EP2057109A2 - Reactions d'addition catalysees par un metal de transition dans des solvants halogenes - Google Patents

Reactions d'addition catalysees par un metal de transition dans des solvants halogenes

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Publication number
EP2057109A2
EP2057109A2 EP07821593A EP07821593A EP2057109A2 EP 2057109 A2 EP2057109 A2 EP 2057109A2 EP 07821593 A EP07821593 A EP 07821593A EP 07821593 A EP07821593 A EP 07821593A EP 2057109 A2 EP2057109 A2 EP 2057109A2
Authority
EP
European Patent Office
Prior art keywords
alkyl
aryl
cycloalkyl
ligands
hydrogen
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP07821593A
Other languages
German (de)
English (en)
Inventor
Jens Rudolph
Rocco Paciello
Christoph JÄKEL
Frank Hettche
Armin BÖRNER
Natalia Dubrovina
Mandy-Nicole Birkholz
Bernhard Breit
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BASF SE
Original Assignee
BASF SE
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Filing date
Publication date
Application filed by BASF SE filed Critical BASF SE
Priority to EP07821593A priority Critical patent/EP2057109A2/fr
Publication of EP2057109A2 publication Critical patent/EP2057109A2/fr
Withdrawn legal-status Critical Current

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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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    • 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
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    • 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
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    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
    • B01J31/2404—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring
    • B01J31/2419—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring comprising P as ring member
    • B01J31/2438—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring comprising P as ring member and further hetero atoms as ring members, excluding the positions adjacent to P
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    • 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
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    • B01J31/2447—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring comprising condensed ring systems and phosphine-P atoms as substituents on a ring of the condensed system or on a further attached ring
    • B01J31/2452—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring comprising condensed ring systems and phosphine-P atoms as substituents on a ring of the condensed system or on a further attached ring with more than one complexing phosphine-P atom
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    • B01J31/2461—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring comprising condensed ring systems and phosphine-P atoms as ring members in the condensed ring system or in a further ring
    • B01J31/2471—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring comprising condensed ring systems and phosphine-P atoms as ring members in the condensed ring system or in a further ring with more than one complexing phosphine-P atom
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    • C07C45/72—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by reaction of compounds containing >C = O groups with the same or other compounds containing >C = O groups
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    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
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    • C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
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    • C07F9/00—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
    • C07F9/6568—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 atoms as the only ring hetero atoms
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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
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    • B01J2231/341—1,2-additions, e.g. aldol or Knoevenagel condensations
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    • B01J31/2466—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring comprising condensed ring systems and phosphine-P atoms as ring members in the condensed ring system or in a further ring comprising aliphatic or saturated rings
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    • C07B2200/07—Optical isomers

Definitions

  • the present invention relates to a process for reacting compounds containing at least one carbon-carbon or carbon-heteroatom double bond, by 1,2-addition in the presence of a catalyst comprising at least one transition metal complex having at least two ligands, each having a pnico - Have genatom inconvenience group and at least one capable of forming intermolecular, non-co- valent bonds capable of functional group, and in the presence of a chlorinated or fluorinated solvent having at least one hetero atom other than halogen.
  • the present invention further relates to a process for the preparation of chiral compounds in the presence of the catalysts and solvents described above and the use of these catalysts in the presence of such solvents.
  • Addition reactions can additionally be characterized according to the nature of the attached groups, wherein the addition of a hydrogen atom is designated 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.
  • catalysts for asymmetric addition reactions to prochiral ethylenically unsaturated compounds having good catalytic activity and / or high stereoselectivity.
  • 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.
  • 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.
  • Asymmetric hydroformylation is an important method for the synthesis of chiral aldehydes and is of interest for access to chiral building blocks for the production of flavorings, cos- metics, pesticides, and pharmaceuticals.
  • the hydroformylation reaction itself is highly exothermic and generally proceeds 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 are used to influence the activity and / or selectivity with N-, P-, As- or Sb-containing ligands. could have been modified.
  • 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.
  • 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 ligand excesses give satisfactory yields, especially on linear aldehydes.
  • chelating ligands having two phosphorus atom-containing groups capable of coordination has an advantageous effect on the n-selectivity achieved.
  • a disadvantage of the use of chelating ligands is that they often require complex syntheses to prepare them and / or they are obtained only in poor yields. There is thus still a need for readily available ligands which, for example in the case of use as hydroformylation catalysts, enable a high n-selectivity.
  • 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 asymmetric synthesis in the presence of a chiral catalyst comprising at least one complex of a metal of subgroup VIII with ligands capable of dimerization via noncovalent 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.
  • PCT / EP2007 / 059722 (the non-prepublished patent application EP 06120780.9) describes catalysts comprising at least one metal complex having at least two pnicogen atom-containing compounds capable of dimerization via ionic interactions as ligands. Furthermore, methods for reacting by 1,2-addition to compound which contain at least one carbon-carbon or carbon-heteroatom double bond are described in which such catalysts are used.
  • Such ligands can in principle be prepared via intermolecular ionic see interactions form aggregates in the form of ion pairs and thus form pseudochelate complexes.
  • E P-A-1 486 481 describes a hydroformylation process which is suitable for the hydroformylation of 1-olefins with high n-selectivity. They use 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.
  • EP-A-1 486 481 discloses that the high n-selectivity achieved using the monophosphorus ligand hydroformylation catalysts disclosed therein is no longer achieved when hydroformylation results in the formation of intermolecular noncovalent bonds between the ligands by the addition of Acids or protic solvents, such as. As methanol is disturbed.
  • the object of the present invention is to provide processes for the 1,2-addition to carbon-carbon and carbon-heteroatom double bonds whose conditions have a positive influence on reaction time, conversion and selectivity, the catalysts used in these processes being light and easy can be prepared in good yields and preferably have the above-mentioned advantages of the chelate ligand complexes. These methods should be particularly suitable for stereoselective synthesis.
  • transition metal complexes of pnicogen ligands especially monopnicogen ligands which are capable of forming intermolecular interactions in the presence of halogenated solvents having at least one heteroatom other than halogen, even if these, such as trifluoroethanol , are protic and comprise strong aeide protons, is solved.
  • halogenated solvents having at least one heteroatom other than halogen even if these, such as trifluoroethanol , are protic and comprise strong aeide protons.
  • Such ligands seem in principle, even under these conditions, dimerize via intermolecular interactions and thus be able to form pseudochelate complexes.
  • the present invention therefore provides a process for reacting a compound containing at least one carbon-carbon or carbon-heteroatom double bond by 1,2-addition in the presence of a catalyst comprising at least one transition metal complex having at least two ligands, each having a pnicogen atom-containing group and at least one functional group capable of forming intermolecular noncovalent bonds, the complex having dimerized ligands via intermolecular noncovalent bonds, and in the presence of a halogenated solvent additionally having at least one heteroatom other than halogen.
  • Another object of the present invention relates to processes for the preparation of chiral compounds, wherein a prochiral compound containing at least one carbon-carbon or carbon-heteroatom double bond, in the presence of a chiral catalyst, as defined above, and a halogenated solvent, the at least having a hetero atom other than halogen is converted to a chiral compound.
  • the present application relates to the use of the catalysts defined herein in the presence of halogenated solvents having at least one heteroatom other than halogen in 1,2-addition reactions and especially for hydrogenation, hydroformylation, hydrocyanation, carbonylation, hydroacylation, hydroamidation, hydroesterification, hydrosilylation, Hydroboration, aminolysis, alcoholysis, isomerization, metathesis, cyclopropanation, aldol condensation, allylic alkylation, hydroalkylation or [4 + 2] cycloaddition, preferably for hydrogenation or hydroformylation.
  • halogenated solvents having at least one heteroatom other than halogen in 1,2-addition reactions and especially for hydrogenation, hydroformylation, hydrocyanation, carbonylation, hydroacylation, hydroamidation, hydroesterification, hydrosilylation, Hydroboration, aminolysis, alcoholysis, isomerization, metathesis, cyclopropanation, aldol condensation, allylic alkylation, hydro
  • monopnicogen ligands ligands having only one pnicogen atom-containing group per molecule
  • monophosphorus ligands are capable of forming dimers via intermolecular, noncovalent bonds in which the distance between the two pnicogen atoms is within a range such as is customary for chelating ligands, when used in the 1,2-addition in the presence of halogenated solvents which have at least one heteroatom other than halogen, achieve such a high regio- and / or stereoselectivity, which is otherwise achieved only with chelating ligands
  • Ligands capable of forming dimers via intermolecular noncovalent bonds are also referred to herein as pseudochelate ligands.
  • ligands are used which have a functional group which is capable of forming intermolecular, noncovalent bonds. These bonds are preferably hydrogen bonds or ionic bonds, in particular hydrogen bonds. In a preferred embodiment, the functional groups may be tautomeric groups. The functional groups capable of forming intermolecular noncovalent bonds enable the ligands to associate, ie to form aggregates in the form of dimers.
  • Complementary compounds are ligand / ligand pairs that have complementary functional groups. Such pairs are for association, i. H. capable of forming aggregates.
  • the functional groups capable of forming intermolecular noncovalent bonds are selected from hydroxyl, primary, secondary and tertiary amino, mercapto, keto, thioketo, I-, carboxylic acid ester, carboxylic acid amide, amidine, urethane , Urea, sulfoxide, sulfoximine, sulfonamide and sulfonic acid ester groups.
  • these functional groups are so-called self-complementary functional groups, i. H. the formation of the non-covalent bonds takes place between two identical functional groups of the ligands used. If it is just a type of ligand that form the ligand / ligand pairs, so-called "homo-dimers" are called.
  • Functional groups capable of tautomerism may be present in the dimers in the form of the same or different isomers (tautomers), respectively.
  • tautomers isomers
  • At least two different ligands which have functional groups capable of forming intermolecular, noncovalent bonds are used in the method according to the invention.
  • exclusively or at least partially mutually different ligands form the ligand / ligand pairs (so-called "hetero-dimers").
  • the functional groups of the two different ligands which form the noncovalent bond den can be the same or different groups.
  • Functional groups capable of tautomerism may be present in the dimers in the form of the same or different isomers (tautomers), respectively.
  • the molar ratio of the two ligands which form the hetero-dimer is preferably in the range of 30: 1 to 1:30.
  • the distance between the pnicogen atoms of the dimerized ligands is preferably at most 5 ⁇ .
  • the distance is in a range of 2.5 to 4.5 ⁇ , more preferably 3.5 to 4.2 ⁇ .
  • Suitable methods for determining whether the ligands employed are capable of forming dimers include crystal structure analysis, nuclear magnetic resonance spectroscopy, and molecular modeling techniques. It is usually sufficient for the mood to use the ligands in non-complexed form. This is especially true for molecular modeling methods. It has also been found that both solid-state crystal structure analysis and solution-type nuclear magnetic resonance spectroscopy, as well as calculation of the gas phase structure, generally provide reliable predictions of the behavior of the ligands employed under the hydroformylation conditions. Thus, ligands which are capable of forming dimers according to the stated methods of determination usually have properties under the conditions of 1,2-addition properties which are otherwise customary only for chelating ligands.
  • stereoselectivity of the 1,2-addition in particular the hydrogenation
  • regioselectivity of the 1,2-addition in particular the n-selectivity of the hydroformylation of 1-olefins.
  • Preferred pseudochelate ligands are those in which the pnicogen atom spacing is less than 5 ⁇ in the calculated dimer structure.
  • the pnicogen atom of the ligands of the catalyst used is a phosphorus atom.
  • the ligands capable of forming intermolecular ionic interactions are selectively monodentate
  • Phosphine, phosphinite, phosphonite, phosphoramidite and phosphite compounds especially among phosphine compounds.
  • the transition metal used according to the invention is a metal of subgroup VIII of the Periodic Table of the Elements (i.e., Fe, Co, Ni, Ru, Rh, Pd, Os, Ir, Pt).
  • the transition metal is cobalt, nickel, ruthenium, rhodium, iridium palladium or platinum.
  • alkyl includes straight-chain and branched alkyl groups. These are 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 particularly preferably C 1 -C 4 -alkyl groups. Examples of alkyl groups are in particular methyl, ethyl, n-propyl, isopropyl, n-butyl, 2-butyl, sec-butyl, tert-butyl, n-pentyl, 2-pentyl, 2-methylbutyl, 3-methylbutyl,
  • 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 are preferably selected from cycloalkyl, aryl, hetaryl, halogen, NE 1 E 2 , NE 1 E 2 E 3+ , carboxylate and sulfonate, where E 1 , E 2 , E 3 are each identical or different radicals selected from hydrogen, alkyl , Cycloalkyl, acyl and aryl. A preferred perfluoroalkyl group is trifluoromethyl.
  • alkylene in the context of the present invention stands for straight-chain or branched alkanediyl groups having preferably 1 to 5 carbon atoms.
  • cycloalkyl for the purposes of the present invention comprises unsubstituted and substituted cycloalkyl groups, preferably C5-C7-cycloalkyl groups, such as cyclopentyl, cyclohexyl or cycloheptyl. In the case of a substitution, these may in general carry 1, 2, 3, 4 or 5, preferably 1, 2 or 3 and particularly 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 replaced by heteroatoms selected from the elements oxygen, nitrogen and sulfur and which may optionally be substituted, wherein in the case of a substitution, these heterocycloaliphatic groups may carry 1, 2 or 3, preferably 1 or 2, particularly preferably 1, substituent.
  • substituents are preferably selected from alkyl, aryl, COOR 0 , COO-M + and NE 1 E 2 , wherein E 1 and E 2 have the meanings given above and R 0 is alkyl, cycloalkyl, acyl, aryl or hetaryl; particularly preferred are alkyl radicals.
  • heterocycloaliphatic groups examples include pyrrolidinyl, piperidinyl, 2,2,6,6-tetramethylpiperidinyl, imidazolidinyl, pyrazolidinyl, oxazolidinyl, morpholidinyl, thiazolidinyl, isothiazolidinyl, isoxazolidinyl, piperazinyl, tetrahydrothiophenyl, tetrahydrofuranyl, tetrahydropyranyl, dioxanyl.
  • aryl in the context of the present invention comprises unsubstituted and substituted aryl groups, and is preferably phenyl, ToIyI, XyIyI, mesityl, naphthyl, fluorenyl, anthracenyl, phenanthrenyl or naphthacenyl, particularly preferably phenyl or naphthyl, said aryl groups in the case a substitution generally 1, 2, 3, 4 or 5, preferably 1, 2 or 3 and more preferably 1
  • Substituents selected from the group alkyl, alkoxy, carboxylate, trifluoromethyl, sulfonate, NE 1 E 2 , alkylene-NE 1 E 2 , nitro, cyano or halogen, can carry.
  • 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.
  • heterocycloaromatic groups may be substituted in the case of substitution in the Generally 1, 2 or 3 substituents selected from the groups alkyl, alkoxy, carboxylate, sulfonate, NE 1 E 2 , alkylene-NE 1 E 2 or halogen, carry, wherein E 1 and E 2 have the meanings given above.
  • Carboxylate and sulfonate are in the context of the present invention preferably a derivative of a carboxylic acid function or a sulfonic acid function, in particular a metal carboxylate or sulfonate, a carboxylic ester or sulfonic acid ester function or a carboxylic acid or sulfonic acid amide function. 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, pivaloyl, benzoyl or naphthoyl group.
  • the groups NE 1 E 2 , NE 4 E 5 and NE 7 E 8 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 denotes fluorine, chlorine, bromine and iodine, preferably fluorine, chlorine and bromine.
  • a halogenated solvent means a solvent which carries at least one halogen atom. for example 3, 4, 5, 6, 7, 8 or 9), these may be identical or different halogen atoms, Preferably, the halogenated solvents used according to the invention carry at least one halogen atom which is selected from fluorine and chlorine.
  • pnicogen stands for phosphorus, arsenic, antimony and bismuth, in particular phosphorus.
  • M + stands for a cation equivalent, ie for a monovalent cation or the fraction of a polyvalent cation corresponding to a positive single charge.
  • the cation M + serves only as a counter ion for the neutralization of negatively charged substituent groups.
  • pen such as the carboxylate or the sulfonate anion and can be chosen arbitrarily in principle.
  • 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- only as a counterion of positively charged substituent groups, such as. B. the ammonium groups or Iminiumgrup- pen, and can be arbitrarily selected from monovalent anions and a negative single charge portions of a polyvalent anion X n ", such as Ch, Br,
  • R' is a linear or branched aliphatic or alicyclic alkyl or C ⁇ -Cis-aryl containing 1 to 12
  • polycyclic compound in the context of the present invention broadly includes compounds containing at least two rings, regardless of how these rings are linked. These may be carbocyclic and / or heterocyclic rings. The rings may be linked via single 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 between ortho-fusing in fused ring systems, ie each ring has one edge or two atoms in common with each adjacent ring, and one peri-fused ring in which one carbon atom is more than belongs to two rings. Preferred among the fused ring systems are ortho-fused ring systems.
  • novel processes for the reaction of compounds which contain at least one carbon-carbon or carbon-heteroatom double bond are preferably hydrogenation, hydroformylation, hydrocyanation, carbonylation, hydroacylation (intramolecular and intermolecular), hydroamines - hydroxination, hydrosilation, hydrosilylation, hydroboration, aminolysis (hydroamination), alcoholysis (hydroxy-alkoxy-addition), isomerization, transfer hydrogenation, metathesis, cyclopropanation, aldol condensation, allylic alkylation or a
  • the 1,2-addition is a hydroformylation, by reaction with carbon monoxide and hydrogen, in the presence of a halogenated solvent, one of the catalysts described within the scope of this invention being used as the hydroformylation catalyst.
  • asymmetric catalysts based on the ligand pairs described in the context of the present invention using halogenated solvents which have at least one heteroatom other than halogen are particularly advantageously suitable for use in asymmetric synthesis.
  • high stereoselectivities can be achieved as otherwise can only be achieved with chelating ligands.
  • ligands in the solvents of the present invention are capable of forming dimers via intermolecular ionic interactions.
  • the catalysts of the invention in chlorinated or fluorinated solvents having at least one heteroatom other than halogen for asymmetric synthesis, it is generally advantageous to have the ligands of formula I in a molar ratio of at least 2: 1, based on the transition metal, especially on the metal of VIII. Subgroup to use. This effect, without being tied to any theory, is due to the fact that the ligands are capable of forming dimers through intermolecular ionic interactions, where the distance between the two phosphorus atoms is within a range common to chelating ligands.
  • Another object of the invention is a process for the preparation of chiral compounds by reacting a prochiral compound containing at least one carbon-carbon or carbon-heteroatom double bond, with a substrate in the presence of a chiral catalyst, as described in the context of the present invention, and in the presence of a chlorinated or fluorinated solvent used according to the invention. 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 to one atom of the double bond, hydrogen and to the other a carbon atom-containing group is bound. Double bond isomerizations during addition are allowed.
  • 1-hydro-2-carboo addition in unsymmetrical substrates is not intended to refer to a preferred addition of the carbon fragment to the C2 atom, since the selectivity with respect to the orientation of the addition is generally dependent on the agent to be added and the used catalyst is dependent.
  • “1-hydro-2-carbo-” is in this sense synonymous with "1-carbo-2-hydro-”.
  • reaction conditions of the processes according to the invention for preparing chiral compounds generally correspond to those of corresponding asymmetric processes.
  • Suitable reactors and reaction conditions The expert can thus refer to the relevant literature on the respective process and adapt routinely.
  • 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. As described in Ullmann's Encyclopedia of Industrial Chemistry, Vol.
  • the processes according to the invention are carried out in a suitable chlorinated or fluorinated solvent which is inert under the respective reaction conditions and which has at least one heteroatom other than halogen.
  • a suitable chlorinated or fluorinated solvent which is inert under the respective reaction conditions and which has at least one heteroatom other than halogen.
  • all organic compounds which have at least one halogen atom and a heteroatom other than halogen and are present in the liquid state of aggregation under the given reaction conditions are suitable for this purpose.
  • the halogen atoms are preferably selected from chlorine and fluorine atoms.
  • the heteroatom other than halogen is selected from nitrogen and oxygen. In particular, it is oxygen.
  • Suitable classes of solvents are halogenated, and especially chlorinated and / or fluorinated, alcohols, amines, ketones, esters and amides. These are distinguished, in particular, by the polarity of the functional group comprising heteroatom other than halogen.
  • the solvent used according to the invention is preferably selected from fluorinated solvents which have at least one heteroatom other than halogen.
  • Particularly suitable solvents are polar fluorinated compounds such as fluorinated alcohols, fluorinated amines, fluorinated ketones or fluorinated esters.
  • fluorinated, polar, protic compounds and, in particular, fluorinated alcohols, such as, for example, 2-fluoroethanol, trifluoroethanol, hexafluoroisopro panol, are particularly suitable as solvents in the process according to the invention.
  • the solvent used according to the invention is selected from solvents which are sparingly comprise at least one perfluorinated methyl and / or methylene unit, or mixtures of such solvents.
  • solvents are alcohols, such as 2-fluoroethanol, 2,2-difluoroethanol, 2,2,2-trifluoroethanol,
  • Ethers such as bis (2,2,2-trifluoroethyl) ether or amines, such as 2,2,2-trifluoroethylamine or perfluorotriethylamine.
  • Preferred solvents are fluorinated alcohols such as 2-fluoroethanol, 2,2-difluoroethanol, 2,2,2-trifluoroethanol, 2,2,3,3,3-pentafluoro-n-propanol, 1,1,1,3,3 , 3-hexafluoro-2-propanol (hexafluoroisopropanol), 1-fluoro-2-propanol, 1,1-difluoro-2-propanol, 1,1,1-trifluoro-2-propanol, 1,3-difluoro-2- propanol, 1,1,3,3-tetrafluoro-2-propanol, perfluoro-1-butanol, 1,1,3,3,3,3-hexafluoro-2-methyl-2-propanol, 2,2,3, 3,4,4-hexafluoro-1, 5-pentanediol or ⁇ -trifluoromethylbenzyl alcohol. Also suitable are mixtures of two or more than two of the aforementioned fluor
  • the solvent used according to the invention is particularly preferably selected from fluorinated C 1 -C 6 -alcohols and in particular from 2,2,2-trifluoroethanol, 2,2-difluoroethanol, 2-fluoroethanol, hexafluoroisopropanol and mixtures thereof.
  • Suitable inert solvents for such mixtures are, for example, aromatics, such as toluene and xylene, hydrocarbons or mixtures of hydrocarbons, halogenated, in particular chlorinated hydrocarbons, such as dichloromethane, chloroform or 1, 2-dichloroethane, esters of aliphatic carboxylic acids with alkanols, such as ethyl acetate or Texanol ®, ethers such as tert-butyl methyl ether, 1, 4-dioxane and tetrahydrofuran, dimethylformamide, alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, or ketones such as acetone and methyl ethyl ketone, etc As a, aromatics, such as toluene and xylene, hydrocarbons or mixtures of hydrocarbons, halogenated,
  • the fluorinated solvent used according to the invention represents the major amount of the solvent mixture.
  • the solvent mixture preferably comprises at least 60% by volume of one of the solvents used according to the invention, more preferably at least 80% by volume and in particular at least 99 ° C. -%.
  • Suitable prochiral compounds having at least one carbon-carbon or carbon-heteroatom double bond for use in the process according to the invention are, in principle, all prochiral compounds which have one or more unsaturated carbon-carbon or carbon-heteroatom double bonds contain.
  • prochiral olefins hydrogenation, hydroformylation, intermolecular hydroacylation, hydrocyanation, hydrosilylation, carbonylation, hydroamidation, hydroesterification, aminolysis, alcoholysis, cyclopropanation, hydroboration, Diels-Alder reaction, metathesis
  • unsubstituted and substituted aldehydes intramolecular hydroacylation, aldol condensation, allylic alkylation
  • ketones hydroogenation, hydrosilylation, aldol condensation, transfer hydrogenation, allylic alkylation
  • imines hydrogenation, hydrosilylation, transfer hydrogenation, Mannich reaction
  • Suitable prochiral olefins are generally compounds of the formula
  • R A and R B and / or R c and R D are radicals of different definitions.
  • 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 substituents, or two or more of the radicals R A , R B , R c and R D together with the carbon-carbon double bond to which they are attached, for a mono - or polycyclic compound.
  • Suitable prochiral olefins are olefins having at least 3, in particular 4 carbon atoms and terminal or internal double bonds which are straight-chain, branched or of cyclic 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 non-ionic mixtures, branched te, 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- fluorobiphenyl,
  • Suitable olefins are furthermore o-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, methyl 4-pentenoate, oleic acid methyl ester, methyl acrylate, methacrylic acid methyl esters, unsaturated nitriles, such as 3-pentenenitrile, 4-pentenenitrile, acrylonitrile, vinyl ethers, such as vinyl methyl ether, vinyl ethyl ether, vinyl propyl ether, etc., vinyl chloride, allyl chloride, C 3 -C 20 -alkenols, C 3 -C 20 -alkenediols and C2o-alkadienols such as allyl alcohol, hex-1-en-4-ol,
  • Suitable substrates are also diioder 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 which are important as synthesis building blocks are, for example, P-isobutylstyrene, 2-vinyl-6-methoxynaphthalene, (3-ethenylphenyl) phenyl ketone, (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. For example, 2,3-dihydro-1, 4-oxazines
  • the catalysts used according to the invention are prepared in situ in the reactor used for the reaction. If desired, however, the catalysts used according to the invention can also be prepared separately and isolated by customary processes. For in situ preparation of the catalysts 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.
  • suitable rhodium complexes such as Rh 4 (CO) 12, rhodium bis-acylacetylacetonate, acetylacetonato-bis-ethyl rhodium (1), etc.
  • ruthenium salts or compounds are, for example, ruthenium (III) chloride, ruthenium (IV), ruthenium (VI) or ruthenium (VIII) oxide, alkali metal salts of ruthenium oxygen acids such as K 2 RUO 4 or KRuO 4 or complex compounds, such as.
  • 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. For example, triphenylphosphine complexes or triethylphosphine complexes, halides, eg.
  • 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 1: 2 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 carbon-carbon or carbon-heteroatom double bond with hydrogen in the presence of a halogenated solvent and a chiral catalyst, as described in the present invention, to corresponding chiral Compounds with a single bond instead of the double 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 contain at least one transition metal, especially a 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 is used. tor 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 stated 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.
  • Open-chain and cyclic ethers such as diethyl ether, methyl tert-butyl ether, tetrahydrofuran or 1,4-dioxane and alcohols, in particular Ci, are suitable as additional solvents in solvent mixtures according to the invention with halogenated solvents which have at least one heteroatom other than halogen C3 alkanols, such as methanol, ethanol, n-propanol or isopropanol, or combinations thereof.
  • halogenated solvents which have at least one heteroatom other than halogen C3 alkanols, such as methanol, ethanol, n-propanol or isopropanol, or combinations thereof.
  • the hydrogen required for the hydrogenation can be used both in pure form and in the form of hydrogen-containing gas mixtures.
  • the latter must not contain harmful amounts of catalyst poisons, such as sulfur compounds or CO.
  • suitable hydrogen-containing gas mixtures are those from the reforming process.
  • 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 used according to the invention. This reaction solution is then preferably mixed with the hydrogenation catalysed before 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, Rhackrau- and industrial 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 of these are conventional stirred tanks, which are preferably equipped with a Siedekühlung, suitable mixers, introduction devices, optionally heat exchanger elements and inerting.
  • 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 generally 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 techniques for removing solids from solutions, such as centrifugation, 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.
  • 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 transfer hydrogenation.
  • a hydrogen donor is used instead of molecular hydrogen.
  • the hydrogen donor also serves as an additional solvent for the reaction to be catalyzed.
  • Typical hydrogen donors are, for example, alkanols (for example isopropanol) or formic acid, the latter often in combination with amines, especially triethylamine.
  • the hydrogen donor used for transfer hydrogenation by the process according to the invention preferably contains at least one formic acid component which is selected from formic acid, salts of formic acid (formates) and adducts of salts of formic acid with formic acid.
  • the hydrogen donor used is formic acid in combination with triethylamine.
  • the hydrogen donor used is preferably a mixture of formic acid and triethylamine in a molar ratio of from 0.5: 1 to 5: 1, more preferably from 1: 1 to 3: 1.
  • Particularly preferred is the use of formic acid to triethanolamine in a molar ratio of 5: 2, which corresponds to the azeotrope of these two liquids.
  • At least one salt of formic acid (formate) is used as the hydrogen donor.
  • Preferred salts are the alkali metal salts, in particular the sodium and potassium salts, the ammonium salts and the alkaline earth metal salts, in particular the calcium and magnesium salts.
  • salts of formic acid in addition to the hydrogenation in solution, hydrogenation in suspension is also possible.
  • the liquid medium used then contains at least one of the previously described halogenated solvents which have at least one heteroatom other than halogen.
  • the hydrogen donor used is at least one adduct of salts of formic acid with formic acid.
  • formic acid formates which are usually present in solid form, and their preparation are known, for. B. from Gmelin's Handbook of Inorganic Chemistry, 8th edition, No. 21, pp. 816-819, Verlag Chemie GmbH, Berlin 1928 and No. 22, pp. 919-921, Verlag Chemie GmbH, Berlin 1937. These are z , B. by dissolving formic acid salts, such as potassium formate or sodium formate, in heated formic acid and subsequent cooling.
  • adducts of formic acid are used as the hydrogen donor, in addition to the hydrogenation in solution, hydrogenation in suspension is also possible.
  • the hydrogenation takes place independently of the hydrogen donor used in the presence of an additional solvent.
  • the additional solvent is preferably selected from water, C 1 -C 8 -alkanols, aliphatic carboxylic acid alkyl esters, aliphatic carboxylic acid amides, dialkylsulfoxides, haloalkanes, dialkyl ethers, cyclic ethers, aromatics and mixtures thereof.
  • Suitable d-Cs alkanols are, for.
  • Suitable aliphatic carboxylic acid alkyl esters are, for. Methyl acetate, ethyl acetate, n-propyl acetate, methyl propionate, etc.
  • Suitable N, N-dialkylated aliphatic carboxylic acid amides are e.g. Dimethylformamide, dimethylacetamide, dimethylpropionamide, etc.
  • a suitable dialkylsulfoxide is dimethylsulfoxide.
  • Suitable haloalkanes are, for. Dichloromethane, 1,2-dichloroethane, trichloromethane, carbon tetrachloride, etc.
  • Suitable dialkyl ethers are diethyl ether, di-n-propyl ether, etc.
  • Suitable cyclic ethers are tetrahydrofuran, dioxane, etc.
  • Suitable aromatics are benzene, Toluene and the isomeric xylenes.
  • the transfer hydrogenation according to the invention is generally carried out at a temperature in the range of approximately - 50 to 150 0 C, more preferably - 20 to 100 0 C is performed.
  • the reaction can be carried out at ambient pressure and at reduced and elevated pressures, eg. B. in a range between 0.1 and 5 bar, take place.
  • the reaction time is generally in a range of about 1 minute to 48 hours, such as. In a range of 10 minutes to 24 hours.
  • a typical reaction time is about 1 to 16 hours.
  • 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 chlorinated or fluorinated solvents or of a solvent mixture.
  • the molar ratio of pseudochelate ligand to transition metal, in particular to metal of VIII. Subgroup is generally in a range of about 1: 1 to 1000: 1, preferably 2: 1 to 500: 1.
  • hydroformylation catalyst is prepared in situ, at least one ligand pair usable 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 for the reaction brings.
  • 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 of 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 can be separated off from the effluent 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 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 also generally have a high regioselectivity.
  • the catalysts generally have a high stability under the hydroformylation conditions, so that they are usually achieved longer catalyst life than with known from the prior art catalysts based on conventional chelating ligands.
  • the catalysts 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 transition metal, especially a metal of the 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 used according to the invention. Hydrocyanation process 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 transition metal, especially a metal of the VIII subgroup, preferably nickel, cobalt, iron, ruthenium, rhodium and palladium, in particular palladium.
  • a transition metal especially a metal of the VIII subgroup, 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.
  • chiral ketones are obtained by reacting a prochiral olefin with an acyl halide in the presence of a chiral catalyst, as described in the present application. Suitable methods of hydroacylation are described in J. March, Advanced Organic Chemistry, 4th Ed., P. 81 1, which is incorporated herein by reference.
  • Another important 1,2-addition is hydroamidation.
  • a prochiral compound containing at least one carbon-carbon or carbon-heteroatom double bond with carbon monoxide and ammonia, a primary or a secondary amine in the presence of a chiral catalyst, as described in the present application, to chiral Amies.
  • Another important 1,2-addition is hydroesterification.
  • chiral esters are obtained by reacting a prochiral compound containing at least one carbon-carbon or carbon-heteroatom double bond with carbon monoxide and an alcohol in the presence of a chiral catalyst as described in this application.
  • hydroboration Another important 1,2-addition is hydroboration.
  • a prochiral compound containing at least one carbon-carbon or carbon-heteroatom double bond with borane or a borane source in the presence of a chiral catalyst, as described in the present application, to chiral trialkylboranes, which are primary alcohols (For example, with NaOH / H2 ⁇ 2) 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 carbon-carbon or carbon-heteroatom double bond with a silane in the presence of a chiral catalyst as described in this application, 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, for example, platinum in finely divided form (“platinum black”), platinum chloride and platinum complexes such as hexachloroplatinic acid or divinyldisiloxane-platinum complexes, eg tetramethyldivinyldisiloxane-platinum complexes
  • Suitable rhodium catalysts include (RhCl (P (C6H 5 3) 3) and RhCb. Further suitable catalysts are RuCb and IrCb. Suitable catalysts furthermore include Lewis acids such as AICb or TiCU and also peroxides.
  • Suitable silanes are z. Halogenated silanes such as trichlorosilane, methyldichlorosilane, dimethylchlorosilane and trimethylsiloxydichlorosilane; Alkoxysilanes, such as trimethoxysilane, triethoxysilane, methyldimethoxysilane, phenyldimethoxysilane,
  • the reaction temperature in the silylation is preferably in a range from 0 to 140 ° C., particularly preferably 40 to 120 ° C.
  • the reaction is usually Normal pressure carried out, 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 in the presence of one of the chlorinated or fluorinated solvents used according to the invention or a mixture thereof.
  • solvent mixtures with toluene, tetrahydrofuran and chloroform are preferred.
  • Another important 1,2-addition is aminolysis (hydroamination).
  • a prochiral compound containing at least one carbon-carbon or carbon-heteroatom double bond with ammonia, a primary or a secondary amine in the presence of a chiral catalyst, as described in the present application, to chiral primary , secondary or tertiary amines.
  • Suitable methods for hydroamination are in
  • alcoholysis hydro-alkoxy-addition
  • a prochiral compound containing at least one carbon-carbon double bond with alcohols in the presence of a chiral catalyst, as described in the present application, to 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 isomerization.
  • a prochiral compound containing at least one ethylenically unsaturated double bond in the presence of a chiral catalyst, as described in the present application, to chiral compounds.
  • Another important reaction is metathesis.
  • a prochiral compound containing at least one carbon-carbon double bond with another olefin in the presence of a chiral catalyst, as described in the present application, to chiral hydrocarbons.
  • Another important reaction is the aldol condensation.
  • a prochiral ketone or aldehyde with a silyl enol ether in the presence of a chiral catalyst, as described in the present application, to chiral aldols.
  • 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 in the present application, to obtain chiral hydrocarbons.
  • 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,
  • 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 is possible by customary methods 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.
  • ligand / ligand pairs used according to the invention can be represented schematically as follows:
  • a and B are radicals with mutually complementary functional groups, between which a non-covalent interaction exists
  • R 1 and R 2 are as defined below.
  • the phosphorus atom-containing group is preferably selected from groups of the general formula wherein
  • R 1 and R 2 independently of one another represent alkyl, alkoxy, cycloalkyl, cycloalkoxy, heterocycloalkyl, heterocycloalkoxy, aryl, aryloxy, hetaryl or hetaryloxy or
  • R 1 and R 2 together with the phosphorus atom to which they are attached, for a
  • 5- to 8-membered heterocycle which is optionally additionally fi-,, or threefold fused with cycloalkyl, heterocycloalkyl, aryl or hetaryl, wherein the heterocycle and, if present, the fused groups independently of one another, two, may carry three or four substituents which are selected from alkyl, cycloalkyl, heterocycloalkyl, aryl, hetaryl, COOR C , COO-M + , SO 3 R C , SO 3 -M + , PO 3 (R c ) (R d ) , (PO 3 ) 2 - (M + ) 2 , NE 4 E 5 , (NE 4 E 5 E 6 ) + X-, OR e , SR e , (CHR f CH 2 O) y R e , (CH 2 NE 4 ) y R e , (CH 2 CH 2 NE 4 ) y R e , halogen, nitro
  • R c and R d are each the same or different radicals selected from alkyl, cycloalkyl, aryl or hetaryl,
  • R e , E 4 , E 5 , E 6 each represent identical or different radicals selected from hydrogen, alkyl, cycloalkyl, aryl or hetaryl,
  • R f is hydrogen, methyl or ethyl
  • M + is a cation equivalent
  • R 1 and R 2 are not bridged together. Then R 1 and R 2 are preferably independently selected from alkyl, cycloalkyl, aryl and hetaryl, as defined above.
  • At least one of the radicals R 1 and R 2 and more preferably R 1 and R 2 are both aryl, in particular both are phenyl.
  • At least one of the radicals R 1 and R 2 is preferably a pyrrole group bonded to the phosphorus atom via the pyrrole nitrogen atom.
  • R 1 and R 2 are both attached to the phosphorus via the pyrrole nitrogen atom.
  • atom-bound pyrrole group, where R 1 and R 2 may represent the same or different pyrrole groups.
  • 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 can be covalently linked to a phosphorus atom.
  • 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 a substitution in the Generally 1, 2 or 3, preferably 1 or 2, particularly preferably a substituent selected from the groups alkyl, alkoxy, acyl, carboxylate, sulfonate, NE 4 E 5 , alkylene- NE 4 E 5 or halogen, can carry.
  • Preferred pyrrole groups are 3- (C 1 -C 4 -alkyl) indolyl groups, such as the 3-methylindolyl group (skatolyl group).
  • R 1 and R 2 are bridged together.
  • the phosphorus atom-containing group is preferably a group of the formula
  • r and s are independently 0 or 1
  • D together with the phosphorus atom and optionally with the oxygen atom (s) to which it is attached represent a 5- to 8-membered heterocycle which is optionally mono-, di- or trisubstituted by cycloalkyl, heterocycloalkyl, aryl and / or hetaryl is fused, wherein the fused groups independently of one another each one, two, three or four substituents selected from alkyl, alkoxy, halogen, sulfonate, NE 4 E 5 , alkylene-NE 4 E 5 , nitro, cyano and carboxylate , and / or D may have one, two or three substituents which are selected from alkyl, alkoxy, optionally substituted cycloalkyl and optionally substituted aryl, and / or D may be interrupted by 1, 2 or 3 optionally substituted heteroatoms.
  • the radical D preferably represents a C 2 -C 6 -alkylene bridge fused once or twice with aryl and / or having one substituent selected from alkyl, optionally substituted cycloalkyl and optionally substituted aryl can and / or which may be interrupted by an optionally substituted heteroatom.
  • the fused aryls of the radicals D 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 substituents previously mentioned in the fused benzene rings.
  • alkyl is preferably C 1 -C 4 -alkyl and in particular methyl, isopropyl and tert-butyl.
  • Alkoxy is preferably d-C4-alkoxy and especially methoxy.
  • Alkoxycarbonyl is preferably C 1 -C 4 -alkoxycarbonyl.
  • C 2 -C 6 -alkylene bridge of the radical D 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 D When the C 2 -C 6 -alkylene bridge of the radical D 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 D is a C 3 -C 6 -alkylene bridge, which is fused and / or substituted as described above and / or interrupted by optionally substituted heteroatoms.
  • the radical D is a Cs-C ⁇ -alkylene bridge fused once or twice with phenyl and / or naphthyl, wherein the phenyl or naphthyl groups can carry 1, 2 or 3 of the abovementioned substituents.
  • the radical D together with the phosphorus atom and the oxygen atom (s) to which it is attached is a 5- to 8-membered heterocycle, wherein D is a radical selected from the radicals Formulas 11.1 to II.5,
  • T is O, S or NR 1 , where
  • R 1 is alkyl, cycloalkyl or aryl
  • T is a C 1 -C 5 -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 ,
  • R 1 , R 11 , R 111 , R IV , R V , R V ", R VM , R VIII , R IX , R X , R XI and R x " are independently hydrogen, alkyl, cycloalkyl, aryl, alkoxy , Halogen, sulfonate, NE 4 E 5 , alkylene-NE 4 E 5 , trifluoromethyl, nitro, alkoxycarbonyl or cyano.
  • At least one of the ligands used according to the invention has a functional group capable of tautomerism and of forming intermolecular noncovalent bonds. This is preferably selected from groups of
  • Y is O, S or NR 4 , wherein R 4 is hydrogen, alkyl, cycloalkyl, heterocycloalkyl, aryl or hetaryl.
  • keto-enol tautomerism especially the carboxylic acid amide-imidocarboxylic acid tautomerism and the amidine tautomerism:
  • the ligands used according to the invention preferably have at least one structural element of the general formulas I.a or I.b.
  • R 1 and R 2 independently of one another are alkyl, alkoxy, cycloalkyl, cycloalkoxy, heterocycloalkyl, heterocycloalkoxy, aryl, aryloxy, hetaryl or hetaryloxy,
  • R 3 is hydrogen or has one of the meanings given for R 1 and R 2 ,
  • X represents a divalent bridging group having 1 to 5 bridge atoms between the flanking bonds
  • Y is O, S or NR 4 , where R 4 is hydrogen, alkyl, cycloalkyl, heterocycloalkyl, aryl or hetaryl,
  • the divalent bridging group X has 1 to 4, more preferably 1 to 3 bridge atoms between the flanking bonds.
  • X is a Ci-Cs-alkylene bridge, which may have one or two double bonds. Furthermore, preferably at least two of the bridging atoms of the bridge X together with the structural element of the formula I.a or I.b to which they are attached may stand for a mono- or polycyclic compound.
  • Such ring systems in which one of the tautomers can form an aromatic ring system are particularly stable.
  • the rings mentioned may be unsubstituted or have one, two, three, four or five of the abovementioned substituents. These are preferably selected from C 1 -C 4 -alkyl, particularly preferably methyl, ethyl, isopropyl or tert-butyl, C 1 -C 4 -alkoxy, especially methoxy, ethoxy, isopropyloxy or tert-butyloxy, and also aryl, preferably phenyl.
  • said rings have at least one double bond, wherein the radicals bound to this double bond stands for a fused ring system having 1, 2 or 3 further rings. These are preferably benzene or naphthalene rings.
  • Anellated benzene rings are preferably unsubstituted or have 1, 2 or 3 substituents selected from alkyl, alkoxy, carboxylate, sulfonate, halogen, NE 1 E 2 , trifluoromethyl, nitro, alkoxycarbonyl, acyl and cyano.
  • Anellated naphthalene rings are preferably unsubstituted or have in the non-fused and / or in the fused ring each 1, 2 or 3 of the substituents previously mentioned in the fused benzene rings.
  • the ligands used according to the invention are preferably selected from compounds of the general formulas 1.1 to 1.3
  • one of the radicals R 5 to R 9 is a group of the formula - W-PR 1 R 2 , wherein
  • W is a single bond, a heteroatom, a heteroatom-containing group or a divalent bridging group having 1 to 4 bridging atoms between the flanking bonds, R 1 and R 2 are as defined above,
  • radicals R 5 to R 9 which do not stand for --W - PR 1 R 2 , independently of one another represent hydrogen, alkyl, cycloalkyl, heterocycloalkyl, aryl, hetaryl, WCOOR 0 ,
  • W represents a single bond, a heteroatom, a heteroatom-containing group or a divalent bridging group having 1 to 20 bridging atoms
  • R 0 and RP are each the same or different radicals selected from alkyl, cycloalkyl, acyl, aryl and hetaryl,
  • R q , E 1 , E 2 , E 3 are each the same or different radicals selected from hydrogen, alkyl, cycloalkyl, acyl or aryl,
  • R r is hydrogen, methyl or ethyl
  • M + is a cation equivalent
  • x is an integer from 1 to 240
  • R a and R b are hydrogen, alkyl, acyl, cycloalkyl, heterocycloalkyl, aryl or hetaryl.
  • ligands of the general formulas 1.1 to 1.3 are used, wherein R 5 and R 6 and / or R 7 and R 8 represent a fused ring system with 1, 2 or 3 further rings.
  • R 5 and R 6 and / or R 7 and R 8 represent a fused-ring system, it is 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, SO 3 H, sulfonate, NE 1 E 2 , alkylene-NE 1 E 2 , Trifluoromethyl, nitro, COOR 0 , alkoxycarbonyl, acyl and cyano.
  • Anellated naphthalene rings are preferably unsubstituted or have in the non-fused ring and / or in the fused ring each 1, 2 or 3, in particular 1 or 2 of the substituents previously mentioned in the fused benzene rings.
  • R 7 and R 8 are a fused ring system.
  • R 6 and R 9 are preferably both hydrogen or one of these radicals is hydrogen and the other is a substituent selected from C 1 -C 8 -alkyl, preferably C 1 -C 4 -alkyl, especially methyl, ethyl, isopropyl or part , Butyl.
  • the radical R 5 is preferably a group of the formula -W-PR 1 R 2 , as defined above.
  • the radicals R 1 and R 2 are preferably, independently of one another, C 1 -C 8 -alkyl, such as methyl, ethyl, isopropyl and tert. Butyl, Cs-C ⁇ -cycloalkyl, such as cyclohexyl, or aryl, such as phenyl.
  • the radicals R 1 and R 2 are both aryl, in particular both are phenyl.
  • the radicals R 6 , R 7 , R 8 and R 9 are preferably independently selected from hydrogen, C 1 -C 4 -alkyl, C 1 -C 4 -alkoxy, carboxylate, sulfonate, NE 1 E 2 , Halogen, trifluoromethyl, nitro, alkoxycarbonyl, acyl and cyano.
  • R 6 , R 7 , R 8 and R 9 are hydrogen.
  • the radicals R 7 and R 8 are preferably together with the ring carbon atoms to which they are bonded, for a fused ring system, as defined above, in particular for a benzene ring. Then the radicals R 6 and, if present, R 9 are preferably hydrogen.
  • the radical R a is preferably hydrogen
  • Ci-Cs-alkyl such as methyl, ethyl, isopropyl and tert.
  • R a is particularly preferably acyl, in particular alkanoyl, such as acetyl, propanoyl, butanoyl, isobutanoyl and pivaloyl.
  • the radical R b is preferably hydrogen,
  • C 1 -C 6 -alkyl such as methyl, ethyl, isopropyl and tert-butyl
  • C 3 -C 8 -cycloalkyl such as cyclohexyl
  • C 6 -C 10 -aryl such as phenyl, or hetaryl.
  • the ligands used according to the invention are preferably selected from compounds of the general formulas I.i to I.iii
  • a 0 or 1
  • R 1 and R 2 are as defined above,
  • R 6 to R 9 independently of one another represent hydrogen, C 1 -C 4 -alkyl, C 1 -C 4 -alkoxy, acyl, aryl, heteroaryl, halogen, C 1 -C 4 -alkoxycarbonyl or carboxylate,
  • R a and R b are hydrogen, alkyl, acyl, cycloalkyl, aryl or hetaryl.
  • the radicals R 1 and R 2 independently of one another are C 1 -C 6 -alkyl, such as methyl, ethyl, isopropyl and tert-butyl, C 3 -C 8 -cycloalkyl, such as cyclohexyl, or aryl, such as phenyl.
  • the radicals R 1 and R 2 are both aryl, in particular both are phenyl.
  • the radicals 4 -alkyl in the compounds li to l.iii R 6, R 7, R 8 and R 9 are independently selected from hydrogen, Ci-C alkyl, -C 4 -alkoxy, carboxylate, sulfonate, NE 1 E 2 , Halogen, trifluoromethyl, nitro, alkoxycarbonyl, acyl and cyano.
  • R 6 , R 7 , R 8 and R 9 are hydrogen.
  • the radicals R 7 and R 8 are preferably together with the ring carbon atoms to which they are attached are, for a fused ring system as defined above, in particular for a benzene ring. Then R 6 and, if present, R 9 are preferably hydrogen.
  • the radical R a is preferably hydrogen, C 1 -C 6 -alkyl, such as methyl, ethyl, isopropyl and tert-butyl, C 3 -C 8 -cycloalkyl, such as cyclohexyl, or C 3 -C 4 -cycloalkyl.
  • Cio-aryl such as phenyl.
  • R a is particularly preferably acyl, in particular alkanoyl, such as acetyl, propanoyl, butanoyl, isobutanoyl and pivaloyl.
  • the radical R b is preferably hydrogen, C 1 -C 6 -alkyl, such as methyl, ethyl, isopropyl and tert-butyl, C 5 -C 8 -cycloalkyl, such as cyclohexyl, C 6 -C 10 -Aryl, such as phenyl, or hetaryl.
  • ligands of the formulas 1.1 to 1.3 are suitable both as sole ligands, assuming homo-dimer formation, as well as in ligand combinations assuming at least partial hetero-dimer formation.
  • all ligands may be selected from ligands of formulas 1.1 to 1.3 and especially among ligands of formulas I.i to I.iii, more particularly (1) to (12).
  • one of the radicals R 10 to R 14 is a group of the formula -W-PR 1 R 2 , wherein
  • W is a single bond, a heteroatom, a heteroatom-containing group or a divalent bridging group having 1 to 4 bridge atoms between the flanking bonds
  • R 1 and R 2 independently of one another are alkyl, alkoxy, cycloalkyl, cycloalkoxy, heterocycloalkyl, heterocycloalkoxy, aryl, aryloxy, hetaryl or hetaryloxy,
  • the radicals R 10 to R 14 which are not -W-PR 1 R 2 , independently of one another represent hydrogen, alkyl, cycloalkyl, heterocycloalkyl, aryl, hetaryl, WCOOR 5 , WCOO-M + , W (SO 3 ) R 5 , W (SOs) -M + , WPO 3 (R 5 XR 1 ), W (PO 3 ) 2 - (M + ) 2 , WNE 7 E 8 , W (NE 7 E 8 E 9 ) + X-, WOR U , WSR U , (CHR V CH 2 O) Z R U , (CH 2 NE 7 ) Z R U , (CH 2 CH 2 NE 7 ) Z R U , halogen, nitro, acyl or cyano,
  • W represents a single bond, a heteroatom, a heteroatom-containing group or a divalent bridging group having 1 to 20 bridging atoms
  • R s and R 1 are each the same or different radicals selected from alkyl, cycloalkyl, acyl or aryl,
  • R u , E 7 , E 8 , E 9 are each identical or different radicals selected from hydrogen, alkyl, cycloalkyl, acyl or aryl,
  • R v is hydrogen, methyl or ethyl
  • M + is a cation equivalent
  • z is an integer from 1 to 240
  • the radical R 10 is preferably a group of the formula -W-PR 1 R 2 , as defined above.
  • the radicals R 1 and R 2 are preferably, independently of one another, C 1 -C 6 -alkyl, such as methyl, ethyl, isopropyl and tert-butyl, C 3 -C 8 -cycloalkyl, such as cyclohexyl, or aryl like phenyl.
  • the radicals R 1 and R 2 are both aryl, in particular both are phenyl.
  • the radicals R 11 , R 12 , R 13 and R 14 are preferably selected independently from among hydrogen, C 1 -C 4 -alkyl, C 1 -C 4 -alkoxy, carboxylate, sulfonate, NE 1 E 2 , halogen, Trifluoromethyl, nitro, alkoxycarbonyl, acyl and cyano.
  • R 6 , R 7 , R 8 and R 9 are hydrogen.
  • the radicals R 12 and R 13 are preferably together with the ring carbon atoms to which they are bonded, for a fused ring system, as defined above, in particular for a benzene ring.
  • the radicals R 11 and R 14 are preferably hydrogen.
  • a preferred compound of formula II is 2- (diphenylphosphino) pyridine.
  • the catalysts used in 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, they may also contain at least one further ligand, which is preferably selected from halides, amines, carboxylates, acetylacetonate, aryl or alkylsulfonates, 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.
  • Another object of the present invention is the use of a catalyst, as described above, in the presence of a chlorinated or fluorinated solvent having at least one heteroatom other than halogen for hydrogenation, hydroformylation, hydrocyanation, carbonylation, hydroacylation, hydroamidation, hydroesterification, hydrosilylation, hydroboration , Aminolysis, alcoholysis, isomerization, metathesis, cyclopropanation, aldol condensation, allylic alkylation, hydroalkylation or [4 + 2] cycloaddition, in particular for hydrogenation or hydroformylation.
  • a chlorinated or fluorinated solvent having at least one heteroatom other than halogen for hydrogenation, hydroformylation, hydrocyanation, carbonylation, hydroacylation, hydroamidation, hydroesterification, hydrosilylation, hydroboration , Aminolysis, alcoholysis, isomerization, metathesis, cyclopropanation, aldol condensation, allylic alkylation,
  • a process for producing phosphinopyridinones and / or tautomers thereof comprises reacting a pyridine compound bearing a protected hydroxyl group and a nucleophilic displaceable group with a solution of a phosphine and an alkali metal in liquid ammonia to obtain at least one pyridine compound having a protected hydroxyl group and carries a phosphino group, followed by deprotection of the hydroxy function.
  • This method is the subject of DE 10 2004 014 474.
  • chlorinated Phosphepinen z.
  • the chlorinated Phosphepins I) is carried out starting from enantiomerically pure diols, eg. B. BINOL (2,2'-dihydroxy-1, 1'-binaphthyl), according to literature methods: a) D. Xiao, Z. Zhang, X. Zhang, Org. Lett, 1999, 1, 1679-1681. b) K. Junge, G. Oehme, A. Monsees, T. Riermeier, U.umblerdissen, M. Beller, Tetrahedron Lett. 2002, 43, 4977-4980. c. K. Junge, B. Hagehmann, S. Enthaler, A. Spannenberg, M. Michalik, G. Oehme, A. Monsees, T. Riermeier, M. Beller, M. Tetrahedron: Asymmetry 2004, 15, 2621 -2631.
  • the compounds of formulas 1.1 to 1.3, as defined above, are also suitable, regardless of their ability to form intermolecular, noncovalent bonds, as ligands in catalysts for reacting compounds containing at least one carbon-carbon or carbon-heteroatom double bond by 1,2-addition in the presence of a chlorinated and / or fluorinated solvent having at least one heteroatom other than halogen.
  • a chlorinated and / or fluorinated solvent having at least one heteroatom other than halogen.
  • suitable and preferred chlorinated and fluorinated solvent is fully referred to the previous embodiments.
  • ligands of the formulas li to l.iii as defined above.
  • Particularly suitable are the ligands of the formulas (1) to (12), as defined above.
  • they are suitable as ligands in hydrogenation catalysts and hydroformylation catalysts, the hydrogenation or the hydroformylation taking place in the presence of a chlorinated and / or fluorinated solvent which has at least one heteroatom other than halogen.
  • the invention therefore also provides a catalyst system comprising at least one chlorinated and / or fluorinated solvent which has at least one heteroatom other than halogen and at least one compound of the general formulas 1.1 to 1.3
  • Another object of the invention is the use of such a catalyst system for hydrogenation, hydroformylation, hydrocyanation, carbonylation, hydroacylation, hydroamidation, hydroesterification, hydrosilylation, hydroboration, aminolysis, alcoholysis, isomerization, metathesis, cyclopropanation, aldol condensation, allylic alkylation, hydroalkylation or [4 + 2] cycloaddition.
  • Specific embodiments are the use of such a catalyst system for hydrogenation or hydroformylation.
  • Another object of the invention are compounds of general formulas IA to lC 4i
  • one of the radicals R 5 to R 9 is a group of the formula PR 1 R 2 , wherein
  • R 1 and R 2 together with the phosphorus atom to which they are attached represent a 7-membered heterocycle which is optionally fused once, twice or three times to cycloalkyl, heterocycloalkyl, aryl and / or hetaryl, the fused groups independently of one another can carry one, two, three or four substituents selected from alkyl, alkoxy, halogen, sulfonate, NE 4 E 5 , alkylene-NE 4 E 5 , nitro, cyano and carboxylate, and / or 7-membered heterocycle may have one, two or three substituents which are selected from alkyl, alkoxy, optionally substituted cycloalkyl and optionally substituted aryl,
  • the radicals R 5 to R 9 which do not stand for PR 1 R 2 , independently of one another represent hydrogen, alkyl, cycloalkyl, heterocycloalkyl, aryl, hetaryl, WCOOR 0 , WCOO-M + , W (SO 3 ) R 0 , W ( SOs) -M + , WPO 3 (R 0 XR P ), W (PO 3 ) 2 - (M + ) 2 , WNE 1 E 2 , W (NE 1 E 2 E 3 ) + X " , WORD, WSR , R , (CHR r CH 2 O) ⁇ R q , (CH 2 NE 1 ) x R q , (CH 2 CH 2 NE 1 ) x R q , halogen, nitro, acyl or cyano,
  • W represents a single bond, a heteroatom, a heteroatom-containing group or a divalent bridging group having 1 to 20 bridging atoms
  • R 0 and RP are each the same or different radicals selected from alkyl, cycloalkyl, acyl, aryl and hetaryl,
  • R q , E 1 , E 2 , E 3 are each identical or different radicals selected from hydrogen, alkyl, cycloalkyl, acyl or aryl, R r is hydrogen, methyl or ethyl,
  • M + is a cation equivalent
  • x is an integer from 1 to 240
  • R a and R b are hydrogen, alkyl, acyl, cycloalkyl, heterocycloalkyl, aryl or hetaryl.
  • the radical R 5 is a group of the formula PR 1 R. 2
  • the group of the formula PR 1 R 2 is
  • Method b): in situ hydrogenation with [Rh (COD) 2 ] BF 4 : ligand: substrate 1: 2.1: 50 (0.005 mmol: 0.0105: 0.25 mmol) in a suitable solvent (7 , 5 ml), at a temperature of 25 0 C, under a hydrogen atmosphere, at a pressure of 1 bar.
  • the product mixture was analyzed by chiral HPLC.
  • Ligand 1 was prepared according to literature synthesis and converted into the [Rh (COD) L 2 ] BF 4 complex.
  • the chlorinated phosphepin I) is prepared starting from enantiomerically pure BINOL (2,2'-dihydroxy-1,1'-binaphthyl) according to literature methods: a) D. Xiao, Z. Zhang, X. Zhang, Org. Lett , 1999, 1, 1679-1681. b) K. Junge, G. Oehme, A. Monsees, T. Riermeier, U. Dingerdissen, M. Beller, Tetrahedron Lett. 2002, 43, 4977-4980. C) K. Junge, B. Hagemann, S. Enthaler, A. Spannenberg, M. Michalik, G. Oehme, A. Monsees, T. Riermeier, M. Beller, M. Tetrahedron: Asymmetry 2004, 15, 2621-2631.

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Abstract

L'invention concerne un procédé de transformation de composés, qui contiennent au moins une double liaison carbone-carbone ou carbone-hétéroatome, par une addition 1,2 en présence d'un catalyseur, comprenant au moins un complexe de métal de transition avec au moins deux ligands qui présentent respectivement un groupe contenant un atome de pnictogène et au moins un groupe fonctionnel apte à former des liaisons intermoléculaires non covalentes, et en présence d'un solvant halogéné qui présente au moins un hétéroatome différent de l'halogène. L'invention concerne également un procédé de préparation de composés chiraux en présence des catalyseurs et solvants décrits ci-dessus, ainsi que l'utilisation de ces catalyseurs en présence de tels solvants.
EP07821593A 2006-10-20 2007-10-19 Reactions d'addition catalysees par un metal de transition dans des solvants halogenes Withdrawn EP2057109A2 (fr)

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