WO2008031889A2 - Ligands pseudochélatés contenant du pnicogène - Google Patents

Ligands pseudochélatés contenant du pnicogène Download PDF

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Publication number
WO2008031889A2
WO2008031889A2 PCT/EP2007/059722 EP2007059722W WO2008031889A2 WO 2008031889 A2 WO2008031889 A2 WO 2008031889A2 EP 2007059722 W EP2007059722 W EP 2007059722W WO 2008031889 A2 WO2008031889 A2 WO 2008031889A2
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Prior art keywords
ligands
alkyl
aryl
catalyst
cycloalkyl
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PCT/EP2007/059722
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German (de)
English (en)
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WO2008031889A3 (fr
Inventor
Jens Rudolph
Rocco Paciello
Henrik GULYÁS
Zoraida Freixa
Petrus Wilhelmus Nicolaas Maria Van Leeuwen
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Basf Se
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Publication of WO2008031889A2 publication Critical patent/WO2008031889A2/fr
Publication of WO2008031889A3 publication Critical patent/WO2008031889A3/fr

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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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • 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
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    • 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
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    • 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
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    • 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
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    • C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
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    • 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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    • B01J2531/0286—Complexes comprising ligands or other components characterized by their function
    • B01J2531/0291—Ligands adapted to form modular catalysts, e.g. self-associating building blocks as exemplified in the patent document EP-A-1 479 439
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Definitions

  • the present invention relates to catalysts comprising at least one metal complex having at least two pnicogen atom-containing compounds capable of dimerization via ionic interactions as ligands, and to processes in which such catalysts are used.
  • Asymmetric synthesis refers to reactions in which a chiral moiety is generated from a prochiral moiety, resulting in unequal amounts of the stereoisomeric products (enantiomers or diastereomers).
  • the asymmetric synthesis has gained immense importance, especially in the pharmaceutical industry, since often 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.
  • addition reactions can be characterized by the nature of the attached groups, wherein the addition of a hydrogen atom is referred to by hydro-addition and the addition of a carbon-containing fragment by carbo-addition.
  • a 1-hydro-2-carbo-addition refers to an addition of hydrogen and a carbon atom-containing group.
  • Important representatives of this reaction are z.
  • Hydroformylation or oxo synthesis is another important industrial process and is used 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 see hydroformylation is an important method for the synthesis of chiral aldehydes and is as access to chiral building blocks for the production of flavorings, cosmetics, pesticides and pharmaceuticals of interest.
  • 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 with N, P, As or Sb-containing ligands could be.
  • olefins having more than two C atoms it may be due to the possible CO addition to each of the two carbon atoms of a double bond to form mixtures of isomeric aldehydes.
  • the use of olefins having at least four carbon atoms by a double bond isomerization may lead to the formation of mixtures of isomeric olefins and optionally also isomeric aldehydes.
  • the use of chiral catalysts can lead to the formation of mixtures of enantiomeric aldehydes. For efficient asymmetric hydroformylation, therefore, the following must be considered
  • phosphorus-containing ligands for the stabilization and / or activation of the catalyst metal in the rhodium-low-pressure hydroformylation.
  • Suitable phosphorus ligands are z.
  • phosphines, phosphinites, phosphonites, phosphites, phosphoramidites, phospholes and phosphabenzenes are triarylphosphines, such as.
  • triphenylphosphine and sulfonated triphenylphosphine since they have a sufficient stability under the reaction conditions.
  • a disadvantage of these ligands is that generally only very high excess ligands provide satisfactory yields, especially on linear aldehydes.
  • E P-A-1 486 481 describes a hydroformylation process which is suitable for the hydroformylation of 1-olefins with high n-selectivity.
  • hydroformylation catalysts based on monophosphorus ligands which are capable of forming intermolecular noncovalent bonds. Such ligands can in principle dimerize via intermolecular noncovalent bonds and thus form pseudochelate complexes.
  • WO 93/03839 (EP-B-0 600 020) describes an optically active metal-ligand complex catalyst comprising an optically active phosphorus compound as ligand and processes for asymmetric synthesis in the presence of such a catalyst.
  • WO 2005/051964 relates to a process for the 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.
  • WO 2006/045597 relates to phosphorus chelate compounds and catalysts based thereon and their use for the preparation of chiral compounds with high stereoselectivity and high reactivity.
  • ligands which are capable of aggregation via ionic interactions or with their use in catalyst complexes for use, for example, in asymmetric synthesis. It is an object of the present invention to provide ligands and catalysts based thereon which are advantageously suitable for use in 1,2-additions to carbon-carbon and carbon-heteroatom double bonds and at the same time can be prepared easily and in good yields , Preferably, they should have the above-mentioned advantages of chelating ligands. These catalysts should be particularly suitable for stereoselective synthesis.
  • the invention therefore provides a catalyst comprising at least one metal complex having at least two ligands each having at least one pnicogen atom and at least one functional group capable of forming intermolecular, ionic interactions, the complex having dimerized ligands via intermolecular ionic interactions.
  • Another object of the invention is a process for the reaction of a compound containing at least one carbon-carbon or carbon-heteroatom double bond (hereinafter also referred to as ethylenically unsaturated double bond), by 1, 2-addition in the presence of a catalyst according to the invention.
  • ligands are used which have a functional group which is capable of forming intermolecular, ionic interactions.
  • the functional groups capable of forming intermolecular ionic interactions enable the ligands to associate; H. for the formation of aggregates in the form of ion pairs.
  • Monodentate ligands capable of forming dimers through intermolecular ionic interactions are also referred to herein as pseudo chelate ligands.
  • the distance between the pnicogen atoms of the pseudochelate ligands is preferably at most 5 ⁇ , more preferably in a range from 2.5 to 4.5 ⁇ , especially 3.5 to 4.2 ⁇ .
  • Complementary functional groups A pair of functional groups of two ligands capable of forming intermolecular ionic interactions are referred to in the present invention as "complementary functional groups.”
  • “Complementary compounds” are ligand / ligand pairs having complementary functional groups. Such pairs are for association, i. H. qualified for the training of aggregates.
  • ligand / ligand pairs may also be formed from ligands of the same charge or ligands capable of accepting the same charge using at least one oppositely charged / chargeable compounds complementary to these ligands.
  • Such combinations of identically charged / chargeable ligands and oppositely charged / chargeable compounds are also capable of association.
  • alkyl includes straight-chain and branched alkyl groups, preferably straight-chain or branched C 1 -C 20 -alkyl, preferably C 1 -C 12 -alkyl, more preferably C 1 -C 8 -alkyl- and very particular preference is given to C 1 -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,
  • alkyl also includes substituted alkyl groups which generally have 1, 2, 3, 4 or 5, preferably 1, 2 or 3 and particularly preferably 1 substituent, these being preferably selected from cycloalkyl, aryl, hetaryl, halogen, NE 1 e 2, NE 1 e 2 e 3+, carboxylate and sulfonate.
  • a preferred perfluoroalkyl is trifluoromethyl.
  • alkylene in the context of the present invention stands for straight-chain or branched alkanediyl groups having 1 to 5 carbon atoms.
  • cycloalkyl includes unsubstituted or substituted cycloalkyl groups, preferably C 5 -C 7 -cycloalkyl groups, such as cyclopentyl, cyclohexyl or cycloheptyl, which in the case of a substitution, generally 1, 2, 3, 4 or 5, preferably 1, 2 or 3 and more preferably 1 substituent, preferably these substituents are selected from alkyl, alkoxy and halogen.
  • 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 represented by heteroatoms selected from the elements oxygen, nitrogen and sulfur, in the case of a substitution, these heterocycloaliphatic groups may carry 1, 2 or 3, preferably 1 or 2, more preferably 1 substituent, these substituents are preferably selected from among
  • Alkyl, aryl, carboxylate and NE 1 E 2 particularly preferred are alkyl radicals.
  • alkyl radicals are pyrrolidinyl, piperidinyl, 2,2,6,6-tetramethylpiperidinyl, imidazolidinyl, pyrazolidinyl, 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, carboxylate, trifluoromethyl, sulfonate, NE 1 E 2 , alkylene NE 1 E 2 , nitro, cyano or halogen
  • a preferred perfluoroaryl group is pentafluorophenyl.
  • heterocycloaromatic groups preferably the groups pyridyl, quinolinyl, acridinyl, pyridazinyl, pyrimidinyl, pyrazinyl, pyrrolyl, imidazolyl, pyrazolyl, indolyl, purinyl, indazolyl, benzotriazolyl , 1, 2,3-triazolyl, 1, 3,4-triazolyl and carbazolyl.
  • these heterocycloaromatic groups may in general have 1, 2 or 3 substituents selected from the groups alkyl, alkoxy, carboxylate, sulfonate, NE 1 E 2 , alkylene-NE 1 E 2 or halogen.
  • Carboxylate, phosphonate, phosphinate, sulfonate, sulfinate and boronate in the context of the present invention are a derivative of a carboxylic acid function, a phosphonic acid function, a phosphinic acid function, a sulfonic acid function, a sulfinic acid function or a boronic acid function.
  • these terms are a metal carboxylate, phosphonate, phosphinate, sulfonate, sulfinate or boronate or the esters and amides of the corresponding acids. These include z.
  • esters with Ci-C4-alkanols such as methanol, ethanol, n-propanol, isopropanol, n-butanol, sec-butanol and tert-butanol.
  • 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, hepta noyl, 2-ethylhexanoyl, 2-propylheptanoyl, benzoyl or naphthoyl group.
  • the radicals E 1 to E 5 are independently selected from hydrogen, alkyl, cycloalkyl and aryl.
  • the groups NE 1 E 2 and NE 4 E 5 are preferably for
  • Halogen is fluorine, chlorine, bromine and iodine, preferably fluorine, chlorine and bromine.
  • Pnicogen stands for phosphorus, arsenic, antimony and bismuth, in particular phosphorus.
  • M + stands for a cation equivalent, ie for a monovalent cation or the portion 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 carboxylate or the sulfonate anion, and can in principle be chosen arbitrarily.
  • alkali metal in particular Na + , K + , Li + ions or onium ions, such as ammonium, iminium, mono-, di-, tri-, tetraalkylammonium, phosphonium, tetraalkylphosphonium, Tetraarylphosphonium ions or polyvalent cations, such as Mg 2+ , Zn 2+ , Fe 2+ , Fe 3+ or Al 3+ used.
  • anion equivalent X " which is used only as a counterion of positively charged substituent groups, such as, for example, the ammonium groups or iminium groups. pen, serves and can be chosen arbitrarily among monovalent anions and the negative single charge portions of a polyvalent anion X n ", such as Ch, Br,
  • R ' is alkyl, cycloalkyl or aryl.
  • R ' is preferably a linear or branched aliphatic or alicyclic alkyl or C ⁇ -Cis-aryl, C ⁇ sds-aryl-Ci-C ⁇ -alkyl or Ci-Ce-alkyl-C ⁇ -Cis-aryl-containing 1 to 12 carbon atoms. Radical which may be substituted by halogen atoms.
  • polycyclic compound in the context of the present invention broadly encompasses compounds containing at least two rings, regardless of how these rings are linked, which may be carbocyclic and / or heterocyclic rings or double bonds (“polynuclear compounds"), linked by annulation (“fused ring systems”) or bridged (“bridged ring systems", “cage compounds”) Preferred polycyclic compounds are fused ring systems.
  • Condensed ring systems may be fused (fused) aromatic, hydroaromatic and cyclic compounds.
  • Condensed ring systems consist of two, three or more than three rings. Depending on the type of linkage, a distinction is made in condensed ring systems between an ortho-annulation, 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 catalyst complex according to the invention comprises two ligands with functional groups complementary to one another or two dimerized ligands via a divalent ionic and / or ionogenic compound which is complementary to the functional groups.
  • ionic and / or ionogenic compounds according to the second of the abovementioned variants, depending on the functional groups of the compounds used as ligands, at least divalent cation or anion equivalents are suitable.
  • suitable metal cations such as Mg 2+ , Zn 2+ , Fe 2+ , Fe 3+ , Co 2+ , Co 3+ , Ni 2+ , Cu 2+ , Pt 2+ , Mn 2+ , Al 3+ , Pd 2+ , Rh 3+ , Ru 2+ , Ru 3+ or V 2+ .
  • Particularly suitable anion equivalents are SO 4 2 " , PO 4 3" , HPO 4 2 " , C 2 O 4 2” or malonate dianion.
  • the ligands capable of forming intermolecular ionic interactions are selected from compounds of the general formula (I)
  • Pn stands for a pnicogen atom
  • a, b and c are independently O or 1,
  • X 1 , X 2 and X 3 independently of one another represent O, S, NR a , or SiR b R c , where R a , R b and R c independently of one another represent hydrogen, alkyl, cycloalkyl, heterocycloalkyl, aryl or hetaryl stand,
  • R ⁇ , R ⁇ and R ⁇ independently of one another are alkyl, cycloalkyl, heterocycloalkyl, aryl or hetaryl, the alkyl radicals optionally having 1, 2, 3, 4 or 5 substituents selected from cycloalkyl, heterocycloalkyl, aryl, hetaryl, alkoxy , Cycloalkoxy, heterocycloalkoxy, aryloxy, hetaryloxy, hydroxy, mercapto, polyalkylene oxide, polyalkyleneimine, halogen, nitro, acyl or cyano, and wherein the cycloalkyl, heterocycloalkyl, aryl and hetaryl radicals optionally 1, 2, 3 , 4 or 5 substituents which are selected from alkyl and the substituents mentioned above for the alkyl radicals R ⁇ , R ⁇ and R ⁇ ,
  • R ⁇ , R ⁇ , R ⁇ carries an ionogenic and / or ionic group which is capable of forming an ionic interaction with a pnicogenatomhal- term ligand with complementary functional group.
  • R ⁇ , R ⁇ and R ⁇ are preferably independently selected from alkyl, cycloalkyl, aryl and hetaryl.
  • at least one of the radicals R ⁇ , R ⁇ and R ⁇ , and particularly preferably at least two of the radicals R ⁇ , R ⁇ and R ⁇ are aryl, in particular phenyl.
  • R ⁇ and R ⁇ are bridged together.
  • the pnicogen atom-containing ligand is preferably a compound of the formula (II)
  • a together with the pnicogen atom and if present is together with the radicals X 1 and X 2 represents a 5- to 8-membered heterocycle which may additionally be, two-, three- or four-fused with cycloalkyl, heterocycloalkyl, aryl or hetaryl wherein the heterocycle and, if present, the fused groups independently of one another can each carry one, two, three or four substituents which are selected from alkyl, cycloalkyl, heterocycloalkyl, aryl, hetaryl, hydroxy, mercapto, polyalkylene oxide, polyalkyleneimine , Alkoxy, halogen, nitro, alkoxycarbonyl, acyl and cyano.
  • the radical A is a C2-C6-alkylene bridge which is fused 1- or 2-fold with aryl and / or which may have a substituent selected from alkyl, optionally substituted cycloalkyl and optionally substituted aryl, and / or which may be interrupted by an optionally substituted heteroatom.
  • the fused aryls of the radicals A are preferably benzene or naphthalene.
  • Anellated 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, sulfonate, NE 4 E 5 , alkylene-NE 4 E 5 , trifluoromethyl, nitro, carboxylate , 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 the previously mentioned in the fused benzene rings th 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 in particular methoxy.
  • Alkoxycarbonyl is preferably C 1 -C 4 -alkoxycarbonyl.
  • C 2 -C 6 -alkylene bridge of the radical A is interrupted by 1, 2 or 3, optionally substituted heteroatoms, these are preferably selected from O, S or NR h , where R h is alkyl, cycloalkyl or aryl.
  • the C 2 -C 6 -alkylene bridge of the radical A When the C 2 -C 6 -alkylene bridge of the radical A is substituted, it preferably has 1, 2 or 3, in particular a substituent which is / are selected from alkyl, cycloalkyl, heterocycloalkyl, aryl and hetaryl, where the cycloalkyl- , Heterocycloalkyl, aryl and Hetarylsubstituenten in each case 1, 2 or 3 of the initially mentioned as suitable for these radicals substituents.
  • the radical A is a Cs-C ⁇ -alkylene bridge which is fused and / or substituted as described above and / or interrupted by optionally substituted heteroatoms.
  • the radical A is a Cs-C ⁇ -alkylene bridge which is fused once or twice with phenyl and / or naphthyl, where the phenyl or naphthyl groups may carry 1, 2 or 3 of the abovementioned substituents.
  • the radical A together with the pnicogen atom and the heteroatom (s) to which it is attached, represents a 5- to 8-membered heterocycle, A preferably being a radical which is selected from the radicals of the formulas III.1 to III.5,
  • T is O, S or NR 1 , wherein R 1 is alkyl, cycloalkyl or aryl.
  • R 1 , R 11 , R 111 , R IV , R v , R V “, RVII, RVIII, RIX, RX, RXI and R x " are each independently hydrogen, alkyl, cycloalkyl, aryl, alkoxy, halogen, sulfonate, NE 4 E 5 , alkylene- NE 4 E 5 , trifluoromethyl, nitro, alkoxycarbonyl or cyano;
  • T is a C 1 -C 3 -alkylene bridge which may have a double bond and / or an alkyl, cycloalkyl or aryl substituent, where the aryl substituent may carry one, two or three of the substituents mentioned for aryl,
  • T is a C 2 -C 3 -alkylene bridge interrupted by O, S or NR 1 , wherein R 1 is alkyl, cycloalkyl or aryl.
  • the pnicogen atom is a phosphorus atom.
  • the ligands capable of forming intermolecular ionic interactions are selected from monodentate phosphine, phosphinite, phosphonite, phosphoramidite and phosphite compounds; especially among phosphine compounds.
  • the functional groups capable of forming intermolecular ionic interactions are selected from cationic groups such as primary, secondary and tertiary ammonium or iminium groups, and / or anionic functional groups such as carboxylate, phosphonate, phosphinate, sulfonate, sulfinate or boronate groups.
  • cationic groups such as primary, secondary and tertiary ammonium or iminium groups
  • anionic functional groups such as carboxylate, phosphonate, phosphinate, sulfonate, sulfinate or boronate groups.
  • the ligands capable of forming intermolecular ionic interactions are selected from triphenylphosphines in which each one of the phenyl radicals comprises a functional group capable of forming intermolecular ionic interactions.
  • triphenylphosphine-3-sulfonate [P (CeH 5 MrTi-CeI-USOsNa)] and / or triphenylphosphine 3-aminohydrochloride [P (C6H5) 2 (m-C6H4NH3Cl)] can be used as a ligand capable of generating intermolecular ionic interactions.
  • a suitable ligand pair is the ion pair of 3-ammonium triphenylphosphine and triphenylphosphine sulfonate.
  • the transition metal used according to the invention is preferably a metal of subgroup VIII of the Periodic Table of the Elements (that is to say Fe, Co, Ni, Ru, Rh, Pd, Os, Ir, Pt).
  • the transition metal is cobalt, nickel, ruthenium, rhodium, iridium, palladium or platinum.
  • the catalysts according to the invention and used according to the invention preferably have two or more than two of the compounds described above as ligands. At least two of the ligands are preferably present in dimerized form. In addition to the ligands described above, 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, PF3, phospholes, phosphabenzenes and mono-, bi- and polydentate phosphine, phosphinite, phosphonite, phosphoramidite and phosphite ligands.
  • the molar ratio of metal to ligand is preferably in a range from about 1: 1 to 1: 100, more preferably 1: 2 to 1:10, in particular 1: 2 to 1: 5.
  • the catalyst is chiral.
  • ligands which have only one pnicogen atom-containing group per ligand are suitable for addition reactions with high regioselectivities. So z.
  • n-selectivities as high as those otherwise achieved with chelating ligands are achieved.
  • the present invention therefore further provides a process for reacting a compound which contains at least one ethylenically unsaturated double bond by 1,2-addition in the presence of a catalyst according to the invention.
  • the processes according to the invention for the reaction of ethylenically unsaturated compounds are preferably hydrogenation, hydroformylation, hydrocyanation, carbonylation, hydroacylation (intramolecular and intermolecular), hydroamidation, hydroesterification, hydrosilylation, hydroboration, aminolysis (aminolation), alcoholysis (Hydroxy-alkoxy addition), isomerization, transfer hydrogenation, metathesis, cyclopropanation, aldol condensation, allylic alkylation or a [4 + 2] cycloaddition (Diels-Alder reaction).
  • the 1,2-addition is a hydroformylation by reaction with carbon monoxide and hydrogen, one of the catalysts described above being used as the hydroformylation catalyst.
  • asymmetric catalysts based on the ligand pairs described above are particularly advantageously suitable for use in asymmetric synthesis.
  • such high stereoselectivities can be achieved as otherwise can only be achieved with chelating ligands.
  • ligands are capable of forming dimers via intermolecular ionic interactions.
  • the ligands of the formula I in a molar ratio of at least 2: 1, based on the metal, especially on the metal of VIII Subgroup, use.
  • Another object of the invention is a process for the preparation of chiral 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. It is only necessary that at least one of the ligands used or the catalytically active species is chiral as a whole.
  • certain transition metal complexes are formed as catalytically active species under the reaction conditions of the individual processes for producing chiral compounds.
  • the catalytically active species can be both homogeneous and heterogeneous.
  • the catalytically active species is 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 producing 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.
  • 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 for the respective process and adapted routinely by the person skilled in the art.
  • Suitable reaction temperatures are generally in a range from -100 to 500 ° C., preferably in a range from -80 to 250 ° C.
  • Suitable reaction pressures are generally in a range from 0.0001 to 600 bar, preferably from 0.5 to 300 bar.
  • the processes may generally be continuous, semi-continuous or batch-wise. Suitable reactors for the continuous reaction are known in the art and z. B. 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.
  • suitable solvents are esters of aliphatic carboxylic acids with alkanols, for example ethyl acetate or Texanol®, ethers, such as tert-butyl methyl ether, 1,4-dioxane and tetrahydrofuran, and dimethylformamide.
  • alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, ketones, such as acetone and methyl ethyl ketone, etc.
  • solvent it is also possible to use an educt, product or by-product of the particular reaction.
  • prochiral olefins hydrogenation, hydroformylation, intermolecular hydroacylation, hydrocyanation, hydrosilylation, carbonylation, hydroamidation, hydroesterification, aminolysis, alcoholysis, cyclopropanation, hydroboration, Diels-
  • Suitable prochiral ethylenically unsaturated olefins are generally compounds of the
  • R A and R B and / or R c and R D are radicals of different definitions. It goes without saying that for the preparation according to the invention of chiral compounds also the substrates reacted with the prochiral ethylenically unsaturated compound and, under certain circumstances, also the stereoselectivity with respect to the addition 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 are preferably independently selected from hydrogen, alkyl, cycloalkyl, heterocycloalkyl, aryl, hetaryl, alkoxy, cycloalkoxy, heterocycloalkoxy, aryloxy, hetaryloxy, hydroxy, mercapto, taking into account the abovementioned condition.
  • 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 radicals R A , R B , R c and R D mentioned substituents, 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 20-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 20 -olefins, such as 2-methyl-2-butene, 2-methyl-2-pentene, 3-methyl-2-pentene, branched, internal mixtures of heptene, branched, internal octenes. Mixtures, branched, internal nonion mixtures, branched, internal decene mixtures, branched, internal undecene mixtures, branched, internal dodecene mixtures, etc.
  • Suitable olefins are furthermore Cs-Cs-cycloalkenes, such as cyclopentene, cyclohexene, cycloheptene, cyclooctene and their derivatives, such as. B. their Ci-C2o-alkyl derivatives having 1 to 5 alkyl substituents.
  • Suitable olefins are furthermore vinylaromatics, such as styrene, ⁇ -methylstyrene, 4-isobutylstyrene, etc., 2-vinyl-6-methoxynaphthalene, (3-ethenylphenyl) phenyl ketone, (4-ethenylphenyl) -2-thienyl ketone, 4-ethenyl-2-ol 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.
  • suitable olefins are o.p.-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, 1 1-dodecadiene, 1, 12-tridecadiene, 1, 13-tetradecadiene, vinylcyclohexene, dicyclopentadiene, 1, 5,9-cyclooctatriene and Butadienhomo- and copolymers.
  • prochiral ethylenically unsaturated compounds are, for. 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 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.
  • catalyst precursors Very suitable as catalyst precursors are 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) i2, rhodium bis-bis- carbonyl acetylacetonate, acetylacetonatobisethylene 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.
  • metal carbonyls of ruthenium such as trisruthenium dodecacarbonyl or hexaruthenium octadecacarbonyl, or mixed forms in which CO has been partially replaced by ligands of the formula PR3, such as Ru (CO) 3 (PPh3) 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).
  • diene complexes eg. B. cyclopentadiene complexes or Cycloocta- dienkomplexe, carbonyl complexes, hetaryl, z. Pyridyl complexes or bipyridyl complexes, phosphine complexes, e.g. B. Triphenylphosphine complexes or Triethylphosphinkomplexe, halides, z. As chlorides, bromides or iodides, hydrides, carboxylates, z.
  • acetylacetonates As acetates or propionates, acetylacetonates, borates, sulfates, sulfides, cyanides, nitrates, nitrile complexes, etc. of iridium, osmium, palladium or platinum, etc.
  • 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 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).
  • a prochiral compound containing at least one ethylenically unsaturated double bond with hydrogen in the presence of a chiral catalyst as described above, one obtains corresponding chiral compounds having a single bond.
  • Prochiral olefins lead to chiral carbon-containing compounds, prochiral ketones to chiral alcohols, and prochiral imines to chiral amines.
  • the catalysts according to the invention used for the hydrogenation preferably comprise at least one metal of the VIII subgroup which is selected from among Rh, Ir, Ru, Ni, Co, Pd and Pt.
  • the amount of catalyst to be used depends, inter alia, on the respective catalytically active metal and on its form of use and can be determined by the person skilled in the individual case.
  • a Ni or Co-containing hydrogenation catalyst in an amount of preferably 0.1 to 70 wt .-%, particularly preferably from 0.5 to 20 wt .-% and in particular from 1 to 10 wt.%, based on the weight of the compound to be hydrogenated used.
  • the specified amount of catalyst refers to the amount of active metal, ie, the catalytically active component of the catalyst.
  • noble metal catalysts containing, for example, rhodium, ruthenium, platinum or palladium smaller amounts are used by about a factor of 10.
  • the hydrogenation is preferably carried out at a temperature in the range from 0 to 250 ° C., more preferably in the range from 20 to 200 ° C. and in particular in the range from 50 to 150 ° C.
  • the reaction pressure of the hydrogenation reaction is preferably in the range from 1 to 300 bar, particularly preferably in the range from 50 to 250 bar and in particular in the range from 150 to 230 bar.
  • reaction pressure and the reaction temperature depend inter alia on the activity and amount of the hydrogenation catalyst used and can be determined by the skilled person in individual cases.
  • Suitable solvents are those which are inert under the reaction conditions, d. H. neither react with the starting material or product nor be changed themselves, and can be easily separated from the resulting isoalkanes.
  • Suitable solvents include, for example, open-chain and cyclic ethers, such as diethyl ether, methyl tert-butyl ether, tetrahydrofuran or 1,4-dioxane and alcohols, in particular C 1 -C 3 -alkanols, such as methanol, ethanol, n-propanol or isopropanol. Also suitable are mixtures of the abovementioned solvents.
  • the hydrogen required for the hydrogenation can be used both in pure form and in the form of hydrogen-containing gas mixtures. However, the latter must not contain harmful amounts of catalyst poisons, such as sulfur compounds or CO. Examples of suitable hydrogen-containing gas mixtures are those from the reforming process. Preferably, however, hydrogen is used in pure form.
  • the hydrogenation can be configured both continuously and discontinuously.
  • the hydrogenation is generally carried out by initially introducing the compound to be hydrogenated, if appropriate in a solvent. This reaction solution is then preferably added to the hydrogenation catalyst, before then the hydrogen is introduced. Depending on the hydrogenation catalyst used, the hydrogenation is carried out at elevated temperature and / or at elevated pressure.
  • the usual, known from the prior art pressure vessels such as autoclaves, stirred autoclave and pressure reactors can be used. If hydrogen overpressure is not used, the usual state-of-the-art reaction devices which are suitable for atmospheric pressure are considered. Examples thereof are customary stirred tanks, which are preferably equipped with a boiling-cooling system, suitable mixers, introduction devices, optionally heat exchanger elements and inerting devices.
  • the hydrogenation under normal pressure in customary reaction vessels, tubular reactors, fixed bed reactors and the like can be carried out.
  • the catalyst and the solvent are usually removed. If the catalyst is heterogeneous, it is preferably separated by filtration or by sedimentation and removal of the upper, product-containing phase. Other separation methods for removing solids from solutions, such as centrifuging, are also suitable for removing a heterogeneous catalyst.
  • the removal of a homogeneous catalyst according to the invention is carried out by conventional methods for the separation of in-phase mixtures, for example by chromatographic methods.
  • protic solvents eg. B. with water or with Ci-C3-alkanols, such as methanol, ethanol, propanol or isopropanol, which are if necessary basic or acidic.
  • 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 pseudochelate ligand to metal of VIII subgroup is generally in the range of about 1: 1 to 1000: 1, preferably 2: 1 to 500: 1.
  • hydroformylation catalyst is prepared in situ, reacting at least one ligand pair 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.
  • composition of the synthesis gas of carbon monoxide and hydrogen used in the process according to the invention can vary within wide ranges.
  • the molar ratio of carbon monoxide and hydrogen is generally about 5:95 to 70:30, preferably about 40:60 to 60:40. More preferably, a molar ratio of carbon monoxide and hydrogen in the range of about 1: 1 is used.
  • the temperature in the hydroformylation reaction is generally in a range of about 20 to 180 ° C., preferably about 50 to 150 ° C.
  • the pressure is in a range from about 1 to 700 bar, preferably 1 to 600 bar, in particular 1 up to 300 bar.
  • the reaction pressure can be varied depending on the activity of the hydroformylation catalyst of the invention used.
  • the catalysts of the invention based on pnicogen-containing compounds allow a reaction in a range of low pressures, such as in the range of 1 to 100 bar.
  • hydroformylation catalysts used according to the invention and the hydroformylation catalysts according to the invention can be separated off from the hydroformylation reaction output by customary methods known to the person skilled in the art and can generally be used again for the hydroformylation.
  • the asymmetric hydroformylation by the process according to the invention is characterized by a high stereoselectivity.
  • the catalysts according to the invention and the catalysts used according to the invention generally also show 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 known from the prior art catalysts based on conventional chelating ligands.
  • Advantageous- The catalysts according to the invention and used according to the invention continue to show high activity, so that the corresponding aldehydes or alcohols are generally obtained in good yields.
  • the catalysts used for the hydrocyanation include complexes of a metal of VIII. Subgroup, in particular cobalt, nickel, ruthenium, rhodium, palladium, platinum, preferably nickel, palladium and platinum and most 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.
  • An important embodiment of the 1-hydro-2-carbo addition is the 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 special 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. BF3, AICb, ZnCb, 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 methods of hydroacylation are described in J. March, Advanced Organic Chemistry, 4th ed., P. 811, incorporated herein by reference.
  • Another important 1,2-addition is hydroamidation.
  • a prochiral compound containing at least one ethylenically unsaturated double bond with carbon monoxide and ammonia, a primary or a secondary amine in the presence of a chiral catalyst, as described above, to obtain chiral amides.
  • hydroboration Another important 1,2-addition is hydroboration.
  • a prochiral compound containing at least one ethylenically unsaturated double bond with borane or a borane source in the presence of a chiral catalyst as described above, chiral trialkylboranes are obtained which can be converted into primary alcohols (eg with NaOH / H2O2). or can be oxidized to carboxylic acids.
  • Suitable hydroboration processes are described in J. March, Advanced Organic Chemistry, 4th ed., Pp. 783-789, which is incorporated herein by reference.
  • hydrosilylation Another important 1,2-addition is hydrosilylation.
  • a prochiral compound containing 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) 3) 3) and RHCB. Also suitable are RuCb and IrCb.
  • Suitable catalysts are also Lewis acids such as AICb or TiCU and peroxides.
  • Suitable silanes are z.
  • Halogenated silanes such as trichlorosilane, methyldichlorosilane, dimethylchlorosilane and trimethylsiloxydichlorosilane; Alkoxysilanes such as trimethoxysilane, triethoxysilane, methyldimethoxysilane, phenyldimethoxysilane, 1, 3,3,5,5,7,7-heptamethyl-1, 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. in the 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 methods of hydroamination are described in J. March, Advanced Organic Chemistry, 4th ed., Pp. 768-770, which is incorporated herein by reference.
  • alcoholysis hydro-alkoxy-addition
  • a prochiral compound containing at least one ethylenically unsaturated double bond with alcohols in the presence of a chiral catalyst as described above, one obtains chiral ethers.
  • Suitable methods for alcoholysis are described in J. March, Advanced Organic Chemistry, 4th Ed., Pp. 763-764, which is incorporated herein by reference.
  • Another important reaction is cyclopropanation.
  • a prochiral compound containing at least one ethylenically unsaturated double bond contains, with a diazo compound in the presence of a chiral catalyst as described above, to chiral cyclopropanes.
  • 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, to obtain chiral hydrocarbons.
  • 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 of 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.
  • optically active compounds are in Kirk Othmer, Encyclopedia of Chemical Technology, Third Edition, 1984, and The Merck Index, An Encyclopedia of Chemicals, Drugs and Biologicals, Eleventh Edition, 1989, which is incorporated herein by reference.
  • 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.
  • optically active aldehydes of an oxidation to carboxylic acids, reduction to alcohols, aldol condensation to ⁇ , ß-unsaturated compounds, reductive amination to amines, amination to imines, etc. be subjected.
  • a preferred derivatization comprises the oxidation of an aldehyde prepared by the asymmetric hydroformylation process according to the invention to 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.
  • dimers include crystal structure analysis, nuclear magnetic resonance spectroscopy and molecular modeling methods. It is usually sufficient to determine the ligands to use in non-complexed form. This is especially true for molecular modeling methods. It was also found that both by crystal structure analysis, which takes place on the solid, as well as by nuclear magnetic resonance spectroscopy in solution, as well as by calculating the structure for the gas phase in general, reliable predictions about the behavior of the ligands used under the hydroformylation be achieved. Thus, ligands which are capable of forming dimers according to the stated determination methods generally have properties under hydroformylation conditions which are otherwise customary only for chelating ligands. This includes in particular the achievement of a high n-selectivity in the hydroformylation of 1-olefins.
  • DFT density functional theory
  • B-P86 AD Becke, Phys. Rev. A 1988, 38, 3098, JP Perdew, Phys. Rev. B 1986, 33, 8822; 1986, 34, 7406 (E)
  • P base SV
  • Preferred pseudochelate ligands are those in which the distance of the pnicogen atoms in the calculated dimer structure is less than 5 ⁇ .
  • FIGS. 1 to 3 show X-ray structures of complexes according to the invention and those of non-limiting explanation of the present invention.
  • Fig. 1 shows the X-ray structure of cis-Pt (TPPMS) (3- (diphenylphosphino) aniline) Cl2.
  • Fig. 2 shows the X-ray structure of trans-Pd (TPPMS) (3- (diphenylphosphino) aniline) -
  • FIG. 3 shows the X-ray structure trans-Rh (TPPMS) (N- (2-propylidene) -3- (diphenylphosphinyl) aniline) (CO) Cl.
  • Method A 0.04 mmol Pt (COD) Cl 2 and 0.042 mmol each of TPPMS (1) and 3- (diphenylphosphanyl) aniline hydrochloride (3) were placed in a Schlenk flask. Subsequently, the solvent (see Table 1) was added and the resulting mixture was stirred for 10 to 30 minutes.
  • Method B A solution of 0.042 mmol each of ligands (1) and (3) in the solvent indicated in square brackets in Table 1 was added to a solution of 0.04 mmol of the precursor complex (Pt (COD) Cb in Table 1 The reaction mixture was stirred for 10 to 30 minutes.
  • the yield of the complex according to the invention depends on the solvent used The results are summarized in Table 1. The deuterated solvents were used exclusively to identify the resulting complexes by NMR spectroscopy. To enable spectroscopy.
  • the catalysts according to the invention can be obtained from a suitable metal precursor complex and at least two pnicogen atom-containing ligands capable of dimerization via ionic interactions.

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Abstract

La présente invention concerne des catalyseurs, comprenant au moins un complexe métallique avec au moins deux ligands, lesdits ligands contenant au moins un atome de pnicogène et au moins un groupement fonctionnel permettant la formation d'effets réciproques ioniques et intermoléculaires. Selon l'invention, le complexe comporte des ligands dimérisés par effets réciproques ioniques et intermoléculaires. L'invention concerne également un procédé de transformation d'un composé, contenant au moins une double liaison carbone-carbone ou carbone-hétéroatome, par 1,2-addition en présence du catalyseur selon l'invention.
PCT/EP2007/059722 2006-09-15 2007-09-14 Ligands pseudochélatés contenant du pnicogène WO2008031889A2 (fr)

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CN104248994A (zh) * 2013-06-25 2014-12-31 中国石油化工股份有限公司 羰基化铑膦催化剂的活性恢复方法

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