EP2254895A1 - Composés de phosphore contenant des groupes imidazole - Google Patents

Composés de phosphore contenant des groupes imidazole

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Publication number
EP2254895A1
EP2254895A1 EP09709901A EP09709901A EP2254895A1 EP 2254895 A1 EP2254895 A1 EP 2254895A1 EP 09709901 A EP09709901 A EP 09709901A EP 09709901 A EP09709901 A EP 09709901A EP 2254895 A1 EP2254895 A1 EP 2254895A1
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EP
European Patent Office
Prior art keywords
butyl
alkyl
methyl
tert
hydrogen
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EP09709901A
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German (de)
English (en)
Inventor
Peter Hofmann
Patrick Hanno-Igels
Oleg Bondarev
Christoph JÄKEL
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BASF SE
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BASF SE
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Priority to EP09709901A priority Critical patent/EP2254895A1/fr
Publication of EP2254895A1 publication Critical patent/EP2254895A1/fr
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B53/00—Asymmetric syntheses
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • 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
    • C07F9/645—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having two nitrogen atoms as the only ring hetero atoms
    • C07F9/6503—Five-membered rings
    • C07F9/6506—Five-membered rings having the nitrogen atoms in positions 1 and 3
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • 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
    • C07F9/65683—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 the ring phosphorus atom being part of a phosphine
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • 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
    • C07F9/65685—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 the ring phosphorus atom being part of a phosphine oxide or thioxide
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • 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
    • C07F9/6571—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms
    • C07F9/657163—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms the ring phosphorus atom being bound to at least one carbon atom
    • C07F9/657181—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms the ring phosphorus atom being bound to at least one carbon atom the ring phosphorus atom and, at least, one ring oxygen atom being part of a (thio)phosphonic acid derivative

Definitions

  • the present invention relates to imidazole group-containing phosphorus compounds, using these, prepared optically active ligands, transition metal complexes containing such ligands, and catalysts comprising such transition metal complexes. Furthermore, the present invention relates to the respective processes for preparing the phosphorus compounds, the optically active ligands, the transition metal complexes and the catalysts, and the use of the catalysts for organic transformation reactions.
  • Organic transformation reactions for example asymmetric hydrogenations, hydroformylations or polymerizations, are important reactions in the large-scale chemical industry. These organic transformation reactions are predominantly homogeneously catalyzed.
  • chiral ligands are required.
  • a backbone for chiral ligands could be NHCP ligands, which harbor potential through a sterically protected phosphorus atom and a carbene as a strong ⁇ -donor.
  • Ph is phenyl and "Ar” is 2,6-diisopropylphenyl or 2,4,6-trimethylphenyl.
  • radical R1 is selected from the group consisting of a) hydrogen, b) linear or branched, saturated or unsaturated, aliphatic or alicyclic alkyl groups having 1 to 20 carbon atoms, c) heteroaryl, heteroaryl-Ci-C ⁇ - alkyl groups with 3 to 8 carbon atoms in the heteroaryl radical and at least one heteroatom selected from N, O and S, which may be substituted by at least one group selected from Ci-C ⁇ -alkyl groups and / or halogen atoms, d) aryl, aryl-Ci-C ⁇ -alkyl groups with 5 to 16 carbon atoms in the aryl radical which may optionally be substituted by at least one C 1 -C 6 -alkyl group and / or one halogen atom and the radical R is selected from the group consisting of a) linear b) heteroaryl-C 1 -C 8 -alkyl groups having 3 to 8 carbon atoms in the heteroaryl radical and
  • the cited documents disclose various ways of preparing the ionic liquids described. It is also described that the ionic liquids are used as solvents, as phase transfer catalysts, as extractants, as heat carriers, as operating fluids in process machines or as extraction medium or as constituents of the reaction medium for extractions of polarizable impurities / substrates.
  • These ligands should be synthesized with industrially inexpensive starting materials and reagents and without considerable expenditure on equipment.
  • the ligands or the catalyst should be prepared in a one-step process.
  • both enantiomers of the respective ligands should be preparable with similar efficiency.
  • the ligands, or the catalysts prepared therefrom should be suitable for use in organic transformation reactions with high stereoselectivity and / or good regioselectivity.
  • the organic transformation reactions should have a comparable yield to the prior art.
  • the catalysts prepared from the NHCP ligands characterized in more detail below have a good efficiency compared to the prior art at significantly lower synthesis costs.
  • the NHCP ligands are not only simple and inexpensive to produce, they are also extremely robust. Furthermore, even both enantiomers can be produced with little effort.
  • 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 5 -synyl.
  • Alkyl and very particularly preferably C 1 -C 4 -alkyl groups are in particular methyl, ethyl, propyl, isopropyl, n-butyl, 2-butyl, sec-butyl, tert-butyl, n-pentyl, 2-pentyl , 2-methylbutyl, 3-methylbutyl, 1, 2-dimethylpropyl, 1, 1-dimethylpropyl, 2,2-dimethylpropyl, 1-ethylpropyl, n-hexyl, 2-hexyl, 2-methylpentyl, 3-methylpentyl, 4 Methylpentyl, 1, 2-dimethylbutyl, 1, 3-dimethylbutyl, 2,3- Dimethylbutyl, 1,1-dimethylbutyl, 2,2-dimethylbutyl, 3,3-dimethylbutyl, 1,1,2-trimethylpropyl, 1,2,2-trimethylpropyl, 1-ethylbut
  • alkyl also includes substituted alkyl groups which generally have 1, 2, 3, 4 or 5, preferably 1, 2 or 3, and more preferably 1, substituents, which are preferably selected from alkoxy, cycloalkyl, aryl, hetaryl, hydroxyl , Halogen, NE 1 E 2 , NE 1 E 2 E 3+ , carboxylate and sulfonate
  • a preferred perfluoroalkyl group is trifluoromethyl.
  • 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, these 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.
  • Carboxylate and sulfonate in the context of this invention preferably represent a derivative of a carboxylic acid function or a sulfonic acid function, in particular a metal carboxylate or sulfonate, a carboxylic acid 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 for alkanoyl or aroyl groups having generally 2 to 1 1, preferably 2 to 8 carbon atoms, for example for the formyl, acetyl, propanoyl, butanoyl, pentanoyl, hexanoyl , Heptanoyl, 2-ethylhexanoyl, 2-propylheptanoyl, benzoyl or naphthoyl group.
  • the radicals E 1 to E 3 are independently selected from hydrogen, alkyl, cycloalkyl and aryl.
  • the group NE 1 E 2 is preferably N, N-dimethylamino, N, N-diethylamino, N, N-dipropylamino, N, N-diisopropylamino, N, N-di-n-butylamino, N, N-di-t .-butylamino, N, N-dicyclohexylamino or N, N-diphenylamino.
  • Halogen is fluorine, chlorine, bromine and iodine, preferably fluorine, chlorine and bromine.
  • the term "leaving group" in the context of the invention stands for those structural elements which can be substituted by attack of or reaction with nucleophiles. These leaving groups are generally known to the person skilled in the art and, for example, chlorine, bromine, iodine, trifluoroacetyl, acetyl, benzoyl, Tosyl, nosyl, triflate, nonaflate, camphor-10-sulfonate and the like.
  • the invention relates to imidazole-containing phosphorus compounds of the general formula I or II:
  • R1 and R2 represent different radicals and are selected from the group consisting of alkyl and alkyl (variant ⁇ )
  • R 1 and R 2 are different radicals and are selected from the group consisting of alkyl and aryl (variant ⁇ ),
  • R1 and R2 together with W form a chiral 7-membered ring selected from the general formulas 1 to 6 (variant ⁇ ):
  • R 10 to R 19 are each the same or different radicals and are selected from the group consisting of alkyl, aryl, alkoxy, aryloxy, acyloxy, hydroxyl,
  • both radicals R 13 form a 7- to 12-membered ring
  • z is each the same or different radicals and is selected from the group consisting of hydrogen, alkyl, acetyl, trifluoroacetyl, benzoyl, tosyl and nosyl,
  • R1 and R2 together with W form a chiral 5-membered ring selected from the general formulas 7 to 9 (variant ⁇ ):
  • R 20 is a radical selected from the group consisting of methyl, ethyl, propyl, butyl, isopropyl and phenyl,
  • R 21 and R 22 are each the same or different radicals and are selected from the group consisting of hydrogen, alkyl, aryl and alkoxy, or R 21 and R 22 form a 4- to 6-membered ring which, in addition to carbon atoms, has up to two oxygen atoms. May have atoms in the ring skeleton, each z is the same or different radicals and is selected from the
  • R3 and R4 are each the same or different radicals selected from the group consisting of hydrogen, alkyl and aryl,
  • R5 is alkyl or aryl
  • R 6 and R 7 are each the same or different radicals selected from the group consisting of hydrogen, alkyl, aryl and a 6-membered aliphatic or aromatic ring,
  • R 8 and R 9 independently of one another represent hydrogen or alkyl
  • X stands for a leaving group.
  • W is phosphorus.
  • the one alkyl radical is preferably adamantyl, tert-butyl, sec-butyl or isopropyl, in particular tert.
  • Butyl, and the other alkyl radical is methyl, ethyl, propyl, butyl, pentyl or hexyl, in particular methyl or ethyl, particularly preferably methyl.
  • the aryl radical is preferably phenyl, ToIyI, XyIyI, mesityl, naphthyl, fluorenyl, anthracenyl, in particular phenyl
  • the alkyl radical is methyl, adamantyl, tert-butyl, sec-butyl, isopropyl, especially tert-butyl and methyl.
  • alkyl and alkyl are preferred over the combination of alkyl and aryl (variant ⁇ ).
  • R 10 to R 19 are preferably each identical or different radicals selected from the group consisting of alkyl, in particular methyl, ethyl, Isopropyl, tert-butyl, adamantyl, alkoxy, in particular methoxy, ethoxy, isopropoxy, tert-butyloxy, adamantyloxy, hydroxyl, chlorine, bromine and hydrogen, more preferably independently of one another hydroxyl, bromine and hydrogen, are R12 and R13 independently of one another are preferred for dialkylamino, in particular N, N-dimethylamino, N, N-diethylamino, N, N-diisopropylamino, N, N-dicyclohexylamino or N, N-diphenylamino, or acylamino, in particular formylamino,
  • z is independently alkyl, in particular methyl, ethyl, isopropyl, tert-butyl, adamantyl, acetyl or tosyl.
  • R 20 is preferably methyl, ethyl, isopropyl or phenyl
  • R 21 and R 22 are preferably, independently of one another, hydrogen or alkoxy, in particular methoxy, ethoxy, isopropoxy and tert-butyloxy, furthermore a 5-membered aliphatic ring having two oxygen atoms is preferred
  • z is preferably alkyl, in particular methyl, ethyl, isopropyl, tert-butyl, adamantyl, aryl, in particular Phenyl, ToIyI, XyIyI, mesityl, naphthyl,
  • R3 and R4 independently of one another preferably represent hydrogen, methyl, ethyl or benzyl, in particular hydrogen.
  • R 5 is preferably methyl, ethyl, isopropyl, tert-butyl, adamantyl, mesityl, phenyl, ToIyI, xylyl, naphthyl, fluorenyl, anthracenyl, in particular methyl, isopropyl, tert-butyl, adamantyl and mesityl.
  • R6 and R7 are preferably each independently hydrogen or a 6-membered aromatic ring.
  • R 8 and R 9 independently of one another are preferably hydrogen, alkyl, in particular methyl, ethyl, isopropyl, tert-butyl, adamantyl, (CH 4 ) 4 -ketone or aryl, in particular phenyl, toyl, xylyl, mesityl, naphthyl, fluorenyl, anthracenyl.
  • R 8 and R 9 independently of one another are hydrogen, phenyl or a (CH 2 ) 4 chain.
  • the present invention relates to a process for the preparation of imido zol phenomenon termed by imido zol phenomenon termed by imido zol phenomenon into general formula I or II, which is characterized in that compounds of general formula A
  • the reaction at a temperature of 50 to 150 0 C, in particular at a temperature of 80 to 120 0 C, performed.
  • the reaction time is typically 1 to 10 days, preferably 10 to 150 hours.
  • the optimal reaction time can be determined by the skilled person by simple routine tests.
  • solvents it is possible to use all solvents known to the person skilled in the art, for example toluene, xylene, acetonitrile, preferably the compound B or C serves as solvent.
  • imidazole-containing phosphorus compounds of the general formula I and II serve as precursor for the preparation of optically active ligands (carbenes) of the general formulas III and IV:
  • the invention therefore further provides optically active ligands of the general formula III:
  • R1 and R2 represent different radicals and are selected from the group consisting of alkyl and alkyl (variant ⁇ )
  • R 1 and R 2 are different radicals and are selected from the group consisting of alkyl and aryl (variant ⁇ ),
  • R10 to R19 are each the same or different groups and are selected from the group consisting of alkyl, aryl, alkoxy, aryloxy, acyloxy, hydroxyl, trialkylsilyl, sulfonyl, dialkylamino, acylamino, fluoro, chloro, bromo and iodo, or in relation to the radicals R12 and R13: the adjacent radicals R 12 and R 13 in each case form a 5- to 6-membered saturated ring, wherein the 5- to 6-membered ring in addition to carbon atoms may also contain nitrogen or oxygen atoms in the ring skeleton, or with respect to the radicals R13 both radicals R 13 form a 7- to 12-membered ring, z are each the same or different radicals and is selected from the group consisting of hydrogen, alkyl, acetyl, trifluoroacetyl, benzoyl, tosyl and nosyl,
  • R1 and R2 together with W form a chiral 5-membered ring selected from the general formulas 7 to 9 (variant ⁇ ):
  • R20 is a radical selected from the group consisting of methyl, ethyl, propyl, butyl, isopropyl and phenyl
  • R21 and R22 each represent identical or different radicals and are selected from the group consisting of hydrogen, alkyl, aryl and alkoxy
  • R 21 and R 22 form a 4- to 6-membered ring which, in addition to carbon atoms, can have up to two oxygen atoms in the ring skeleton
  • z is in each case identical or different radicals and is selected from the group consisting of hydrogen, alkyl , Acetyl, trifluoroacetyl, benzoyl, tosyl and nosyl,
  • R3 and R4 are each the same or different radicals selected from the group consisting of hydrogen, alkyl and aryl,
  • R5 is alkyl or aryl
  • R6 and R7 are each the same or different radicals selected from the group consisting of hydrogen, alkyl, aryl and a 6-membered aliphatic see or aromatic ring.
  • the preferences of the radicals R 1 to R 7, and R 10 to R 22, W and z correspond to the preferences for the general formula I shown above on page 8, line 1 to page 14, line 5.
  • step (i) preference is given to using a hydride donor as reducing agent, for example
  • PMHS polymethylhydrosiloxane
  • EtO polymethylhydrosiloxane
  • (EtO) 3 SiH, HSiCl 3 , H 3 SiPh, AlH 3 / Ti (OiPr) 4 , AlH 3 / TiCl 4 , AlH 3 / TiCp 2 Cl 2 (Cp cyclopentadienyl)
  • PMHS polymethylhydrosiloxane
  • Suitable Lewis acids in step (i) are all Lewis acids known to those skilled in the art, for example TiCl 4 , Ti (OiPr) 4 or TiCp 2 Cb.
  • the solvent used in step (i) is preferably a stable solvent or mixtures of such solvents, for example ethereal, halogenated or aromatic solvents such as THF, diethyl ether, tert-butyl methyl ether, dibutyl ether, toluene, hexane, chlorobenzene, chloroform , preferably THF, diethyl ether, chlorobenzene, chloroform.
  • ethereal, halogenated or aromatic solvents such as THF, diethyl ether, tert-butyl methyl ether, dibutyl ether, toluene, hexane, chlorobenzene, chloroform , preferably THF, diethyl ether, chlorobenzene, chloroform.
  • reaction time of step (i) is typically 5 to 100 hours, preferably 10 to 50 hours.
  • General references can be found, for example, in (a) T. Coumbe, NJ Lawrence, F. Arabic, Tetrahedron: Letters 1994, 35, 625-628; (b) Y. Hamada, F. Matsuura, M. Oku, K. Hatano, T. Shioiri, Tetrahedron: Letters, 1997, 38, 8961-8964, and (c) A. Ariffin, AJ Blake, RA Ewin, W.-S. Li, NS Simpkins, J.Chem.Soc, Perkin Trans. 1, 1999, 3177-3189.
  • step (ii) typical strong bases known in the art, preferably having a pKa of at least 14, are used.
  • typical strong bases known in the art preferably having a pKa of at least 14, are used.
  • KOt-Bu, KOEt, KOMe, KOH, NaOt-Bu, NaOEt, NaOMe, NaOH, LiOH, LiOtBu, LiOMe, in particular KOt-Bu, KOEt, KOMe, NaOt-Bu, NaOEt, NaOMe are used.
  • step (ii) it is possible to use all ethereal or other aprotic solvents known to the person skilled in the art, for example diethyl ether, tert-butyl methyl ether, dibutyl ether, toluene or mixtures thereof.
  • reaction time of step (ii) is typically 1 minute to 10 hours, preferably 10 minutes to 5 hours, especially 2 to 3 hours.
  • the reaction temperature in step (ii) is preferably from -60 to 40 ° C., in particular from -20 to 30 ° C.
  • the invention relates to transition metal complexes containing as ligands at least one compound of general formula III or IV.
  • transition metal complexes correspond to the general formula V and VI:
  • transition metals preference is given to using metals of group 8 to 11, in particular Ru, Fe, Co, Rh, Ir, Ni, Pd, Pt, Ag, Cu or Au, more preferably Ru, Rh, Ir, Ni, Pd ,
  • X is further, optionally different, ligands, preferably cod (cyclooctadiene), norbornadiene, Cl, Br, I, CO, allyl, benzyl, Cp (cyclopentadienyl), PCy3, PPhi3, MeCN, PhCN, dba (dibenzylideneacetone) , acetate, CN, acac (acetylacetonate), methyl and H, especially cod, norbornadiene, Cl, CO, allyl, benzyl, acac, PCy3, MeCN, methyl and H.
  • n varies between O and 4 and is accordingly dependent on selected transition metal.
  • the definitions and preferences for the radicals R 1 to R 22, W and z correspond to the preferences for the compounds of the general formulas III and IV or of the general formulas I and II on page 5, line 17 to page 14, line 5. Furthermore, the present invention relates to a process for the preparation of transition metal complexes, which is characterized in that either
  • optically active ligands of the general formula III are reacted with metal complexes at a temperature of -80 0 C to +120 0 C, using at least one solvent for 5 minutes to 72 hours, or
  • RuCI 2 (PCy 3 ) 2 CHPh, (PCy 3 ) Cl 2 RuCl (OiPrO-Ph), Ru (cod) (methallyl) 2 , [Pd (allyl) Cl] 2 , Pd 2 (dba) 3 , CuCN, Cu (CF 3 SOs) 2 , [Ni (allyl) Cl] 2 , Ni (cod) 2 especially [Ir (cod) Cl] 2 , [Rh (COd) Cl] 2 , Rh (cod) acac, Rh (cod) 2 X, Rh (norbornadiene) 2 X, Ir (cod) 2 X (with X BF 4 , CIO 4 , CF 3 SO 3 , CH 3 SO 3 , HSO 4 , B (phenyl) 4 , B [bis (3 , 5-trifluoromethyl) phenyl] 4 , PF 6 , SbCl 6 , AsF 6 , SbF 6 ),
  • the reaction temperature is advantageously from -80 ° C to + 120 ° C, preferably from 0 ° C to + 50 ° C.
  • the reaction time is advantageously from 5 minutes to 72 hours, preferably from 1 to 24 hours.
  • the solvents used may be any of the solvents customary in the art, for example THF, diethyl ether, hexane, pentane, CHCl 3 , CH 2 Cl 2 , toluene, benzene, DMSO or acetonitrile, preferred are THF, diethyl ether, CH 2 Cl 2 , toluene or hexane.
  • the preferences relative to the strong base and the ethereal or other aprotic solvent correspond to those described for step (ii) on page 20.
  • the reaction temperature is advantageously from - 80 0 C to +120 0 C, preferably from 0 ° C to +50 0 C.
  • the reaction time is advantageously from 5 minutes to 72 hours, preferably from 1 to 24 hours.
  • the present invention relates to catalysts comprising at least one complex with a transition metal containing as ligands at least one compound of general formula III or IV.
  • transition metals of group 8 to 11 in particular Ru, Fe, Co, Rh, Ir, Ni, Pd, Pt, Ag or Au, particularly preferably Ru, Rh, Ir, Ni or Pd.
  • the compounds of the general formula I are reduced in a separate precursor using in each case at least one reducing agent and a Lewis acid, or (variant 2) by reacting optically active ligands of the general formula III with metal complexes at one temperature from -80 0 C to +120 0 C, using at least one ether or other aprotic solvent for 5 minutes to 72 hours, if W is phosphite, then the compounds of general formula III in a separate precursor are using each of at least one Reducing agent and a Lewis acid reduced, or
  • variant (a) represents the possibility of in situ synthesis of homogeneous catalysts.
  • the preferred reaction parameters of variants 1 and 2 can be found on pages 21, line 38 to page 22, line 2 (variant 1) and page 22, lines 4 to 8 (variant 2).
  • Another object of the invention is the use of catalysts, comprising at least one complex with a transition metal containing as ligands at least one compound of the general formula III or IV - as described above - for organic transformation reactions.
  • Organic transformation reactions are understood as meaning, for example, hydrogenation, hydroboration, hydroamination, hydroamidation, hydroalkoxylation, hydrovinylation, hydroformylation, hydrocarboxylation, hydrocyanation, hydrosilylation, carbonylation, cross-coupling, allylic substitution, aldol reaction, olefin metathesis, C-H activation and polymerization.
  • FIG. 1 shows the X-ray structure analysis of 1 - ⁇ [(S) -ertert-
  • N-tert-butylimidazole (1) and N-mesitylimidazole (2) were synthesized according to a literature procedure. [A. J. Arduengo, III et al. US Pat. US 6,177,575 B1]
  • Racemic tert-butyl (phenyl) phosphine oxide (3) was synthesized via a Grignard reaction. [RK Haynes, TL. Au-Yeung, WK. Chan, WL. Lam, ZY Li, LL Yeung, ASC Chan, P. Li, M. Koen. C.R. Mitchell, SC Vonwiller, Eur. J. Org. Chem., 2000, 3205-3216].
  • the chiral tert-butyl (phenyl) phosphine oxide was obtained by crystallization of the phosphine oxide - (+) - (S) -mandelic acid adduct. [J. Drabowicz, P. Lyzwa, J. Olemanczuk, KM Pietrusiewicz, M. Mikolajczyk, Tetrahedron: Asymmetry 1999, 10, 2757-2763]
  • the reaction suspension was stirred at room temperature overnight.
  • 50 ml of dichloromethane and 25 ml of water were added and the phases were separated in a separating funnel.
  • the aqueous phase was extracted several times with dichloromethane.
  • the combined organic phases were washed with 50 ml of saturated sodium chloride solution, dried over sodium sulfate, filtered and concentrated on a rotary evaporator.
  • Butyl (phenyl) (tosylmethyl) phosphine oxide ((Sp) -6) with 1.86 g (10 mmol) of N-Mesitylimidazol (2), the apparatus was placed under argon and heated to 100 0 C for four days. The yellowish, air-stable oil obtained after cooling to room temperature was diluted with a little methylene chloride and crystallized with diethyl ether. The precipitated white, very voluminous solid was filtered off and washed with diethyl ether. Yield: 3.75 g, 70%; Colorless solid; 31 P NMR (CDCl 3 ), ⁇ P 48.0.
  • tert-Butyldimethylphosphine-borane was synthesized from phosphorus trichloride by reaction with Grignard compounds and borane-THF adduct in a one-pot reaction.
  • Butyl (hydroxymethyl) (methyl) phosphine-borane was obtained by enantioselective deprotonation with sec-butyllithium / (-) - sparteine followed by oxidation with atmospheric acid.
  • reaction suspension was stirred at room temperature overnight.
  • 40 ml of water and 35 ml of dichloromethane were added and the phases were separated in a separating funnel.
  • Butyl (methyl) phosphinooxy) methyl] imidazolium (1 S) -campher-10-sulfonate ((Sp) 1 (IS) - 12) and 3.4 ml of poly (methylhydrosiloxane) in 20 ml of chloroform (abs.).
  • To the reaction solution 1.48 ml (5.0 mmol) of titanium (IV) tetraisopropylate were added and the reaction mixture was heated at 75 ° C. for 6 days to reflux. After 2 days reaction time, another 0.50 ml (1.7 mmol, 0.3 eq.) Of titanium (IV) tetraisopropylate was added.
  • the light brown solution was diluted with 20 ml of dichloromethane (abs.) And washed three times with 10 ml of oxygen-free, saturated sodium chloride solution.
  • the combined aqueous phases were extracted twice with 10 ml of dichloromethane, the combined organic phases dried over sodium sulfate and filtered through a protective gas frit.
  • the drying agent was washed twice with 15 ml of dichloromethane.
  • the solvents were condensed off in vacuo and the resulting yellow oil was precipitated from a mixture of 20 ml of pentane (abs.) And 10 ml of hexane (abs.) In an ultrasonic bath.
  • the crude product is precipitated by addition of 10 ml of tetrahydrofuran and 15 ml of diethyl ether by treatment in an ultrasonic bath and filtered off.
  • the solid is recrystallized from tetrahydrofuran and dried in vacuo over calcium chloride.
  • the catalyst 11 (2 mg, 1.5 ⁇ 10 "6 mol) was weighed in the glove box in an autoclave. It was added 50 ml of toluene. The autoclave was then connected to a pressure apparatus, flushed several times with ethylene and below the desired temperature After the desired reaction time, the oligomerization was stopped and the autoclave was opened, and the resulting solution was analyzed by GC / MS analysis The oligomer distribution after 12 hours was identical to the distribution after 2 hours.
  • the ligands of the prior art are characterized by elaborate syntheses, especially both optical antipodes.
  • the ligands according to the invention can be prepared simply and with comparable efficiencies in the form of both optical antipodes.

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Abstract

La présente invention concerne des composés de phosphore contenant des groupes imidazole en utilisant des ligands optiquement actifs produits, des complexes de métaux de transition qui contiennent ces ligands  et des catalyseurs qui comprennent des complexes de métaux de transition. La présente invention concerne en outre le procédé correspondant de production de composés de phosphore, de ligands optiquement actifs, de complexes de métaux de transition et de catalyseurs et l'utilisation des catalyseurs pour des réactions de transformation organique, W désignant le phosphore (P) ou le phosphite (P=O).
EP09709901A 2008-02-15 2009-02-13 Composés de phosphore contenant des groupes imidazole Withdrawn EP2254895A1 (fr)

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EP09709901A EP2254895A1 (fr) 2008-02-15 2009-02-13 Composés de phosphore contenant des groupes imidazole
PCT/EP2009/051677 WO2009101162A1 (fr) 2008-02-15 2009-02-13 Composés de phosphore contenant des groupes imidazole

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US20120190806A1 (en) * 2009-07-31 2012-07-26 Basf Se Phosphine Borane Compounds Comprising Imidazol Groups And Method For Producing Phosphine Borane Compounds Comprising Imidazol Groups
CN103785469B (zh) * 2012-11-01 2016-08-03 中国石油化工股份有限公司 一种合成丙烯酸的金属配合物催化剂的制备方法
DE102013201665A1 (de) * 2013-02-01 2014-08-07 Evonik Industries Ag Phosphor-Liganden und Verfahren zur selektiven Ruthenium-katalysierten Hydroaminomethylierung von Olefinen
WO2014138113A2 (fr) * 2013-03-04 2014-09-12 President And Fellows Of Harvard College 1,2-hydrosilylation de diènes
CN108031493B (zh) * 2017-12-11 2020-11-06 天津科技大学 用于乙烯选择性齐聚的催化剂体系及乙烯齐聚反应方法
WO2019113752A1 (fr) * 2017-12-11 2019-06-20 天津科技大学 Système catalyseur pour l'oligomérisation sélective de l'éthylène et procédé de réaction d'oligomérisation d'éthylène
CN108939947B (zh) 2018-08-06 2020-12-04 天津工业大学 聚偏氟乙烯和超高分子量聚乙烯共混微孔膜及其制备方法
CN110041174B (zh) * 2019-04-28 2022-04-12 南方科技大学 一种ebinol轴手性化合物及其合成方法和应用
CN111203276B (zh) * 2020-02-27 2022-11-18 郑州大学 手性双齿亚磷酸酯配体的应用、硅氢化反应催化剂及其应用和手性硅烷的制备方法
CN113801161A (zh) * 2020-06-15 2021-12-17 华东师范大学 咪唑类配体衍生物及其制备和在丁二烯调聚反应中的应用

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CA2715225A1 (fr) 2009-08-20

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