CH653338A5 - Phosphorus compounds - Google Patents

Phosphorus compounds Download PDF

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Publication number
CH653338A5
CH653338A5 CH7010/82A CH701082A CH653338A5 CH 653338 A5 CH653338 A5 CH 653338A5 CH 7010/82 A CH7010/82 A CH 7010/82A CH 701082 A CH701082 A CH 701082A CH 653338 A5 CH653338 A5 CH 653338A5
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Switzerland
Prior art keywords
aryl
general formula
compound
rhodium
aryloxy
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CH7010/82A
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German (de)
Inventor
Emil Albin Dr Broger
Yvo Dr Crameri
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Hoffmann La Roche
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Priority to CH7010/82A priority Critical patent/CH653338A5/en
Priority to US06/458,418 priority patent/US4539411A/en
Priority to IT19195/83A priority patent/IT1175910B/en
Priority to DE19833302697 priority patent/DE3302697A1/en
Priority to NL8300354A priority patent/NL8300354A/en
Priority to FR8301684A priority patent/FR2521145B1/en
Priority to GB08303161A priority patent/GB2114134B/en
Priority to AT0039383A priority patent/AT389312B/en
Priority to US06/744,584 priority patent/US4620013A/en
Publication of CH653338A5 publication Critical patent/CH653338A5/en

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
    • B01J31/2495—Ligands comprising a phosphine-P atom and one or more further complexing phosphorus atoms covered by groups B01J31/1845 - B01J31/1885, e.g. phosphine/phosphinate or phospholyl/phosphonate ligands
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D207/00—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D207/02—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D207/04—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members
    • C07D207/10—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D207/12—Oxygen or sulfur atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D207/00—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D207/02—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D207/04—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members
    • C07D207/10—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D207/16—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
    • C07D307/26—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
    • C07D307/30—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D307/32—Oxygen atoms
    • C07D307/33—Oxygen atoms in position 2, the oxygen atom being in its keto or unsubstituted enol form
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
    • C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table compounds of the platinum group
    • C07F15/0073—Rhodium compounds
    • 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
    • C07F9/553—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having one nitrogen atom as the only ring hetero atom
    • C07F9/572—Five-membered rings
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/60—Reduction reactions, e.g. hydrogenation
    • B01J2231/64—Reductions in general of organic substrates, e.g. hydride reductions or hydrogenations
    • B01J2231/641—Hydrogenation of organic substrates, i.e. H2 or H-transfer hydrogenations, e.g. Fischer-Tropsch processes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
    • B01J2531/0238—Complexes comprising multidentate ligands, i.e. more than 2 ionic or coordinative bonds from the central metal to the ligand, the latter having at least two donor atoms, e.g. N, O, S, P
    • B01J2531/0258—Flexible ligands, e.g. mainly sp3-carbon framework as exemplified by the "tedicyp" ligand, i.e. cis-cis-cis-1,2,3,4-tetrakis(diphenylphosphinomethyl)cyclopentane
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
    • B01J2531/82—Metals of the platinum group
    • B01J2531/822—Rhodium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
    • B01J31/1845—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing phosphorus
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
    • B01J31/2404—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring
    • B01J31/2409—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring with more than one complexing phosphine-P atom
    • B01J31/2414—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring with more than one complexing phosphine-P atom comprising aliphatic or saturated rings

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  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
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Abstract

A description is given of novel chiral phosphines of the general formula <IMAGE> in which R represents aryl and R<1> represents the group <IMAGE>, in which R<2> denotes aryl, diarylamino, di-lower alkylamino, hydroxyl, aryloxy or lower alkoxy, and of their preparation and their use in catalysts for asymmetric hydrogenations.

Description

       

  
 



   Die vorliegende Erfindung betrifft neue chirale Phosphine



  der allgemeinen Formel
EMI2.1     
 worin R Aryl und   Rl    die Gruppe
EMI2.2     
 darstellt, wobei R2 Aryl, di-Arylamino, di-niederes Alkylamino, Hydroxy, Aryloxy oder niederes Alkoxy bedeuten.



   Die Erfindung betrifft ferner die Herstellung der Phosphine der Formel I, sowie deren Verwendung für asymmetrische Hydrierungen.



   Der Ausdruck    Aryl     bedeutet im Rahmen der vorliegenden Erfindung Phenyl, welches gegebenenfalls in para-   und/odsr    meta-Stellung niedere Alkyl- oder niedere Alkoxygruppen, vorzugsweise Methyl- oder Methoxygruppen, oder auch di-niederes Alkylamino, vorzugsweise Dimethylaminogruppen, aufweisen kann. Zudem können zwei Arylgruppen am gleichen Phosphoratom über die o-Stellung direkt miteinander verbunden sein oder auch über eine Methylen-, Äthylen- oder Propylengruppe.



  Der Ausdruck  Aryloxy  bedeutet Gruppen, in denen der Arylrest die vorhergehende Bedeutung hat. Der Ausdruck  niederes Alkyl  bedeutet im Rahmen der vorliegenden Erfindung geradkettige und verzweigte Alkylgruppen mit 1 bis 7 Kohlenstoffatomen wie z.B. Methyl, Äthyl, Propyl, Isopropyl, n-Butyl, Isobutyl, tert. Butyl und dergleichen. Der Ausdruck  niederes Alkoxy  bedeutet Gruppen, in denen der Alkylrest die vorhergehende Bedeutung hat. Weiterhin bedeutet das Zeichen     <  ,    dass sich der entsprechende Rest oberhalb der Molekülebene befindet, während das Zeichen  """  bedeutet, dass sich der entsprechende Rest unterhalb der Molekülebene befindet.



   Bevorzugte Phosphine der Formel I sind solche, worin R Phenyl, p-Tolyl, m-Tolyl oder 3,5-Xylyl darstellt und R2 in den Resten   Rl    Phenyl, p-Tolyl, m-Tolyl, Phenoxy oder di-niederes Alkylamino bedeutet.



   Als Beispiel einer bevorzugten Verbindung der Formel 1 kann folgende genannt werden:     {(2S,4S)-2-[(Diphenylphosphino)methyl]-4-(diphenylphos- phino)-l -pyrrodidinyl}diphenylphosphin-sulfid.   



   Die erfindungsgemässen Verbindungen der Formel I können dadurch hergestellt werden, dass man eine Verbindung der allgemeinen Formel
EMI2.3     
 worin R die obige Bedeutung hat, mit einer Verbindung der allgemeinen Formel
EMI2.4     
 worin R2 die obige Bedeutung hat und R3 Chlor oder Fluor bedeutet, umsetzt.



   Sie können ferner dadurch hergestellt werden, dass man eine Verbindung der allgemeinen Formel
EMI2.5     
 worin   Rl    die obige Bedeutung hat und R4 Aryl oder niederes Alkyl bedeutet, mit einer Verbindung der allgemeinen Formel
EMI2.6     
 worin R die obige Bedeutung hat und R5 Lithium, Natrium, Kalium oder Magnesium-halogenid darstellt, umsetzt.



   Die Umsetzung der Verbindungen der Formel II mit derjenigen der Formel IIId kann in an sich bekannter Weise durchgeführt werden, wobei einzig darauf zu achten ist, dass unter striktem Sauerstoffausschluss, also unter Inertgasatmosphäre, z.B. unter Stickstoff, Argon und dergleichen gearbeitet wird.



  Die Umsetzung kann zweckmässig in einem inerten organischen Lösungsmittel wie einem aromatischen Kohlenwasserstoff, z.B.



  Benzol, Toluol und dergleichen, oder in einem Äther wie Di äthyläther, Tetrahydrofuran, Dioxan und dergleichen und gegebenenfalls unter Zusatz eines tert. Amins erfolgen. Die Temperatur und der Druck sind keine kritischen Grössen bei dieser Reaktion, welche somit ohne weiteres bei etwa Raumtemperatur und Atmosphärendruck durchgeführt werden kann.



   Die als Ausgangsmaterial verwendeten Verbindungen der Formeln II und IIId sind bekannte Verbindungen oder Analoge bekannter Verbindungen, welche leicht in zur Herstellung der bekannten Verbindungen analoger Weise hergestellt werden können.



   Die Umsetzung der Verbindungen der Formen IV mit denjenigen der Formel V kann in an sich bekannter Weise durchgeführt werden, wobei einzig darauf zu achten ist, dass unter striktem Sauerstoffausschluss, also unter Inertgasatmosphäre, z.B. unter Stickstoff, Argon und dergleichen, gearbeitet wird.



  Die Umsetzung erfolgt zweckmässig in einem inerten organischen Lösungsmittel wie einem Äther, z.B. Tetrahydrofuran, Dioxan, Diäthyläther und dergleichen, gewünschtenfalls in Gegenwart eines Kohlenwasserstoffes, z.B. Hexan, Benzol, Toluol und dergleichen. Die Reaktion erfolgt zweckmässig bei einer Temperatur von   etwa -15"C    bis etwa Raumtemperatur, vorzugsweise bei   etwa -10"C    bis etwa   0 C.    Der Druck ist keine kritische Grösse in dieser Reaktion, welche somit ohne weiteres bei Atmosphärendruck durchgeführt werden kann.



   Die als Ausgangsmaterial verwendeten Verbindungen der   Formel IV sind neue Verbindungen und als solche ebenfalls Gegenstand der vorliegenden Erfindung. Sie können jedoch in an sich bekannter Weise, z.B. gemäss folgendem Reaktionsschema hergestellt werden. Ts bedeutet die Tosylgruppe und A die Gruppe
EMI3.1     
 Reaktionsschema
EMI3.2     

Die ebenfalls als Ausgangsmaterial verwendeten Verbindungen der Formel V sind bekannte oder Analoge bekannter Verbindungen, welche leicht in zur Herstellung der bekannten Verbindungen analoger Weise hergestellt werden können.



   Die erfindungsgemässen Phosphine der Formel I bilden mit Rhodium Komplexe, welche als Katalysatoren bei asymmetrischen Hydrierungen verwendbar sind. Diese Katalysatoren, d.h.



  die Komplexe aus Rhodium und den Phosphinen der Formel I sind neu und ebenfalls Gegenstand der vorliegenden Erfindung.



  Diese Katalysatoren können in einfacher und an sich bekannter Weise hergestellt werden, z.B. indem man eine Verbindung der Formel I mit einer Rhodium abgebenden Verbindung in einem geeigneten inerten organischen Lösungsmittel umsetzt. Als geeignete, Rhodium abgebende Verbindungen können beispielsweise genannt werden Rhodiumtrichlorid-Hydrat, Rhodiumtribromid-Hydrat, Rhodiumsulfat, oder auch organische Rhodiumkomplexe mit Äthylen, Propylen und dergleichen, sowie mit bis-Olefinen, z.B. 1,5-Cyclooctadien, 1,5-Hexadien, Bicyclo   -2,2, l-hepta-2,5-dien    oder mit weiteren Dienen, welche mit Rhodium leicht lösliche Komplexe bilden. Bevorzugte, Rhodium abgebende Verbindungen sind   u,u'-Dichlor-bis-[bis-(olefin)rho-    dium(I)], z.

  B.   u,u'-Dichlor-bis-[l ,5-cyclooctadienrhodium(I)j    oder auch   u,u'-Dichlor-bis-[(norbornadien)rhodium(I)].   



   Wie bereits erwähnt dienen die erfindungsgemässen Phosphine als Liganden in Rhodium-Komplexen, welche bei asymmetrischen Hydrierungen als Katalysatoren verwendet werden.

 

  Besonders interessant sind sie im Zusammenhang mit der asymmetrischen Hydrierung von a-Keto-carbonsäureestern zu den entsprechenden a-Hydroxy-carbonsäureestern und insbesondere von Dihydro-4,4-dimethyl-2,3-furandion (Ketopantolacton) zum entsprechenden   R-(a-Hydroxy-ss,ss-dimethyl-Y-butyrolac-    ton)   [R-(-)-Pantolacton] .   



   Zur Durchführung der erwähnten asymmetrischen Hydrierung können die Phosphine der Formel I als solche, in einer Lösung einer asymmetrisch zu hydrierenden Verbindung, mit einer Rhodium abgebenden Verbindung in Kontakt gebracht werden. Andererseits können die Phosphine der Formel I zunächst in einem geeigneten Lösungsmittel mit einer Rhodium abgebenden Verbindung zu dem entsprechenden Katalysator-Komplex  umgesetzt werden und dieser dann zu einer Lösung einer asymmetrisch zu hydrierenden Verbindung gegeben werden.



   Sowohl die Umsetzung der Phosphine der Formel I mit Rhodium abgebenden Verbindung wie auch die erwähnten asymmetrischen Hydrierungen können in geeigneten, unter den Reaktionsbedingungen inerten organischen Lösungsmitteln durchgeführt werden. Als solche können insbesondere genannt werden niedere Alkanole wie z.B. Methanol oder Äthanol, aromatische Kohlenwasserstoffe wie Benzol oder Toluoyl, cyclische Äther wie Tetrahydrofuran oder Dioxan, Ester wie z.B. Essigester oder auch Gemische hiervon und dergleichen. Das Verhältnis zwischen Rhodium und den Liganden der Formel I liegt zweckmässig zwischen etwa 0,05 und etwa 5 Mol, vorzugsweise zwischen etwa 0,5 und etwa 2 Mol Rhodium pro Mol Ligand der Formel I. 

  Das Verhältnis zwischen Rhodium, in den Komplexen mit den Liganden der Formel I, und den zu hydrierenden Verbindungen liegt zweckmässig zwischen etwa 0,00001 und etwa 5   Gew.- 10,    vorzugsweise zwischen etwa 0,001 und etwa 0,5 Gew.-%.



   Die asymmetrischen Hydrierungen unter Verwendung von Rhodium-Komplexen mit den Liganden der Formel I können zweckmässig bei Temperaturen von etwa 200C bis etwa   100"C,    vorzugsweise von etwa   40"C    bis etwa   90"C,    durchgeführt werden. Diese Hydrierungen erfolgen zweckmässig unter Druck, insbesondere unter einem Druck von etwa 1 bis 100 bar, vorzugsweise 2 bis 50 bar. 



  
 



   The present invention relates to new chiral phosphines



  the general formula
EMI2.1
 wherein R aryl and Rl the group
EMI2.2
 represents, wherein R2 is aryl, di-arylamino, di-lower alkylamino, hydroxy, aryloxy or lower alkoxy.



   The invention further relates to the preparation of the phosphines of the formula I and their use for asymmetric hydrogenations.



   In the context of the present invention, the term aryl means phenyl, which may optionally have lower alkyl or lower alkoxy groups, preferably methyl or methoxy groups, or else di-lower alkylamino, preferably dimethylamino groups in the para and / or meta position. In addition, two aryl groups on the same phosphorus atom can be directly connected to one another via the o-position or also via a methylene, ethylene or propylene group.



  The term aryloxy means groups in which the aryl radical has the previous meaning. The term lower alkyl in the context of the present invention means straight-chain and branched alkyl groups having 1 to 7 carbon atoms, such as e.g. Methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert. Butyl and the like. The term lower alkoxy means groups in which the alkyl radical has the previous meaning. Furthermore, the sign <means that the corresponding residue is above the molecular level, while the sign "" "means that the corresponding residue is below the molecular level.



   Preferred phosphines of the formula I are those in which R is phenyl, p-tolyl, m-tolyl or 3,5-xylyl and R2 in the radicals R 1 is phenyl, p-tolyl, m-tolyl, phenoxy or di-lower alkylamino.



   The following can be mentioned as an example of a preferred compound of the formula 1: {(2S, 4S) -2 - [(Diphenylphosphino) methyl] -4- (diphenylphosphino) -1-pyrrodidinyl} diphenylphosphine sulfide.



   The compounds of the formula I according to the invention can be prepared by adding a compound of the general formula
EMI2.3
 wherein R has the above meaning, with a compound of the general formula
EMI2.4
 where R2 has the meaning given above and R3 means chlorine or fluorine.



   They can also be prepared by using a compound of the general formula
EMI2.5
 wherein Rl has the above meaning and R4 is aryl or lower alkyl, with a compound of the general formula
EMI2.6
 where R has the meaning given above and R5 represents lithium, sodium, potassium or magnesium halide.



   The reaction of the compounds of the formula II with that of the formula IIId can be carried out in a manner known per se, the only thing to take care of is that under strict oxygen exclusion, i.e. under an inert gas atmosphere, e.g. working under nitrogen, argon and the like.



  The reaction may conveniently be carried out in an inert organic solvent such as an aromatic hydrocarbon, e.g.



  Benzene, toluene and the like, or in an ether such as diethyl ether, tetrahydrofuran, dioxane and the like and optionally with the addition of a tert. Amines are done. The temperature and the pressure are not critical parameters in this reaction, which can therefore be carried out without problems at about room temperature and atmospheric pressure.



   The compounds of the formulas II and IIId used as starting material are known compounds or analogs of known compounds which can easily be prepared in a manner analogous to the preparation of the known compounds.



   The reaction of the compounds of forms IV with those of the formula V can be carried out in a manner known per se, the only thing to be taken into account is that under strict exclusion of oxygen, i.e. under an inert gas atmosphere, e.g. working under nitrogen, argon and the like.



  The reaction is conveniently carried out in an inert organic solvent such as an ether, e.g. Tetrahydrofuran, dioxane, diethyl ether and the like, if desired in the presence of a hydrocarbon, e.g. Hexane, benzene, toluene and the like. The reaction is expediently carried out at a temperature of about -15.degree. C. to about room temperature, preferably at about -10.degree. C. to about 0 C. The pressure is not a critical variable in this reaction, which can therefore be carried out easily at atmospheric pressure.



   The compounds of formula IV used as starting material are new compounds and as such are also the subject of the present invention. However, they can be used in a manner known per se, e.g. be prepared according to the following reaction scheme. Ts means the tosyl group and A the group
EMI3.1
 Reaction scheme
EMI3.2

The compounds of the formula V which are also used as starting material are known or analogs of known compounds which can easily be prepared in a manner analogous to the preparation of the known compounds.



   The phosphines of the formula I according to the invention form complexes with rhodium which can be used as catalysts in asymmetric hydrogenations. These catalysts, i.e.



  the complexes of rhodium and the phosphines of formula I are new and also the subject of the present invention.



  These catalysts can be prepared in a simple and known manner, e.g. by reacting a compound of formula I with a rhodium donating compound in a suitable inert organic solvent. Suitable rhodium-donating compounds which may be mentioned are, for example, rhodium trichloride hydrate, rhodium tribromide hydrate, rhodium sulfate, or else organic rhodium complexes with ethylene, propylene and the like, and with bis-olefins, e.g. 1,5-cyclooctadiene, 1,5-hexadiene, bicyclo -2,2, l-hepta-2,5-diene or with other dienes which form complexes which are readily soluble with rhodium. Preferred rhodium-donating compounds are u, u'-dichlorobis [bis (olefin) rhodium (I)], e.g.

  B. u, u'-dichloro-bis- [1,5-cyclooctadiene rhodium (I) j or also u, u'-dichloro-bis - [(norbornadiene) rhodium (I)].



   As already mentioned, the phosphines according to the invention serve as ligands in rhodium complexes, which are used as catalysts in asymmetric hydrogenations.

 

  They are particularly interesting in connection with the asymmetric hydrogenation of a-keto-carboxylic acid esters to the corresponding a-hydroxy-carboxylic acid esters and in particular of dihydro-4,4-dimethyl-2,3-furandione (ketopantolactone) to the corresponding R- (a- Hydroxy-ss, ss-dimethyl-Y-butyrolactone) [R - (-) - pantolactone].



   To carry out the asymmetric hydrogenation mentioned, the phosphines of the formula I as such, in a solution of an asymmetrically hydrogenated compound, can be brought into contact with a rhodium-donating compound. On the other hand, the phosphines of the formula I can first be reacted in a suitable solvent with a rhodium-donating compound to give the corresponding catalyst complex, and this can then be added to a solution of an asymmetrically hydrogenated compound.



   Both the reaction of the phosphines of the formula I with rhodium-donating compound and the asymmetric hydrogenations mentioned can be carried out in suitable organic solvents which are inert under the reaction conditions. As such, lower alkanols such as e.g. Methanol or ethanol, aromatic hydrocarbons such as benzene or toluoyl, cyclic ethers such as tetrahydrofuran or dioxane, esters such as e.g. Ethyl acetate or mixtures thereof and the like. The ratio between rhodium and the ligands of the formula I is advantageously between about 0.05 and about 5 moles, preferably between about 0.5 and about 2 moles of rhodium per mole of the ligand of the formula I.

  The ratio between rhodium, in the complexes with the ligands of the formula I, and the compounds to be hydrogenated is advantageously between about 0.00001 and about 5% by weight, preferably between about 0.001 and about 0.5% by weight.



   The asymmetric hydrogenations using rhodium complexes with the ligands of the formula I can expediently be carried out at from about 200 ° C. to about 100 ° C., preferably from about 40 ° C. to about 90 ° C. These hydrogenations are advantageously carried out under pressure, in particular under a pressure of about 1 to 100 bar, preferably 2 to 50 bar.

Claims (7)

PATENTANSPRÜCHE 1. Chirale Phosphine der allgemeinen Formel EMI1.1 - worin R Aryl und Rl die Gruppe EMI1.2 darstellt, wobei R2 Aryl, di-Arylamino, di-niederes Alkylamino, Hydroxy, Aryloxy oder niederes Alkoxy bedeuten.  PATENT CLAIMS 1. Chiral phosphines of the general formula EMI1.1  - wherein R aryl and Rl the group EMI1.2  represents, wherein R2 is aryl, di-arylamino, di-lower alkylamino, hydroxy, aryloxy or lower alkoxy. 2. Chirale Phosphine gemäss Anspruch 1, dadurch gekennzeichnet, dass R Phenyl, p-Tolyl oder m-Tolyl und R2 in dem Rest Rl Phenyl, p-Tolyl oder m-Tolyl darstellen.  2. Chiral phosphines according to claim 1, characterized in that R represents phenyl, p-tolyl or m-tolyl and R2 in the remainder Rl phenyl, p-tolyl or m-tolyl. 3. Verfahren zur Herstellung von chiralen Phosphinen der allgemeinen Formel EMI1.3 worin R Aryl und Rl die Gruppe EMI1.4 darstellt und R2 Aryl, di-Arylamino, di-niederes Alkylamino, Hydroxy, Aryloxy oder niederes Alkoxy bedeuten, dadurch gekennzeichnet, dass man eine Verbindung der allgemeinen Formel EMI1.5 worin R die obige Bedeutung hat, mit einer Verbindung der allgemeinen Formel EMI1.6 worin R2 die obige Bedeutung hat und R3 Chlor oder Fluor bedeutet, umsetzt.  3. Process for the preparation of chiral phosphines of the general formula EMI1.3  wherein R aryl and Rl the group EMI1.4  represents and R2 mean aryl, di-arylamino, di-lower alkylamino, hydroxy, aryloxy or lower alkoxy, characterized in that a compound of the general formula EMI1.5  wherein R has the above meaning, with a compound of the general formula EMI1.6  where R2 has the meaning given above and R3 means chlorine or fluorine. 4. Verfahren zur Herstellung von chiralen Phosphinen der allgemeinen Formel EMI1.7 worin R Aryl und Rl die Gruppe EMI1.8 darstellt, wobei R2 Aryl, di-Arylamino, di-niederes Alkylamino, Hydroxy, Aryloxy oder niederes Alkoxy bedeuten, dadurch gekennzeichnet, dass man eine Verbindung der allgemeinen Formel EMI1.9 worin Rl die obige Bedeutung hat und R4 Aryl oder niederes Alkyl bedeutet, mit einer Verbindung der allgemeinen Formel EMI1.10 worin R die obige Bedeutung hat und R5 Lithium, Natrium, Kalium oder Magnesium darstellt, umsetzt.  4. Process for the preparation of chiral phosphines of the general formula EMI1.7  wherein R aryl and Rl the group EMI 1.8  represents, wherein R2 is aryl, di-arylamino, di-lower alkylamino, hydroxy, aryloxy or lower alkoxy, characterized in that a compound of the general formula EMI1.9  wherein Rl has the above meaning and R4 is aryl or lower alkyl, with a compound of the general formula EMI1.10  where R has the meaning given above and R5 represents lithium, sodium, potassium or magnesium.   5. Rhodiumkomplexe enthaltend als Ligand ein chirales Phosphin der allgemeinen Formel I gemäss einem der Ansprüche 1 oder 2.  5. Rhodium complexes containing as a ligand a chiral phosphine of the general formula I according to one of claims 1 or 2. 6. Verwendung eines Rhodiumkomplexes gemäss Anspruch 5, als Katalysator bei asymmetrischen Hydrierungen.  6. Use of a rhodium complex according to claim 5, as a catalyst in asymmetric hydrogenations. 7. Verbindungen der allgemeinen Formel EMI1.11 worin R4 Aryl oder niederes Alkyl und Rl die Gruppe EMI1.12 darstellt, wobei R2 Aryl, di-Arylamino, di-niederes Alkylamino, Hydroxy, Aryloxy oder niederes Alkoxy bedeuten, als Ausgangsstoffe für das Verfahren gemäss Anspruch 4.  7. Compounds of the general formula EMI 1.11  wherein R4 is aryl or lower alkyl and Rl is the group EMI1.12  represents, where R2 is aryl, di-arylamino, di-lower alkylamino, hydroxy, aryloxy or lower alkoxy, as starting materials for the process according to claim 4.
CH7010/82A 1982-02-05 1982-12-02 Phosphorus compounds CH653338A5 (en)

Priority Applications (9)

Application Number Priority Date Filing Date Title
CH7010/82A CH653338A5 (en) 1982-12-02 1982-12-02 Phosphorus compounds
US06/458,418 US4539411A (en) 1982-02-05 1983-01-17 Rhodium complexes of chiral phosphines
IT19195/83A IT1175910B (en) 1982-02-05 1983-01-20 PHOSPHORUS COMPOUNDS
DE19833302697 DE3302697A1 (en) 1982-02-05 1983-01-27 PHOSPHORIC CONNECTIONS
NL8300354A NL8300354A (en) 1982-02-05 1983-01-31 PHOSPHORUS COMPOUNDS.
FR8301684A FR2521145B1 (en) 1982-02-05 1983-02-03 CHIRAL PHOSPHINES, PROCESSES FOR THEIR PREPARATION, INTERMEDIATE PRODUCTS FOR THEIR PREPARATION, RHODIUM COMPLEXES THEREOF AND USE OF THE SAME IN ASYMMETRIC HYDROGENATIONS
GB08303161A GB2114134B (en) 1982-02-05 1983-02-04 Phosphorus compounds
AT0039383A AT389312B (en) 1982-02-05 1983-02-04 METHOD FOR PRODUCING NEW CHIRAL PHOSPHINES
US06/744,584 US4620013A (en) 1982-02-05 1985-06-14 Chiral phosphines

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