II.2.
  • R ⁇ and R ⁇ independently represent substituents which are not linked together.
  • R ⁇ and R ⁇ are then independently of one another selected from aryl and hetaryl radicals which may have 1, 2, 3, 4 or 5 of the abovementioned substituents.
  • R Y or R ⁇ stands or both of these radicals are aryl, which may have one, two or three substituents which are selected from C 1 -C 4 -alkyl, C 1 -C 4 -alkoxy and combinations thereof , Preferred radicals R Y and R ⁇ are then, for example, phenyl, o-tolyl, m-xylyl and 3,5-dimethyl-4-methoxyphenyl.
  • the bridging group Y is a chiral group which preferably has at least one chiral center, one chiral axis or chirality plane.
  • the bridging groups Y are preferably selected from groups of formulas III.a and III. b
  • Y preferably represents a group of the formula IIIa, in which R IV and R V independently of one another represent C r C 4 -alkyl or C r C 4 -alkoxy.
  • R N and R v are selected from methyl, ethyl, isopropyl, tert -butyl and methoxy.
  • R 1 , R ", R 111 , R v ⁇ , R v " and R v ⁇ " are hydrogen.
  • Y is lll.a a group of the formula wherein R 1 and R VIII "un ⁇ interdependent for -C 4 alkyl or Ci-C 4 -alkoxy. Particularly preferably, R 1 and R VIII" for tert -butyl.. Particularly preferably, in these compounds, R ", R 1", R IV, R V, R VI, R v "is hydrogen. In addition, preferably, in these compounds, R 1" v ⁇ independently C1 and R 4 -alkyl or C 1 -C 4 -alkoxy. Particularly preferred are R MI and R v ⁇ are independently selected from methyl, ethyl, isopropyl, tert-butyl and methoxy.
  • Y is preferably a group of the formula IIIa, in which R “and R v " are hydrogen.
  • R 1, R “v ⁇ , R lv, R v, R and R VIII" 1 independently represent -C 4 alkyl or C 1 -C 4 -alkoxy.
  • R 1 , R 1 ", R IV , R V , R V ⁇ and R v ⁇ " are independently selected from methyl, ethyl, isopropyl, tert-butyl and methoxy.
  • Y is preferably a group of the formula III. b, wherein R 1 to R x "are hydrogen.
  • Y is preferably a group of the formula III. b, wherein R 1 and R x "unab ⁇ pending for C r C 4 alkyl or C 1 -C 4 -alkoxy are from each other.
  • R 1 and R x ' are independently selected from methyl, ethyl, isopropyl, tert. Butyl, methoxy and alkoxycarbonyl, preferably methoxycarbonyl.
  • the radicals R 11 to R x ⁇ are hydrogen.
  • Another object of the invention is a chiral catalyst comprising emerges ⁇ least a complex with a metal of the VIII. Subgroup of the Periodic Table, the at least one chiral phosphorochelate compound as defined above, as defined above.
  • the chiral catalysts according to the invention and used according to the invention have at least one of the compounds described above as ligands.
  • you can still at least one other ligand which is preferably selected from halides, amines, carboxylates, acetylacetonate, aryl or alkyl sulfonates, hydride, CO, olefins, dienes, cycloolefins, nitriles, N-containing heterocycles , Aromatics and heteroaromatics, ethers, PF 3 , phospholes, phosphabenzenes and mono-, di- and polydentate phosphine, phosphinite, phosphonite, phosphoramidite and phosphite ligands aufwei ⁇ sen.
  • the transition metal is preferably a metal of the I., VI., VII. Or VIII. Subgroup of the Periodic Table of the Elements. More preferably, the transition metal is selected from the metals of Group VIII (i.e., Fe, Co, Ni, Ru, Rh, Pd, Os, Ir, Pt). In particular, the transition metal is iridium, ruthenium, rhodium, palladium or platinum.
  • Another object of the invention is a process for preparing chiral Ver ⁇ compounds by reacting a prochiral compound containing at least one ethylenically unsaturated double bond, with a substrate in the presence of a chiral catalyst, as described above. All that is required is that at least one of the ligands used or the catalytically active species is entirely chiral. In general, certain transition metal complexes are formed as catalytically active species under the reaction conditions of the individual processes for producing chiral compounds.
  • catalytically active species of the general formula H x M y (CO) z L q are formed under hydroformylation conditions from the particular catalysts or catalyst precursors used, where M is a transition metal, L is a phosphorochelate compound and q, x, y , z are integers, depending on the valency and type of metal and the binding of ligand L, stand.
  • z and q are independently of one another at least a value of 1, such. B. 1, 2 or 3.
  • the sum of z and q is preferably from 1 to 5.
  • the complexes may, if desired, additionally have at least one of the further ligands described above.
  • the catalytically active species is preferably present as a homogeneous single-phase solution in a suitable solvent.
  • This solution may additionally contain free ligands.
  • the process according to the invention for the preparation of chiral compounds is preferably a hydrogenation, hydroformylation, hydrocyanation, carbonylation, hydroacylation (intramolecular and intermolecular), hydroamidation, hydroesterification, hydrosilylation, hydroboration, aminolysis (hydroamination), alcoholysis (hydroxylation). Alkoxy addition), isomerization, transfer hydrogenation, metathesis, cyclopropanation, aldol condensation, allylic alkylation, or a [4 + 2] cycloaddition (Diels-Alder reaction).
  • the process according to the invention for preparing chiral compounds is particularly preferably a 1,2-addition, in particular a hydrogenation or a 1-hydro-2-carboo addition.
  • 1-Hydro-2-carbo-addition refers to an addition reaction in which, after the reaction, hydrogen is bonded to one atom of the double bond and a carbon atom-containing group is bonded to the other. Double bond isomerizations during addition are allowed.
  • 1-hydro-2-carbo-addition in unsymmetrical substrates should not be referred to as a preferred addition of the carbon fragment to the C2 atom, since the selectivity with respect to the orientation of the addition of the generally to be added and depends on the catalyst used.
  • “1-hydro-2-carbo-” is in this sense synonymous with "1-carbo-2-hydro-”.
  • reaction conditions of the processes according to the invention for the preparation of chiral compounds, except for the chiral catalyst used, generally correspond to those of the corresponding asymmetric processes.
  • Suitable reactors and reaction conditions can thus be taken from the relevant literature on the respective method and routinely adapted by the person skilled in the art.
  • Suitable temperatures Obstem ⁇ are generally in a range from -100 to 500 0 C, preferably in a range from -80 to 250 0 C.
  • Suitable reaction pressures are generally in a range of 0.0001 to 600 bar, preferably from 0.5 to 300 bar.
  • the processes can generally be carried out continuously, semicontinuously or batchwise.
  • Suitable reactors for the continuous reaction are known in the art and z. As described in Ullmann's Encyclopedia of Industrial Chemistry, Vol.
  • suitable solvents are z.
  • aromatics such as toluene and xylene
  • hydrocarbons or mixtures of hydrocarbons are also suitable.
  • halogenated in particular chlorinated hydrocarbons, such as dichloromethane, chloroform or 1, 2-dichloroethane.
  • Further solvents are esters of aliphatic carboxylic acids with alkanols, for example ethyl acetate or Texanol®, ethers, such as tert-butyl methyl ether, dioxane-1, 4 and tetrahydrofuran, and dimethylformamide.
  • ligands are sufficiently hydrophilized, it is also possible to use alcohols, such as methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, ketones, such as acetone and methyl ethyl ketone, etc. Further, as a solvent and so-called “ionic liquids" can be used.
  • liquid salts for example N, N'-dialkylimidazolium salts, such as the N-butyl-N'-methylimidazolium salts, tetraalkylammonium salts, such as the tetra-n-butylammonium salts, N-alkylpyridinium salts, such as the n-butylpyridinium salts, and tetraalkylphosphonium salts, such as Trishexyl (tetradecyl) phosphonium salts, e.g.
  • N, N'-dialkylimidazolium salts such as the N-butyl-N'-methylimidazolium salts
  • tetraalkylammonium salts such as the tetra-n-butylammonium salts
  • N-alkylpyridinium salts such as the n-butylpyridinium salts
  • tetrafluoroborates acetates, tetrachloroaluminates, hexafluorophosphates, chlorides and tosylates.
  • the solvent used may also be a starting material, product or by-product of the particular reaction.
  • Suitable prochiral ethylenically unsaturated compounds for the process according to the invention are in principle all prochiral compounds which contain one or more ethylenically unsaturated carbon-carbon or carbonyl groups.
  • prochiral olefins hydroformylation, intermolecular hydroacylation, hydrocyanation, hydrosilylation, carbonylation, hydroamidation, hydroesterification, aminolysis, alcoholysis, cyclopropanation, hydroboration, Diels-Alder reaction, metathesis
  • Suitable prochiral ethylenically unsaturated olefins are generally compounds of the formula
  • R A and R B and / or R c and R D are radicals of different definitions. It goes without saying that for the production according to the invention of chiral compounds, those reacted with the prochiral ethylenically unsaturated compound Substrates and possibly also the stereoselectivity with respect to the addition of a particular substituent to a particular carbon atom of the CC double bond can be chosen so that at least one chiral carbon atom results.
  • R A, R B, R c and R D in compliance with the above-mentioned condition is independently selected from hydrogen, alkyl, cycloalkyl, heterocyclo alkyl, aryl, hetaryl, alkoxy, cycloalkoxy, heterocycloalkoxy, aryloxy, hetaryloxy, hydroxy, thiol , Polyalkylene oxide, polyalkyleneimine, COOH, carboxylate, SO 3 H, sulfonate, NE 16 E 17 , NE 16 E 17 E 18 X ' , halogen, nitro, acyl, acyloxy or cyano, wherein E 16 , E 17 and E 18 are each the same or different radicals selected from among hydrogen, alkyl, cycloalkyl, or aryl and X- is an anion equivalent,
  • alkyl radicals have 1, 2, 3, 4, 5 or more substituents selected from cycloalkyl, heterocycloalkyl, aryl, hetaryl, alkoxy, cycloalkoxy, heterocycloalkoxy, aryloxy, hetaryloxy, hydroxy, thiol, polyalkylene oxide, polyalkyleneimine, COOH, carboxylate, SO 3 H, sulfonate, NE 19 E 20 , NE 19 E 20 E 21 X ' , halogen, nitro, acyl, acyloxy or cyano, wherein E 19 , E 20 and E 21 are each the same or different radicals selected from hydrogen , Alkyl, cycloalkyl, or aryl and X 'is an anion equivalent,
  • cycloalkyl, heterocycloalkyl, aryl and hetaryl radicals R A , R B , R c and R D may each have 1, 2, 3, 4, 5 or more substituents selected from alkyl and those previously described for the Alkyl substituents R A , R B , R c and R D substituents th, or
  • R A , R B , R c and R D together with the CC double bond to which they are attached represent a mono- or polycyclic compound.
  • Suitable prochiral olefins are olefins having at least 4 carbon atoms and terminal or internal double bonds which are straight-chain, branched or cyclic in structure.
  • Suitable ⁇ -olefins are, for. 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-octadecene, etc.
  • Suitable linear (straight-chain) internal olefins are preferably C 4 -C 2 o-olefins, such as 2-butene, 2-pentene, 2-hexene, 3-hexene, 2-heptene, 3-heptene, 2-octene, 3-octene , 4-octene etc.
  • Suitable branched internal olefins are preferably C 4 -C 2 o-olefins such as 2-methyl butene-2, 2-methyl-2-pentene, 3-methyl-2-pentene, branched, internal heptene mixtures, branched, internal octene mixtures, branched, internal nonene mixtures, branched, internal decene mixtures, branched, internal undecene mixtures, branched, internal dodecene mixtures, etc.
  • C 4 -C 2 o-olefins such as 2-methyl butene-2, 2-methyl-2-pentene, 3-methyl-2-pentene, branched, internal heptene mixtures, branched, internal octene mixtures, branched, internal nonene mixtures, branched, internal decene mixtures, branched, internal undecene mixtures, branched, internal dodecene mixtures, etc.
  • Suitable olefins to be hydroformylated are furthermore C 5 -C 8 -cycloalkenes, such as cyclopentene, cyclohexene, cycloheptene, cyclooctene and their derivatives, such as. B. de ⁇ Ren C 1 -C 20 alkyl derivatives having 1 to 5 alkyl substituents.
  • Suitable olefins to be hydroformylated are furthermore vinylaromatics, such as styrene, ⁇ -methylstyrene, 4-isobutylstyrene, etc., 2-vinyl-6-methoxynaphthalene, (3-ethenylphenyl) phenylketone, (4-ethenylphenyl) -2-thienyl ketone, 4-ethenyl -2-fluorobiphenyl, 4- (1,3-dihydro-1-oxo-2H-isoindol-2-yl) styrene, 2-ethenyl-5-benzoylthiophene, (3-ethenylphenyl) phenyl ether, propenylbenzene, 2-propenylphenol, isobutyl 4-propenylbenzene, phenyl vinyl ethers and cyclic enamides, e.g.
  • 2,3-dihydro-1, 4-oxazines such as 2,3-dihydro-4-tert-butoxycarbonyl-1,4-oxazine.
  • Suitable olefins to be hydroformylated are furthermore ⁇ , ⁇ -ethylenically unsaturated mono- and / or dicarboxylic acids, their esters, monoesters and amides, such as acrylic acid, methacrylic acid, maleic acid, fumaric acid, crotonic acid, itaconic acid, methyl 3-pentenoate,
  • Suitable substrates are also di- or polyenes with isolated or conjugated double bonds. These include z. B. 1, 3-butadiene, 1, 4-pentadiene, 1, 5-hexadiene, 1, 6-heptadiene, 1, 7-octadiene, 1, 8-nonadiene, 1, 9-decadiene, 1, 10-undecadiene, 1, 11-dodecadiene, 1, 12-tridecadiene, 1, 13-tetradecadiene, vinylcyclohexene, dicyclopentadiene, 1, 5,9-cyclooctatriene and Butadienhomo- and copolymers.
  • prochiral ethylenically unsaturated compounds which are important as synthesis building blocks are, for example, P-isobutylstyrene, 2-vinyl-6-methoxynaphthalene, (3-ethenylphenyl) phenylketone, (4-ethenylphenyl) -2-thienyl ketone, 4-ethenyl-2-fluorobiphenyl, 4- (1,3-dihydro-1 -oxo-2H-isoindol-2-yl) styrene, 2-ethenyl-5-benzoylthiophene, (3-ethenylphenyl) phenyl ether, propenylbenzene, 2-propenylphenol, isobutyl-4-propenylbenzene, phenylvinyl ethers and cyclic enamides, e.g.
  • 2,3-dihydro-1, 4-oxazines such as 2,3-dihydro-4-tert-butoxycarbonyl-1, 4-oxazine.
  • the aforementioned olefins can be used individually or in the form of mixtures.
  • the chiral catalysts according to the invention and used according to the invention are prepared in situ in the reactor used for the reaction. If desired, however, the catalysts according to the invention can also be prepared separately and isolated by customary processes.
  • the catalysts of the invention can be z.
  • Suitable activating agents are, for. B. Bronsted acids, Lewis acids, such as. B. BF 3 , AICI 3 , ZnCl 2 , and Lewis bases.
  • Suitable catalyst precursors are very generally transition metals, transition metal compounds and transition metal complexes.
  • Suitable rhodium compounds or complexes are, for. Rhodium (II) and rhodium (III) salts, such as rhodium (III) chloride, rhodium (III) nitrate, rhodium (III) sulfate, potassium rhodium sulfate, rhodium (II) or Rhodium (III) carboxylate, rhodium (II) and rhodium (III) acetate, rhodium (III) oxide, salts of rhodium (III) acid, trisammonium hexachlororhodate (III), etc.
  • Rhodium (II) and rhodium (III) salts such as rhodium (III) chloride, rhodium (III) nitrate, rhodium (III) sulfate, potassium rhodium sulfate, rhodium (II) or Rh
  • rhodium complexes are suitable such as Rh 4 (CO) 12 , rhodiumbiscarbonylacetylacetonate, acetylacetonato-bis-ethyl rhodium (I), etc.
  • ruthenium salts or compounds are, for example, ruthenium (III) chloride, ruthenium (IV), ruthenium (VI) or ruthenium (VIII) oxide, alkali salts of ruthenium oxygen acids such as K 2 RuO 4 or KRuO 4 or complex compounds, such as.
  • RuHCl (CO) (PPh 3 ) 3 ruthenium (III) chloride, ruthenium (IV), ruthenium (VI) or ruthenium (VIII) oxide
  • alkali salts of ruthenium oxygen acids such as K 2 RuO 4 or KRuO 4 or complex compounds, such as.
  • metal carbonyls of ruthenium such as trisruthenium dodecacarbonyl or hexaruthenium octadecacarbonyl, or mixed forms in which CO are partly replaced by ligands of the formula PR 3 , such as Ru (CO) 3 (PPh 3 ) 2 , in the process according to the invention.
  • Suitable iron compounds are for. As iron (III) acetate and iron (III) nitrate and the carbonyl complexes of iron.
  • Suitable nickel compounds are nickel fluoride and nickel sulfate.
  • a suitable for the preparation of a nickel catalyst nickel complex is z. Bis (1,5-cyclooctadiene) nickel (O).
  • the metal concentration in the reaction medium is in a range of about 1 to 10,000 ppm.
  • the molar ratio of monopnicogen ligand to transition metal is generally in the range of about 0.5: 1 to 1000: 1, preferably 1: 1 to 500: 1.
  • catalysts described above can be suitably, for. B. by attachment via suitable as anchor groups functional groups, adsorption, grafting, etc. to a ge suitable carrier, eg. Example of glass, silica gel, resins, polymers, etc., be immobilized. They are then also suitable for use as solid phase catalysts.
  • the process according to the invention is a hydrogenation (1,2-H, H addition). How to get through
  • prochiral compound containing at least one ethylenically unsaturated double bond Reacting a prochiral compound containing at least one ethylenically unsaturated double bond, with hydrogen in the presence of a chiral catalyst, as described above, to corresponding chiral compounds having a single bond.
  • Prochiral olefins lead to chiral carbonaceous compounds, prochiral ketones to chiral alcohols, and prochiral imines to chiral amines.
  • the process according to the invention is a reaction with carbon monoxide and hydrogen, which is referred to below as hydroformylation.
  • the hydroformylation can be carried out in the presence of one of the abovementioned solvents.
  • the molar ratio of mono (pseudo) pnicogen ligand to metal of the VIII. Ne ⁇ ben distr is generally in a range of about 1: 1 to 1000: 1, vorzugswei ⁇ se 2: 1 to 500: 1.
  • hydroformylation catalyst is prepared in situ, at least one ligand which can be used according to the invention, a compound or a complex of a transition metal and optionally an activating agent in an inert solvent under the hydroformylation conditions brings to reaction.
  • the transition metal is preferably a metal of the VIII.
  • Mau ⁇ group of the Periodic Table of the Elements more preferably cobalt, ruthenium, iridium, rhodium and palladium.
  • rhodium is used.
  • composition of the synthesis gas used in the process according to the invention of carbon monoxide and hydrogen can vary within wide ranges.
  • the molar ratio of carbon monoxide and hydrogen is usually about 5:95 to 70:30, preferably about 40:60 to 60:40. Particularly preferred is a molar ratio of carbon monoxide and hydrogen in the range of about 1: 1 is used.
  • the temperature during the hydroformylation reaction is generally in a range from about Be ⁇ 20 to 180 0 C, preferably about 50 to 150 0 C.
  • the pressure is in a range of about 1 to 700 bar, preferably from 1 to 600 bar, in particular 1 to 300 bar.
  • the reaction pressure can be varied depending on the activity of the hydroformylation catalyst of the invention used.
  • the novel catalysts based on phosphorus-containing compounds allow a reaction in a range of low pressures, such as in the range of 1 to 100 bar.
  • hydroformylation catalysts according to the invention and the hydroformylation catalysts according to the invention can be separated off from the starting point of the hydroformylation reaction by customary methods known to the person skilled in the art and can generally be used again for the hydroformylation.
  • the asymmetric hydroformylation according to the process of the invention is characterized by a high stereoselectivity.
  • the catalysts according to the invention and the catalysts used according to the invention also generally have a high regioselectivity.
  • the catalysts generally have a high stability under the hydroformylation conditions, so that with you usually longer catalyst life can be achieved than with the state of Technically known catalysts based on conventional chelating ligands.
  • the catalysts according to the invention and those used according to the invention furthermore exhibit high activity, so that as a rule the corresponding aldehydes or alcohols are obtained in good yields.
  • the catalysts used for the hydrocyanation include complexes of a metal of subgroup VIII, in particular cobalt, nickel, ruthenium, rhodium, palladium, platinum, preferably nickel, palladium and platinum and very particularly preferably nickel.
  • the preparation of the metal complexes can be carried out as described above. The same applies to the in situ preparation of the hydrocyanation catalysts according to the invention. Methods for hydrocyanation are described in J. March, Advanced Organic Chemistry, 4th ed., Pp. 811-812, which is incorporated herein by reference.
  • the 1-hydro-2-carboo addition is a reaction with carbon monoxide and at least one compound having a nucleophilic group, hereinafter referred to as carbonylation.
  • the carbonylation catalysts also include complexes of a metal of subgroup VIII, preferably nickel, cobalt, iron, ruthenium, rhodium and palladium, in particular palladium.
  • a metal of subgroup VIII preferably nickel, cobalt, iron, ruthenium, rhodium and palladium, in particular palladium.
  • the preparation of the metal complexes can be carried out as described above. The same applies to the in situ preparation of the carbonylation catalysts according to the invention.
  • the compounds are having a nucleophilic group selected from water, alcohols, thiols, carboxylic acid esters, primary and secondary amines.
  • a preferred carbonylation reaction is the conversion of olefins with carbon monoxide and water to carboxylic acids (hydrocarboxylation).
  • the carbonylation can be carried out in the presence of activating agents.
  • Suitable activating agents are, for. B. Bronsted acids, Lewis acids, such as. B. BF 3 , AICI 3 , ZnCl 2 , and Lewis bases.
  • hydroacylation Another important 1,2-addition is hydroacylation.
  • asymmetric intramolecular hydroacylation for example, reaction of an unsaturated aldehyde leads to optically active cyclic ketones.
  • Asymmetric intermolecular hydroacylation is achieved by the reaction of a prochiral olefin an acyl halide in the presence of a chiral catalyst as described above to chiral ketones. Suitable processes for the hydroacylation are described in J. March, Advanced Organic Chemistry, 4th ed., P. 811, to which reference is made here.
  • hydroboration Another important 1,2-addition is hydroboration.
  • a prochiral compound which contains at least one ethylenically unsaturated double bond with borane or a borane source in the presence of a chiral catalyst, as described above, to give chiral trialkylboranes which are obtained as primary alcohols (for example with NaOH / H 2 O 2 ) or can be oxidized to carboxylic acids.
  • Suitable processes for hydroboration are described in J. March, Advanced Organic Chemistry, 4th edition, pages 783-789, to which reference is made here.
  • hydrosilylation Another important 1,2-addition is hydrosilylation.
  • a prochiral compound which contains at least one ethylenically unsaturated double bond with a silane in the presence of a chiral catalyst, as described above, chiral silyl-functionalized compounds are obtained.
  • Prochiral olefins result in chiral silyl-functionalized alkanes.
  • Prochiral ketones result in chiral silyl ethers or alcohols.
  • the transition metal is preferably selected from Pt, Pd, Rh, Ru and Ir. It may be advantageous to use combinations or mixtures of one of the aforementioned catalysts with other catalysts.
  • Suitable additional catalysts include platinum in finely divided form (“platinum black”), platinum chloride and platinum complexes such as hexachloroplatinic acid or divinyldisiloxane-platinum complexes, eg. B. Tetramethyldivinyldisiloxan-platinum complexes.
  • Suitable rhodium catalysts are, for example, (RhCl (P (C 6 H 5 ) S ) 3 ) and RhCl 3 . Also suitable are RuCl 3 and IrCl 3 .
  • Suitable catalysts are also Lewis acids such as AICI 3 or TiCl 4 and peroxides.
  • Suitable silanes are, for.
  • Halogenated silanes such as trichlorosilane, methyldichlorosilane, dimethylchlorosilane and trimethylsiloxydichlorosilane; Alkoxysilanes such as trimethoxysilane, triethoxysilane, methyldimethoxysilane, phenyldimethoxysilane, 1, 3,3,5,5,7,7-heptamethyl-i, 1-dimethoxytetrasiloxane and acyloxysilanes.
  • the reaction temperature in the silylation is preferably in a range of 0 to 140 0 C, more preferably 40 to 120 0 C.
  • the reaction is usually carried out under atmospheric pressure, but can also at elevated pressures, such as. B. Be ⁇ range of about 1, 5 to 20 bar, or reduced pressures such. B. 200 to 600 mbar done.
  • the reaction can be carried out without solvent or in the presence of a suitable solvent.
  • Preferred solvents are, for example, toluene, tetrahydrofuran and chloroform.
  • Another important 1,2-addition is aminolysis (hydroamination).
  • a prochiral compound containing at least one ethylenically unsaturated double bond with ammonia, a primary or a secondary amine in the presence of a chiral catalyst, as described above, to chiral primary, secondary or tertiary amines.
  • Suitable processes for hydroamination are described in J. March, Advanced Organic Chemistry, 4th edition, pages 768-770, to which reference is hereby made.
  • alcoholysis hydro-alkoxy-addition
  • a prochiral compound which contains at least one ethylenically unsaturated double bond
  • alcohols in the presence of a chiral catalyst, as described above, to give chiral ethers.
  • Suitable methods for alcoholysis are described in J. March, Advanced Organic Chemistry, 4th ed., Pp. 763-764, to which reference is made here.
  • Another important reaction is cyclopropanation.
  • a prochiral compound containing at least one ethylenically unsaturated double bond is reacted with a diazo compound in the presence of a chiral catalyst as described above to give chiral cyclopropanes.
  • Another important reaction is metathesis.
  • a prochiral compound containing at least one ethylenically unsaturated double bond with another olefin in the presence of a chiral catalyst, as described above leads to chiral hydrocarbons.
  • allylic alkylation Another important reaction is allylic alkylation.
  • a prochiral ketone or aldehyde with an allylic alkylating agent in the presence of a chiral catalyst, as described above, chiral hydrocarbons are obtained.
  • Another object of the invention is the use of catalysts comprising at least one complex of a metal of VIII.
  • optically active compounds which can be prepared by the process according to the invention are substituted and unsubstituted alcohols or phenols, amines, amides, esters, carboxylic acids or anhydrides, ketones, olefins, aldehydes, nitriles and hydrocarbons.
  • Optically active aldehydes prepared by the asymmetric hydroformylation process according to the invention include, for example, S-2- (p-isobutylphenyl) propionaldehyde, S-2- (6-methoxynaphthyl) propionaldehyde, S-2- (3-benzoylphenyl) propionaldehyde, S-2 - (p-thienoylphenyl) propionaldehyde, S-2- (3-fluoro-4-phenyl) phenylpropionaldehyde, S-2- [4- (1,3-dihydro-1-oxo-2H-isoindol-2-yl) -phenyl propionaldehyde, S-2- (2-methylacetaldehyde) -5-benzoylthiophene, etc.
  • Other optically active compounds which can be prepared by the process according to the invention are described in Kirk-Othmer, Encyclopedia of
  • the inventive method allows the production of optically active products with high enantioselectivity and, if necessary, regioselectivity, for. B. in the hydroformylation. Enantiomeric excesses (ee) of at least 50%, preferably at least 60% and in particular at least 70% can be achieved.
  • the isolation of the products obtained succeeds according to customary processes known to the person skilled in the art. These include, for example, solvent extraction, crystallization, distillation, evaporation z. In a wiper blade or falling film evaporator, etc.
  • optically active compounds obtained by the process according to the invention may be subjected to one or more secondary reactions.
  • Such methods are known to the person skilled in the art. These include, for example, the esterification of alcohols, the oxidation of alcohols to aldehydes, N-alkylation of amides, addition of aldehydes to amides, nitrile reduction, acylation of ketones with esters, acylation of amines, etc.
  • asymmetri ⁇ hydroformylation obtained optically active aldehydes of an oxidation to carboxylic acids, reduction to alcohols, aldol condensation to ⁇ , ß-unsaturated Verbindun ⁇ gene, reductive amination to amines, amination to imines, etc., were ⁇ subjected.
  • a preferred derivatization comprises the oxidation of an aldehyde prepared according to the asymmetric hydroformylation process according to the invention to give the corresponding optically active carboxylic acid.
  • a variety of pharmaceutically important compounds such as S-ibuprofen, S-naproxen, S-ketoprofen, S-suprofen, S-fluorobiprofen, S-indoprofen, S-tiaprofenoic acid, etc. can be prepared.
  • Rh (CO) 2 acac and 200 mg of BINASKAT are dissolved in 15.7 g of toluene in an autoclave and stirred with synthesis gas at 9 bar reaction pressure for 4 h at 50 ° C. After addition of 1.75 g of styrene is stirred for 24 h at 50 0 C and 9 bar synthesis gas. The turnover is 93%. The gas chromatographically determined ee value is 66%.

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Abstract

L'invention concerne des composés de chélate de phosphore chiraux, des catalyseurs contenant un tel composé comme ligand et un procédé de synthèse asymétrique en présence d'un tel catalyseur.
EP05799685A 2004-10-26 2005-10-25 Ligands destines a l'hydroformulation asymetrique Withdrawn EP1807437A1 (fr)

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DE102007039526A1 (de) * 2007-08-21 2009-02-26 Lanxess Deutschland Gmbh Katalysator-Systeme und deren Verwendung für Metathese-Reaktionen
EP2027920B1 (fr) * 2007-08-21 2014-10-08 LANXESS Deutschland GmbH Catalyseurs pour les réactions de metathèses
FR2932476B1 (fr) * 2008-06-17 2010-07-30 Rhodia Operations Procede de fabrication de composes nitriles a partir de composes a insaturation ethylenique
FR2932477B1 (fr) 2008-06-17 2013-01-18 Rhodia Operations Procede de fabrication de composes nitriles a partir de composes a insaturation ethylenique
FR2937321B1 (fr) 2008-10-21 2010-10-22 Rhodia Operations Procede de fabrication de composes comprenant des fonctions nitriles
KR101108388B1 (ko) * 2009-12-10 2012-01-30 호남석유화학 주식회사 포스핀-리간드 코발트 담지촉매 및 상기 담지촉매를 이용한 1,3-프로판디올 제조방법
EP2743250A1 (fr) * 2012-12-11 2014-06-18 Studiengesellschaft Kohle mbH Procédé de préparation d'amines
DE102014201122A1 (de) 2014-01-22 2015-07-23 Leibniz-Institut Für Katalyse E.V. An Der Universität Rostock (Likat) Verfahren zur katalytischen Herstellung von ungesättigten Aldehyden
JP6835403B2 (ja) 2016-03-01 2021-02-24 株式会社クラレ ジアルデヒド化合物の製造方法
WO2018189107A1 (fr) * 2017-04-11 2018-10-18 Dsm Ip Assets B.V. Nouveau ligand de diphosphine de biphényle chiral et son procédé de préparation
CN108525704B (zh) * 2018-04-25 2019-10-18 四川大学 用于烯烃氢甲酰化反应的催化剂及其制备方法和应用
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