WO2001007449A1 - Phosphine/palladium complex catalysts for arylation of olefins - Google Patents

Phosphine/palladium complex catalysts for arylation of olefins Download PDF

Info

Publication number
WO2001007449A1
WO2001007449A1 PCT/FR2000/002148 FR0002148W WO0107449A1 WO 2001007449 A1 WO2001007449 A1 WO 2001007449A1 FR 0002148 W FR0002148 W FR 0002148W WO 0107449 A1 WO0107449 A1 WO 0107449A1
Authority
WO
WIPO (PCT)
Prior art keywords
substituents
radical
group
phosphine
independently
Prior art date
Application number
PCT/FR2000/002148
Other languages
French (fr)
Inventor
Jean-Michel Brunel
Gérard Buono
Andréas HEUMANN
Original Assignee
Centre National De La Recherche Scientifique
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Centre National De La Recherche Scientifique filed Critical Centre National De La Recherche Scientifique
Priority to AU70084/00A priority Critical patent/AU7008400A/en
Publication of WO2001007449A1 publication Critical patent/WO2001007449A1/en

Links

Classifications

    • 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
    • C07F15/006—Palladium compounds
    • C07F15/0066—Palladium compounds without a metal-carbon linkage
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
    • B01J31/1845—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing phosphorus
    • B01J31/1865—Phosphonites (RP(OR)2), their isomeric phosphinates (R2(RO)P=O) and RO-substitution derivatives thereof
    • B01J31/187—Amide derivatives thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/24—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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
    • C07C2/86—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation between a hydrocarbon and a non-hydrocarbon
    • C07C2/861—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation between a hydrocarbon and a non-hydrocarbon the non-hydrocarbon contains only halogen as hetero-atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • 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
    • C07C67/333—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton
    • C07C67/343—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
    • 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
    • C07F9/28—Phosphorus compounds with one or more P—C bonds
    • C07F9/48—Phosphonous acids [RP(OH)2] including [RHP(=O)(OH)]; Thiophosphonous acids including [RP(SH)2], [RHP(=S)(SH)]; Derivatives thereof
    • C07F9/4883—Amides or esteramides thereof, e.g. RP(NR'2)2 or RP(XR')(NR''2) (X = O, S)
    • 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
    • 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
    • C07F9/576—Six-membered rings
    • C07F9/59—Hydrogenated pyridine rings
    • 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
    • C07F9/6581—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and nitrogen atoms with or without oxygen or sulfur atoms, as ring hetero atoms
    • C07F9/6584—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and nitrogen atoms with or without oxygen or sulfur atoms, as ring hetero atoms having one phosphorus atom as ring hetero atom
    • C07F9/65848—Cyclic amide derivatives of acids of phosphorus, in which two nitrogen atoms belong to the ring
    • 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
    • B01J2231/30—Addition reactions at carbon centres, i.e. to either C-C or C-X multiple bonds
    • B01J2231/32—Addition reactions to C=C or C-C triple bonds
    • B01J2231/323—Hydrometalation, e.g. bor-, alumin-, silyl-, zirconation or analoguous reactions like carbometalation, hydrocarbation
    • 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
    • B01J2231/40—Substitution reactions at carbon centres, e.g. C-C or C-X, i.e. carbon-hetero atom, cross-coupling, C-H activation or ring-opening reactions
    • B01J2231/42—Catalytic cross-coupling, i.e. connection of previously not connected C-atoms or C- and X-atoms without rearrangement
    • B01J2231/4205—C-C cross-coupling, e.g. metal catalyzed or Friedel-Crafts type
    • B01J2231/4261—Heck-type, i.e. RY + C=C, in which R is aryl
    • 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
    • B01J2531/824—Palladium
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2531/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • C07C2531/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • C07C2531/24—Phosphines

Definitions

  • the present invention relates to phosphines and their use for the development of palladium complexes, useful as catalysts in particular for the arylation of olefins.
  • the object of the present invention is to provide new phosphine / palladium complexes which are useful as catalysts for the arylation of functionalized or non-functionalized olefins, which have markedly improved performance compared to the phosphine / palladium complexes of the prior art, which are easy to prepare and which can carry chiral ligands.
  • the subject of the present invention is phosphines, their use for the preparation of phosphine / palladium complexes useful as catalysts, in particular for the arylation of olefins, functionalized or not.
  • a phosphine according to the present invention is characterized in that it comprises a phosphorus atom carrying on the one hand an o-tolyl group optionally carrying substituents, and on the other hand two secondary or tertiary amine substituents.
  • phosphines according to the invention which are particularly preferred are those which correspond to the general formula (D:
  • the substituents RI, R2, R3 and R4 independently of one another represent a hydrogen atom, an alkyl radical, an alkenyl radical or an aryl radical, it being understood that at most one of the substituents RI and R2 is a hydrogen atom and at most one of the substituents R3 and R4 is a hydrogen atom; either the substituents R1 and R2 on the one hand, and / or the substituents R3 and R4 on the other hand form together a biradical which forms an aromatic heterocycle or not with the nitrogen atom which carries them, or else the one of the substituents RI or R2 forms with the substituents R3 and R4 a trivalent radical which forms heterocycles condensed aromatic or not with the segment -NPN-; the substituents Zi, Z 2 , Z 3 and Z 4 represent independently of each other: * an alkyl group, an aryl group, a cycloalkyl group, an alkenyl group; * a group R'
  • R ' a group (R '") 3 Si- in which the substituents R represent, independently of each other, H, an alkyl radical, an aryl radical, an alkyloxy radical or an aryloxy radical;
  • the substituents of the amino groups carried by the phosphorus may be identical or different.
  • the Zi substituents can be of the same nature or not. Likewise, the substituents R ', R ", R" 1 or R'"can be identical or different.
  • substituents R 1 and the substituents Z 1 represent an alkyl radical having from 1 to 18 carbon atoms, a cycloalkyl group having from 5 to 18 carbon atoms or an aryl group having from 6 to 14 carbon atoms.
  • substituents R 1 represents a methyl radical and each of the substituents Z x represents a hydrogen atom are particularly preferred.
  • a [bis (dimethylamino)] -o-tolylphosphine of the present invention can be prepared by a process consisting in condensing the magnesium of the appropriate 2-halotoluene with chloro [bis (dimethylamino)] phosphine, according to the following reaction scheme: MgXCl
  • the process for obtaining a [bis (dimethylamino)] -o-tolylphosphine of the invention comprises the following steps: a1) slow addition of an o-tolylmagnesium halide carrying the Zi substituents suitable for chloro [bis-
  • step a1) makes it possible to modify the aromatic part of the phosphine of the invention.
  • the simplest compound is an o-tolylmagnesium halide shown in the reaction scheme above. It is also possible to use an o-tolylmagnesium halide carrying the appropriate substituents Zi.
  • the hydrolysis of step c1) is preferably carried out at approximately 0 ° C., for example by operating in a mixture of ice water and of solvent.
  • hydrocarbon solvent there may be mentioned, for example, pentane, dichloromethane, trichloromethane or petroleum ether.
  • oxygenated solvent there may be mentioned for example ethyl acetate, diethyl ether or tetrahydro- furan. Diethyl ether is a preferred solvent for the preparation of [bis (dimethylamino)] -o-tolylphosphine.
  • the phosphines according to the invention in which one or more substituents R 1 are not methyl radicals can be obtained by reacting the [bis (dimethylamino)] -o-tolylphosphine with the appropriate amine (s) under reflux of an aprotic solvent such as than toluene, benzene, xylene or cyclohexane.
  • an aprotic solvent such as than toluene, benzene, xylene or cyclohexane.
  • aminophosphines of the present invention are advantageously used for the development of phosphine / palladium complexes useful as catalysts for various reactions.
  • a catalyst complex according to the invention can be obtained by reacting a source of palladium with an aminophosphine of the invention, at a temperature between 20 ° C and 120 ° C, in a polar solvent, preferably chosen from DMSO, acetonitrile, DMF or dimethyl acetamide, in the presence of a quaternary ammonium salt R 4 NX in which the substituents R are chosen independently from one another from alkyl radicals having from 3 to 10 atoms of carbon, preferably 4 to 6 carbon atoms, and benzyl, and X is halogen.
  • a quaternary ammonium salt R 4 NX in which the substituents R are chosen independently from one another from alkyl radicals having from 3 to 10 atoms of carbon, preferably 4 to 6 carbon atoms, and benzyl, and X is halogen.
  • a quaternary ammonium salt R 4 NX in which the substituents R are chosen independently from one another from alkyl radical
  • the phosphine / palladium complex When it is desired to use the phosphine / palladium complex as a catalyst for an arylation or hydroarylation reaction of an olefin without first extracting it from the reaction medium in which it is obtained, it is not necessary to '' introduce a quaternary ammonium salt into the reaction medium during the preparation of the phosphine / Pd complex.
  • the halide phosphine / palladium complex in the dry state has a higher stability than the acetate type phosphine / palladium complex obtained without the addition of quaternary ammonium salt.
  • the reaction is preferably carried out at a temperature in the region of 60 ° C.
  • the source of palladium PdX 2 is a palladium compound in its degree of oxidation +11.
  • palladium diacetate Pd (OAc) 2 bis (acetylacetonate) of palladium Pd (Acac) 2 and PdCl 2 (CH 3 CN) 2 .
  • Pd (OAc) 2 is particularly preferred.
  • the reagents are used in proportions such that the phosphine / Pd molar ratio is between 1/1 and 4/1.
  • the solvent can be chosen from dimethyl sulfoxide
  • DMSO dimethylformamide
  • DMF dimethylformamide
  • toluene acetonitrile
  • dimethylacetamide dimethyl trichloride
  • An aminophosphine / Pd complex of the invention can be extracted from the reaction medium by evaporation under vacuum and recrystallization from a solvent. Petroleum ether is particularly suitable.
  • An aminophosphine / Pd complex according to the invention is an air-stable compound. It can therefore be prepared and stored for later use.
  • aminophosphine / Pd complex corresponds to formula (II):
  • the particularly preferred complexes are the complexes corresponding to formula (II) in which the substituents Ri and the substituents Zi represent an alkyl radical having from 1 to 18 carbon atoms, a cycloalkyl group having from 5 to 18 carbon atoms or a group aryl having 6 to 14 carbon atoms.
  • Complexes in which each of the substituents R 1 represents a methyl radical and each of the substituents Z ⁇ represents a hydrogen atom are particularly preferred.
  • An aminophosphine / Pd complex according to the present invention can be used as catalyst for arylation or hydroarylation reactions of olefins, functionalized or not.
  • the complex which is to be used as catalyst is prepared in situ. This mode of implementation is particularly advantageous because of the simplicity of implementation of the process for preparing the complex and its stability in air.
  • the process for arylating an olefin using an aminophosphine / Pd complex according to the invention consists in reacting 1 olefin with an arylating agent in a solvent chosen from toluene, acetonitrile, DMSO, THF or DMF at a temperature of 20 ° C. to 110 ° C. in the presence of an aminophosphine / Pd complex according to the invention, in proportions such that the ligand / Pd ratio is 1/4 to 1/1, preferably 1 , 1/1 to 1.6 / 1.
  • a ligand / Pd ratio of 1.5 / 1 is particularly advantageous. It is particularly advantageous to prepare the aminophosphine / Pd complex in si tu.
  • the arylating agent is chosen from the compounds Ph-X 1 in which X 1 represents a halogen atom or a trifluorosulfonyl substituent (OTf) and Ph represents an aromatic radical.
  • Ph can be an aromatic radical with condensed nuclei, an aromatic ring carrying substituents, or a heteroaromatic ring.
  • iodobenzene By way of example, mention may be made in particular of iodobenzene.
  • An aminophosphine / Pd complex of the invention can also be used as a catalyst for the hydroarylation of an olefin, functionalized or not.
  • the hydroarylation process consists in reacting the olefin with an arylating agent in a polar solvent at a temperature between 20 and 110 ° C. in the presence of an aminophosphine / Pd complex according to the invention, a weak base and d an acid in proportions such that the ligand / Pd ratio is from 1/4 to 1/1, preferably from 1.1 / 1 to 1.6 / 1.
  • a ligand / Pd ratio of 1.5 / 1 is particularly advantageous.
  • the compound to aryler / arylating agent ratio is 1/3 and 1/1 to 3/1.
  • the arylating agent is chosen from Ph-X compounds of the same nature as the arylating agents mentioned above for the arylation of olefins. Iodobenzene is cited as an example.
  • the base is preferably chosen from triethylamine, pyridine, sodium or potassium acetate.
  • the acid is preferably chosen from weak acids such as formic acid and ammonium chloride solutions.
  • the polar solvent can be toluene, acetonitrile, DMSO, THF or DMF.
  • the catalyst complexes according to the invention have various advantages over the palladium complexes of the prior art. Their use for arylation or hydroarylation reactions makes it possible to obtain better TONs (which represents the number of moles of product obtained per mole of Pd) and therefore requires a lower overall amount of catalyst. In addition, they are active at significantly lower concentrations than the palladium complexes of the prior art.
  • the o-tolylmagnesium bromide was prepared in the following manner. In a three-necked flask equipped with an argon inlet, a magnetic bar, a cooler surmounted by an oil bubbler and a dropping funnel, it was introduced at room temperature (20-30 ° C. ) 6.9 g (0.3 mole) of magnesium in turnings and 100 ml of anhydrous and degassed THF. An iodine crystal was added to initiate the reaction, and then dropwise 51.3 g (0.3 mole) of 2-bromotoluene. After the addition was complete, the mixture was stirred for one hour at room temperature.
  • the chloro [bis (dimethylamino)] phosphine was prepared in parallel according to the following procedure.
  • a 1 1 reactor comprising a nitrogen inlet, a condenser fitted with an oil bubbler, a dropping funnel and a stirring system, 13.7 g (0 , 1 mole) of phosphorus trichloride.
  • 32.6 g (0.2 mole) of tris (dimethylamino) phosphine was added slowly while cooling with ice. After the addition was complete, the mixture was heated at 100 ° C for 20 minutes.
  • the chloro [bis (dimethylamino)] phosphine was then diluted in 400 ml of anhydrous diethyl ether and degassed.
  • the o-tolylmagnesium bromide solution was added at 0 ° C to the ethereal solution of chloro [bis (dimethylamino)] - phosphine over a period of 2 hours.
  • the reaction mixture was allowed to return to room temperature, then allowed to stir overnight.
  • the reaction medium was hydrolyzed with a solution of 96.0 g of ethylene diamine tetra- acetic acid (EDTA) and 55.2 g of NaOH in 600 ml of ice water and 200 ml of diethyl ether. After a few minutes of stirring, then decantation, the aqueous phase was extracted with 2x200 ml of diethyl ether. The combined organic phases were dried over potassium carbonate. After filtration and evaporation of the solvent, the product was distilled under reduced pressure.
  • EDTA ethylene diamine tetra- acetic acid
  • the catalyst complex was prepared according to the following reaction scheme:
  • the product was obtained with a yield of 99% in the form of a colorless oil. Its characteristics are as follows.
  • the catalyst complex according to the invention makes it possible to obtain very advantageous performances.
  • An olefin conversion rate of 100% can be achieved when the solvent for the reaction medium is DMSO.
  • the choice of an arylating agent of the iodide type makes it possible to obtain very high TONs, greater than 10 6 with yields of 98 to 99%.
  • the product was obtained with a yield of 99% in the form of a colorless oil. Its characteristics are as follows.
  • the product was obtained with a yield of 99% in the form of a colorless oil. Its characteristics are as follows.
  • Tests 1 to 3 were carried out using a complex in which the ligand L is phosphine corresponding to formula 4 below, corresponding to [bis (dimethylamino)] -o-tolylphosphine.
  • Tests No. 8 to 10 were carried out using a complex in which the ligand L is phosphine corresponding to formulas 1, 2 and 3 respectively.
  • Tests No. 4 to 7 are comparative examples carried out using a so-called Herrmann catalyst complex, corresponding to the following formula:

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Biochemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Molecular Biology (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)

Abstract

The invention concerns phosphines and their use for preparing palladium complexes, useful as catalysts for arylation and hydroarylation of olefins. The phosphines comprise a phosphorus atom bearing an o-tolyl group optionally substituted, and two secondary or tertiary amine groups. The substituents of the amines are selected among hydrogen, an alkyl radical, an alkenyl radical or an aryl radical, not more than one of the substituents R1 and R2 is a hydrogen atom, and not more than one of the substituents R3 and R4 is a hydrogen atom; or the substituents R1 and R2, and/or the substituents R3 and R4 together form a biradical which constitutes a heterocycle with the nitrogen atom bearing them, or still one of the substituents R1 or R2 forms with the substituents R3 and r4 a trivalent radical which constitutes condensed heterocycles with the -N-P-N- segment.

Description

COMPLEXES DE PHOSPHINE/PALLADIUM CATALYSEURS POUR L'ARYLATION D'OLEFINES PHOSPHINE / PALLADIUM COMPLEXES CATALYSTS FOR OLEFIN ARYLATION
La présente invention concerne des phosphines et leur utilisation pour l'élaboration de complexes de palladium, utiles comme catalyseurs notamment pour l'arylation d'oléfines .The present invention relates to phosphines and their use for the development of palladium complexes, useful as catalysts in particular for the arylation of olefins.
De nombreuses réactions de synthèse organique sont effectuées en présence de catalyseurs organométalliques . Les complexes du palladium constituent une classe intéressante de tels catalyseurs. Ils sont particulièrement utiles pour les réactions d'alkylation allylique ou pour les réactions de condensation d'un halogénure aromatique sur une oléfine fonctionnalisée ou non (dites « réactions de Heck ») . EP-0719758 (W. A. Herrmann, et al., 1996) décrit des cataly- seurs obtenus à partir de N,N' -dialkyle imidazole et d'un complexe du Pd(II), efficaces dans la réaction de Heck, notamment pour la condensation du bromobenzène sur des esters acryliques. On connaît par W. A. Herrmann, et al., (Angew. Chem. Int. Ed. Engl . 1994, 33, 2379-2411) des complexes obtenus à partir de tri o-tolyl phosphine et d'acétate de palladium. Il s'agit d'un complexe très stable utile notamment pour la réaction entre un bromure d' aryle et le bishydroxy aryl borane pour l'obtention d'un di-aryle (couplage dit de Susuki) . Par M. Nouroozian, et al., (Congrès de Gôttingen, 1997), on connaît des complexes du type furanique, similaires au complexe de Herrmann cité ci-dessus.Many organic synthesis reactions are carried out in the presence of organometallic catalysts. Palladium complexes are an interesting class of such catalysts. They are particularly useful for allylic alkylation reactions or for condensation reactions of an aromatic halide on a functionalized or non-functionalized olefin (called "Heck reactions"). EP-0719758 (WA Herrmann, et al., 1996) describes catalysts obtained from N, N '-dialkyle imidazole and a Pd (II) complex, effective in the Heck reaction, in particular for the condensation of bromobenzene on acrylic esters. We know from W. A. Herrmann, et al. (Angew. Chem. Int. Ed. Engl. 1994, 33, 2379-2411) of complexes obtained from tri-tolyl phosphine and palladium acetate. It is a very stable complex useful in particular for the reaction between an aryl bromide and bishydroxy aryl borane to obtain a di-aryl (so-called Susuki coupling). By M. Nouroozian, et al. (Gôttingen Congress, 1997), complexes of the furan type are known, similar to the Herrmann complex cited above.
On connaît en outre des complexes diazaphospholidines chirales et d'un sel de palladium (0. Legrand, et al., .Che .Also known are chiral diazaphospholidine complexes and a palladium salt (0. Legrand, et al., .Che.
Eur. J. 1998, 4, 1061-167), utilisés pour des réactions de catalyse homogène asymétrique. On connaît également les complexes phosphine/Pd décrits par J.M. Brunel, et al. (Tetrahedron Letters, 1997, vol. 38, n° 34, 5971-5974).Eur. J. 1998, 4, 1061-167), used for asymmetric homogeneous catalysis reactions. The phosphine / Pd complexes described by J.M. Brunel, et al. Are also known. (Tetrahedron Letters, 1997, vol. 38, n ° 34, 5971-5974).
La présente invention a pour but de fournir de nouveaux complexes phosphine / palladium utiles comme catalyseurs pour l'arylation d'oléfines fonctionnalisées ou non, qui ont des performances nettement améliorées par rapport aux complexes phosphine / palladium de l'art antérieur, qui sont aisés a préparer et qui peuvent porter des ligands chiraux. C'est pourquoi la présente invention a pour objets des phosphines, leur utilisation pour l'élaboration de complexes phosphine / palladium utiles comme catalyseurs, notamment pour l'arylation d'oléfines fonctionnalisées ou non.The object of the present invention is to provide new phosphine / palladium complexes which are useful as catalysts for the arylation of functionalized or non-functionalized olefins, which have markedly improved performance compared to the phosphine / palladium complexes of the prior art, which are easy to prepare and which can carry chiral ligands. This is why the subject of the present invention is phosphines, their use for the preparation of phosphine / palladium complexes useful as catalysts, in particular for the arylation of olefins, functionalized or not.
Une phosphine selon la présente invention est caractérisée en ce qu'elle comprend un atome de phosphore portant d'une part un groupe o-tolyle portant éventuellement des substituants, et d'autre part deux substituants aminé secondaire ou tertiaire.A phosphine according to the present invention is characterized in that it comprises a phosphorus atom carrying on the one hand an o-tolyl group optionally carrying substituents, and on the other hand two secondary or tertiary amine substituents.
Les phosphines selon l'invention particulièrement préférées sont celles qui répondent à la formule générale (D :The phosphines according to the invention which are particularly preferred are those which correspond to the general formula (D:
Figure imgf000003_0001
Figure imgf000003_0001
dans laquelle : - les substituants RI, R2 , R3 et R4 représentent indépendamment les uns des autres un atome d'hydrogène, un radical alkyle, un radical alcenyle ou un radical aryle, étant entendu que au plus l'un des substituants RI et R2 est un atome d'hydrogène et au plus l'un des substituants R3 et R4 est un atome d'hydrogène ; ou bien les substituants RI et R2 d'une part, et/ou les substituants R3 et R4 d'autre part forment ensemble un biradical qui forme un heterocycle aromatique ou non avec l'atome d'azote qui les porte, ou bien l'un des substituants RI ou R2 forme avec les substituants R3 et R4 un radical trivalent qui forme des heterocycles condensés aromatiques ou non avec le segment -N-P-N- ; les substituants Zi, Z2, Z3 et Z4 représentent indépendamment les uns des autres : * un groupe alkyle, un groupe aryle, un groupe cycloalkyle, un groupe alcenyle ; * un groupe R'O-, dans lequel R' représente H, un radical alkyle, un radical aryle, un radical trialkylsilyle ou un radical triarylsilyle ;in which: the substituents RI, R2, R3 and R4 independently of one another represent a hydrogen atom, an alkyl radical, an alkenyl radical or an aryl radical, it being understood that at most one of the substituents RI and R2 is a hydrogen atom and at most one of the substituents R3 and R4 is a hydrogen atom; either the substituents R1 and R2 on the one hand, and / or the substituents R3 and R4 on the other hand form together a biradical which forms an aromatic heterocycle or not with the nitrogen atom which carries them, or else the one of the substituents RI or R2 forms with the substituents R3 and R4 a trivalent radical which forms heterocycles condensed aromatic or not with the segment -NPN-; the substituents Zi, Z 2 , Z 3 and Z 4 represent independently of each other: * an alkyl group, an aryl group, a cycloalkyl group, an alkenyl group; * a group R'O-, in which R 'represents H, an alkyl radical, an aryl radical, a trialkylsilyl radical or a triarylsilyl radical;
* un groupe (R")2N- dans lequel les substituants R" représentent indépendamment les uns des autres H, un radical alkyle ou un radical aryle ;* a group (R ") 2 N- in which the substituents R" independently of one another represent H, an alkyl radical or an aryl radical;
* un groupe (R'")3Si- dans lequel les substituants R représentent indépendamment les uns des autres H, un radical alkyle, un radical aryle, un radical alkyloxy ou un radical aryloxy ;* a group (R '") 3 Si- in which the substituents R represent, independently of each other, H, an alkyl radical, an aryl radical, an alkyloxy radical or an aryloxy radical;
* un groupe P(R"")2, un groupe PO(R"")2, un groupe PS(R"")2 ou un groupe PSe(R"")2, dans lequel les substituants R"" représentent indépendamment les uns des autres H, un radical alkyle, un radical aryle, un radical alkyloxy ou un radical aryloxy.* a group P (R "") 2 , a group PO (R "") 2 , a group PS (R "") 2 or a group PSe (R "") 2 , in which the substituents R "" independently represent each other H, an alkyl radical, an aryl radical, an alkyloxy radical or an aryloxy radical.
Dans un composé répondant à la formule (I), les substituants des groupes aminés portés par le phosphore peuvent être identiques ou différents.In a compound corresponding to formula (I), the substituents of the amino groups carried by the phosphorus may be identical or different.
Les substituants Zi peuvent être de même nature ou non. De même, les substituants R', R", R"1 ou R'" peuvent être identiques ou différents.The Zi substituents can be of the same nature or not. Likewise, the substituents R ', R ", R" 1 or R'"can be identical or different.
Parmi les composés de formule (I), on préfère ceux dans lesquels les substituants Ri et les substituants Zi représentent un radical alkyle ayant de 1 à 18 atomes de carbone, un groupe cycloalkyle ayant de 5 à 18 atomes de carbone ou un groupe aryle ayant de 6 à 14 atomes de carbone. Les composés dans lesquels chacun des substituants Ri représente un radical méthyle et chacun des substituants Zx représente un atome d'hydrogène sont particulièrement préférés. Une [bis (diméthylamino) ] -o-tolylphosphine de la présente invention peut être préparée par un procédé consistant à condenser le magnésien du 2-halogénotoluène approprié avec la chloro [bis (diméthylamino) ] phosphine, selon le schéma réactionnel suivant : MgXCl
Figure imgf000005_0001
Among the compounds of formula (I), preferred are those in which the substituents R 1 and the substituents Z 1 represent an alkyl radical having from 1 to 18 carbon atoms, a cycloalkyl group having from 5 to 18 carbon atoms or an aryl group having from 6 to 14 carbon atoms. The compounds in which each of the substituents R 1 represents a methyl radical and each of the substituents Z x represents a hydrogen atom are particularly preferred. A [bis (dimethylamino)] -o-tolylphosphine of the present invention can be prepared by a process consisting in condensing the magnesium of the appropriate 2-halotoluene with chloro [bis (dimethylamino)] phosphine, according to the following reaction scheme: MgXCl
Figure imgf000005_0001
X = Br, Cl, IX = Br, Cl, I
Dans un mode de réalisation particulier, le procédé pour l'obtention d'une [bis (diméthylamino) ] -o-tolylphosphine de l'invention comprend les étapes suivantes : al) addition lente d'un halogénure d' o-tolylmagnésium portant les substituants Zi appropriés à la chloro[bis-In a particular embodiment, the process for obtaining a [bis (dimethylamino)] -o-tolylphosphine of the invention comprises the following steps: a1) slow addition of an o-tolylmagnesium halide carrying the Zi substituents suitable for chloro [bis-
(diméthylamino) phosphine à une température entre -78 °C et(dimethylamino) phosphine at a temperature between -78 ° C and
+30°C, dans un solvant hydrocarboné ou oxygéné, sous atmosphère neutre et anhydre, dans des proportions stœchiométriques ; bl) maintien sous agitation à température ambiante pendant une durée de 8 à 15 heures, de préférence 12 heures ; cl) hydrolyse à une température entre -78°C et +30°C à l'aide d'une solution d'éthylène diamine tétracétate (EDTA) et d'une base choisie parmi NaOH et KOH et dans un solvant hydrocarboné ou oxygéné ; dl) extraction de la [bis (diméthylamino) ] -o-tolylphosphine à l'aide d'un solvant analogue à celui de l'étape cl) ; el) purification de la [bis (diméthylamino) ] -o-tolyl- phosphine par distillation sous pression réduite.+ 30 ° C, in a hydrocarbon or oxygenated solvent, under a neutral and anhydrous atmosphere, in stoichiometric proportions; bl) maintaining stirring at room temperature for a period of 8 to 15 hours, preferably 12 hours; cl) hydrolysis at a temperature between -78 ° C and + 30 ° C using a solution of ethylene diamine tetracetate (EDTA) and a base chosen from NaOH and KOH and in a hydrocarbon or oxygenated solvent; dl) extraction of [bis (dimethylamino)] -o-tolylphosphine using a solvent similar to that of step cl); el) purification of [bis (dimethylamino)] -o-tolylphosphine by distillation under reduced pressure.
Le choix du composé magnésien utilisé dans l'étape al) permet de modifier la partie aromatique de la phosphine de l'invention. Le composé le plus simple est un halogénure d'o- tolylmagnésium représenté dans le schéma réactionnel ci- dessus. On peut utiliser également un halogénure d'o- tolylmagnésium portant les substituants Zi appropriés. L'hydrolyse de l'étape cl) est effectuée de préférence à environ 0°C, par exemple en opérant dans un mélange d'eau glacée et de solvant. Comme solvant hydrocarboné, on peut citer par exemple le pentane, le dichlorométhane, le trichlorométhane ou l'éther de pétrole. Comme solvant oxygéné, on peut citer par exemple l'acétate d'éthyle, l'éther de diéthyle ou le tétrahydro- furane. L'éther de diéthyle est un solvant préféré pour la préparation de la [bis (diméthylamino) ] -o-tolylphosphine.The choice of the magnesium compound used in step a1) makes it possible to modify the aromatic part of the phosphine of the invention. The simplest compound is an o-tolylmagnesium halide shown in the reaction scheme above. It is also possible to use an o-tolylmagnesium halide carrying the appropriate substituents Zi. The hydrolysis of step c1) is preferably carried out at approximately 0 ° C., for example by operating in a mixture of ice water and of solvent. As hydrocarbon solvent, there may be mentioned, for example, pentane, dichloromethane, trichloromethane or petroleum ether. As oxygenated solvent, there may be mentioned for example ethyl acetate, diethyl ether or tetrahydro- furan. Diethyl ether is a preferred solvent for the preparation of [bis (dimethylamino)] -o-tolylphosphine.
Les phosphines selon l'invention dans lesquelles un ou plusieurs substituants Ri ne sont pas des radicaux méthyle peuvent être obtenus en faisant réagir la [bis (diméthylamino) ] -o-tolylphosphine avec la ou les aminés appropriées sous reflux d'un solvant aprotique tel que le toluène, le benzène, le xylène ou le cyclohexane.The phosphines according to the invention in which one or more substituents R 1 are not methyl radicals can be obtained by reacting the [bis (dimethylamino)] -o-tolylphosphine with the appropriate amine (s) under reflux of an aprotic solvent such as than toluene, benzene, xylene or cyclohexane.
Lorsque les substituants Ri sont des radicaux monovalents, on utilise une ou deux aminés secondaires et le schéma réactionnel peut s'écrire de la manière suivante :When the substituents Ri are monovalent radicals, one or two secondary amines are used and the reaction scheme can be written as follows:
Figure imgf000006_0001
Figure imgf000006_0001
Le solvant est ensuite éliminé et le produit purifié par les méthodes classiques, par exemple par distillation sous pression réduite. A titre d'exemple d'aminés utilisables pour la transformation de la [bis (diméthylamino) ] -o-tolylphosphine, on peut citer la pyrrolidine, la pipéridine ou la (S) -2-anilinométhylpyrrolidine.The solvent is then removed and the product purified by conventional methods, for example by distillation under reduced pressure. By way of example of amines which can be used for the transformation of [bis (dimethylamino)] -o-tolylphosphine, mention may be made of pyrrolidine, piperidine or (S) -2-anilinomethylpyrrolidine.
Lorsque les substituants Ri forment des cycles, on effectue une réaction d'échange entre la [bis (diméthylamino) ] -o-tolylphosphine et une diamine chirale, sous reflux du toluène. Un cas particulier est illustré par le schéma réactionnel suivant :
Figure imgf000007_0001
When the substituents Ri form rings, an exchange reaction is carried out between [bis (dimethylamino)] -o-tolylphosphine and a chiral diamine, under reflux of toluene. A particular case is illustrated by the following reaction scheme:
Figure imgf000007_0001
Les aminophosphines de la présente invention sont avantageusement utilisées pour l'élaboration de complexes phosphine / palladium utiles comme catalyseurs pour diverses réactions.The aminophosphines of the present invention are advantageously used for the development of phosphine / palladium complexes useful as catalysts for various reactions.
Un complexe catalyseur selon l'invention peut être obtenu en faisant réagir une source de palladium avec une aminophosphine de l'invention, à une température comprise entre 20°C et 120°C, dans un solvant polaire, choisi de pré- férence parmi le DMSO, 1 ' acétonitrile, le DMF ou le diméthyl- acétamide, en présence d'un sel d'ammonium quaternaire R4NX dans lequel les substituants R sont choisi indépendamment les uns des autres parmi les radicaux alkyle ayant de 3 à 10 atomes de carbone, de préférence de 4 à 6 atomes de carbone, et le benzyle, et X est un halogène. A titre d'exemple, on peut citer les halogénures de tétrabutylammonium et les halo- génures de benzyltributylammonium. La réaction a lieu de manière quasi-instantanée, selon le schéma réactionnel suivant.A catalyst complex according to the invention can be obtained by reacting a source of palladium with an aminophosphine of the invention, at a temperature between 20 ° C and 120 ° C, in a polar solvent, preferably chosen from DMSO, acetonitrile, DMF or dimethyl acetamide, in the presence of a quaternary ammonium salt R 4 NX in which the substituents R are chosen independently from one another from alkyl radicals having from 3 to 10 atoms of carbon, preferably 4 to 6 carbon atoms, and benzyl, and X is halogen. By way of example, mention may be made of tetrabutylammonium halides and benzyltributylammonium halides. The reaction takes place almost instantaneously, according to the following reaction scheme.
Figure imgf000007_0002
Figure imgf000007_0002
Lorsque l'on souhaite utiliser le complexe phosphine / palladium comme catalyseur d'une réaction d'arylation ou d'hydroarylation d'une oléfine sans l'extraire au préalable du milieu réactionnel dans lequel il est obtenu, il n'est pas nécessaire d'introduire un sel d'ammonium quaternaire dans le milieu réactionnel lors de la préparation du complexe phosphine / Pd. Le complexe phosphine / palladium du type halogénure présente à l'état sec une stabilité supérieure à celle du complexe phosphine / palladium du type acétate obtenu sans l'addition de sel d'ammonium quaternaire.When it is desired to use the phosphine / palladium complex as a catalyst for an arylation or hydroarylation reaction of an olefin without first extracting it from the reaction medium in which it is obtained, it is not necessary to '' introduce a quaternary ammonium salt into the reaction medium during the preparation of the phosphine / Pd complex. The halide phosphine / palladium complex in the dry state has a higher stability than the acetate type phosphine / palladium complex obtained without the addition of quaternary ammonium salt.
On effectue la réaction de préférence a une température voisine de 60°C.The reaction is preferably carried out at a temperature in the region of 60 ° C.
La source de palladium PdX2 est un composé de palladium dans son degré d'oxydation +11. A titre d'exemple, on peut citer le diacétate de palladium Pd(OAc)2, le bis (acétyl- acétonate) de palladium Pd(Acac)2 et PdCl2 (CH3CN) 2. Pd(OAc)2 est particulièrement préféré.The source of palladium PdX 2 is a palladium compound in its degree of oxidation +11. By way of example, mention may be made of palladium diacetate Pd (OAc) 2 , bis (acetylacetonate) of palladium Pd (Acac) 2 and PdCl 2 (CH 3 CN) 2 . Pd (OAc) 2 is particularly preferred.
Les réactifs sont utilisés dans des proportions telles que le rapport molaire phosphine / Pd soit compris entre 1/1 et 4/1.The reagents are used in proportions such that the phosphine / Pd molar ratio is between 1/1 and 4/1.
Le solvant peut être choisi parmi le diméthylsulfoxydeThe solvent can be chosen from dimethyl sulfoxide
(DMSO), le diméthylformamide (DMF), le toluène, 1 ' acéto- nitrile, le diméthylacétamide et le trichlorure de méthyle.(DMSO), dimethylformamide (DMF), toluene, acetonitrile, dimethylacetamide and methyl trichloride.
Le DMSO est particulièrement préféré. Un complexe aminophosphine / Pd de l'invention peut être extrait du milieu réactionnel par évaporation sous vide et recristallisation dans un solvant. L'éther de pétrole est particulièrement approprié. Un complexe aminophosphine / Pd selon l'invention est un composé stable à l'air. Il peut donc être préparé et stocké en vue d'une utilisation ultérieure.DMSO is particularly preferred. An aminophosphine / Pd complex of the invention can be extracted from the reaction medium by evaporation under vacuum and recrystallization from a solvent. Petroleum ether is particularly suitable. An aminophosphine / Pd complex according to the invention is an air-stable compound. It can therefore be prepared and stored for later use.
Un complexe aminophosphine / Pd selon l'invention répond à la formule (II) :An aminophosphine / Pd complex according to the invention corresponds to formula (II):
Figure imgf000008_0001
dans laquelle les substituants Ri et Zx sont définis de la même manière que les substituants Ri et Zα des aminophos- phines de formule (I) et X représente un atome d'halogène.
Figure imgf000008_0001
in which the substituents Ri and Z x are defined in the same way as the substituents Ri and Z α of the aminophosphines of formula (I) and X represents a halogen atom.
Les complexes particulièrement préférés sont les complexes répondant à la formule (II) dans laquelle les substituants Ri et les substituants Zi représentent un radical alkyle ayant de 1 à 18 atomes de carbone, un groupe cycloalkyle ayant de 5 à 18 atomes de carbone ou un groupe aryle ayant de 6 à 14 atomes de carbone. Les complexes dans lesquels chacun des substituants Ri représente un radical méthyle et chacun des substituants Z± représente un atome d'hydrogène sont particulièrement préférés.The particularly preferred complexes are the complexes corresponding to formula (II) in which the substituents Ri and the substituents Zi represent an alkyl radical having from 1 to 18 carbon atoms, a cycloalkyl group having from 5 to 18 carbon atoms or a group aryl having 6 to 14 carbon atoms. Complexes in which each of the substituents R 1 represents a methyl radical and each of the substituents Z ± represents a hydrogen atom are particularly preferred.
Un complexe aminophosphine / Pd selon la présente invention peut être utilisé comme catalyseur pour des réactions d'arylation ou d'hydroarylation d'oléfines, fonctionnalisées ou non. Parmi les oléfines qui peuvent être arylées en présence d'un complexe aminophosphine / Pd selon l'invention, on peut citer à titre d'exemple le cyclohexène, le cyclo- pentène, l'acrylate de butyle, le norbornène et le norbor- nadiène. Dans un mode de mise en œuvre préféré, on prépare in situ le complexe que l'on souhaite utiliser comme catalyseur. Ce mode de mise en œuvre est particulièrement avantageux du fait de la simplicité de mise en œuvre du procédé de préparation du complexe et de sa stabilité à l'air. Le procédé pour aryler une oléfine à l'aide d'un complexe aminophosphine / Pd selon l'invention consiste à faire réagir 1 Oléfine avec un agent arylant dans un solvant choisi parmi le toluène, 1 ' acétonitrile, le DMSO, le THF ou le DMF à une température de 20 °C à 110 °C en présence d'un complexe aminophosphine / Pd selon l'invention, dans des proportions telles que le rapport ligand/Pd est de 1/4 à 1/1, de préférence de 1,1/1 à 1,6/1. Un rapport ligand/Pd de 1,5/1 est particulièrement avantageux. Il est particulièrement avantageux de préparer le complexe aminophosphine / Pd in si tu . L'agent arylant est choisi parmi les composés Ph-X1 dans lesquels X1 représente un atome d'halogène ou un substituant trifluorosulfonyle (OTf) et Ph représente un radical aromatique. Ph peut être un radical aromatique à noyaux condensés, un cycle aromatique portant des substituants, ou un cycle hétéroaromatique . A titre d'exemple, on peut citer en particulier 1 ' iodobenzène .An aminophosphine / Pd complex according to the present invention can be used as catalyst for arylation or hydroarylation reactions of olefins, functionalized or not. Among the olefins which can be arylated in the presence of an aminophosphine / Pd complex according to the invention, mention may be made, for example, of cyclohexene, cyclopentene, butyl acrylate, norbornene and norboradadiene . In a preferred embodiment, the complex which is to be used as catalyst is prepared in situ. This mode of implementation is particularly advantageous because of the simplicity of implementation of the process for preparing the complex and its stability in air. The process for arylating an olefin using an aminophosphine / Pd complex according to the invention consists in reacting 1 olefin with an arylating agent in a solvent chosen from toluene, acetonitrile, DMSO, THF or DMF at a temperature of 20 ° C. to 110 ° C. in the presence of an aminophosphine / Pd complex according to the invention, in proportions such that the ligand / Pd ratio is 1/4 to 1/1, preferably 1 , 1/1 to 1.6 / 1. A ligand / Pd ratio of 1.5 / 1 is particularly advantageous. It is particularly advantageous to prepare the aminophosphine / Pd complex in si tu. The arylating agent is chosen from the compounds Ph-X 1 in which X 1 represents a halogen atom or a trifluorosulfonyl substituent (OTf) and Ph represents an aromatic radical. Ph can be an aromatic radical with condensed nuclei, an aromatic ring carrying substituents, or a heteroaromatic ring. By way of example, mention may be made in particular of iodobenzene.
Un complexe aminophosphine / Pd de l'invention peut éga- lement être utilisé comme catalyseur pour 1 ' hydroarylation d'une oléfine, fonctionnalisée ou non. Le procédé d'hydroarylation consiste à faire réagir l' oléfine avec un agent arylant dans un solvant polaire à une température entre 20 et 110°C en présence d'un complexe aminophosphine / Pd selon l'invention, d'une base faible et d'un acide dans des proportions telles que le rapport ligand/Pd est de 1/4 à 1/1, de préférence de 1,1/1 à 1,6/1. Un rapport ligand/Pd de 1,5/1 est particulièrement avantageux. Le rapport composé à aryler /agent arylant est de 1/3 et 1/1 à 3/1. L'agent arylant est choisi parmi les composés Ph-X de même nature que les agents arylants cités ci-dessus pour l'arylation des oléfines . L ' iodobenzène est cité à titre d'exemple. La base est choisie de préférence parmi la triéthylamine, la pyridine, l'acétate de sodium ou de potassium. L'acide est choisi de préférence parmi les acides faibles tels que l'acide formique et les solutions de chlorure d'ammonium. Le solvant polaire peut être le toluène, 1 ' acétonitrile, le DMSO, le THF ou le DMF.An aminophosphine / Pd complex of the invention can also be used as a catalyst for the hydroarylation of an olefin, functionalized or not. The hydroarylation process consists in reacting the olefin with an arylating agent in a polar solvent at a temperature between 20 and 110 ° C. in the presence of an aminophosphine / Pd complex according to the invention, a weak base and d an acid in proportions such that the ligand / Pd ratio is from 1/4 to 1/1, preferably from 1.1 / 1 to 1.6 / 1. A ligand / Pd ratio of 1.5 / 1 is particularly advantageous. The compound to aryler / arylating agent ratio is 1/3 and 1/1 to 3/1. The arylating agent is chosen from Ph-X compounds of the same nature as the arylating agents mentioned above for the arylation of olefins. Iodobenzene is cited as an example. The base is preferably chosen from triethylamine, pyridine, sodium or potassium acetate. The acid is preferably chosen from weak acids such as formic acid and ammonium chloride solutions. The polar solvent can be toluene, acetonitrile, DMSO, THF or DMF.
Les complexes catalyseurs selon 1 ' invention présentent divers avantages par rapport aux complexes de palladium de l'art antérieur. Leur utilisation pour les réactions d'arylation ou d'hydroarylation permet d'obtenir de meilleurs TON (qui représente le nombre de moles de produit obtenu par mole de Pd) et nécessite par conséquent une quantité globale de catalyseur plus faible. En outre, ils sont actifs à des concentrations nettement plus faibles que les complexes de palladium de l'art antérieur.The catalyst complexes according to the invention have various advantages over the palladium complexes of the prior art. Their use for arylation or hydroarylation reactions makes it possible to obtain better TONs (which represents the number of moles of product obtained per mole of Pd) and therefore requires a lower overall amount of catalyst. In addition, they are active at significantly lower concentrations than the palladium complexes of the prior art.
La présente invention est décrite plus en détails à l'aide d'exemples de réalisation, qui sont donnés pour illustrer l'invention. L'invention n'est toutefois pas limitée aux exemples décrits. Exemple 1The present invention is described in more detail with the aid of exemplary embodiments, which are given to illustrate the invention. The invention is however not limited to the examples described. Example 1
Synthèse de la [bis (diméthylamino ) ] -o-tolylphosphineSynthesis of [bis (dimethylamino)] -o-tolylphosphine
La préparation a été effectuée conformément au schéma réactionnel suivant :The preparation was carried out in accordance with the following reaction scheme:
Figure imgf000011_0001
Figure imgf000011_0001
On a préparé le bromure d' o-tolylmagnésium de la manière suivante. Dans un ballon tricol équipé d'une entrée d'argon, d'un barreau aimanté, d'un réfrigérant surmonté d'un bulleur à huile et d'une ampoule à brome, on a introduit à température ambiante (20-30°C) 6, 9 g (0,3 mole) de magnésium en tournures et 100 ml de THF anhydre et dégazé. On a ajouté un cristal d'iode pour amorcer la réaction, puis goutte à goutte 51,3 g (0,3 mole) de 2-bromotoluène . Après la fin de l'addition, le mélange a été agité pendant une heure à température ambiante.The o-tolylmagnesium bromide was prepared in the following manner. In a three-necked flask equipped with an argon inlet, a magnetic bar, a cooler surmounted by an oil bubbler and a dropping funnel, it was introduced at room temperature (20-30 ° C. ) 6.9 g (0.3 mole) of magnesium in turnings and 100 ml of anhydrous and degassed THF. An iodine crystal was added to initiate the reaction, and then dropwise 51.3 g (0.3 mole) of 2-bromotoluene. After the addition was complete, the mixture was stirred for one hour at room temperature.
La chloro [bis (diméthylamino) ] phosphine a été préparée parallèlement selon le mode opératoire suivant. Dans un réacteur de 1 1 comprenant une entrée d'azote, un réfrigérant muni d'un bulleur à huile, d'une ampoule à brome et d'un système d'agitation, on a placé sous argon, 13,7 g (0,1 mole) de trichlorure de phosphore. On a ajouté lentement en refroidissant avec de la glace 32,6 g (0,2 mole) de tris (diméthylamino) phosphine . Après la fin de l'addition, le mélange a été chauffé à 100°C pendant 20 minutes. La chloro [bis (diméthylamino) ] phosphine a ensuite été diluée dans 400 ml d'éther diéthylique anhydre et dégazée.The chloro [bis (dimethylamino)] phosphine was prepared in parallel according to the following procedure. In a 1 1 reactor comprising a nitrogen inlet, a condenser fitted with an oil bubbler, a dropping funnel and a stirring system, 13.7 g (0 , 1 mole) of phosphorus trichloride. 32.6 g (0.2 mole) of tris (dimethylamino) phosphine was added slowly while cooling with ice. After the addition was complete, the mixture was heated at 100 ° C for 20 minutes. The chloro [bis (dimethylamino)] phosphine was then diluted in 400 ml of anhydrous diethyl ether and degassed.
La solution de bromure d ' o-tolylmagnésium a été ajoutée à 0°C à la solution éthérée de chloro [bis (diméthylamino) ] - phosphine sur une période de 2 heures. On a laissé revenir le mélange réactionnel à température ambiante, puis on a laissé sous agitation pendant la nuit. Après addition de 200 ml d'éther diéthylique, on a hydrolyse le milieu réactionnel avec une solution de 96,0 g d'acide éthylène diamine tétra- acétique (EDTA) et 55,2 g de NaOH dans 600 ml d'eau glacée et 200 ml d'éther diéthylique. Après quelques minutes d'agitation, puis décantation, la phase aqueuse a été extraite avec 2x200 ml d'éther diéthylique. Les phases organiques réunies ont été séchées sur carbonate de potassium. Après filtration et évaporation du solvant, le produit a été distillé sous pression réduite.The o-tolylmagnesium bromide solution was added at 0 ° C to the ethereal solution of chloro [bis (dimethylamino)] - phosphine over a period of 2 hours. The reaction mixture was allowed to return to room temperature, then allowed to stir overnight. After adding 200 ml of diethyl ether, the reaction medium was hydrolyzed with a solution of 96.0 g of ethylene diamine tetra- acetic acid (EDTA) and 55.2 g of NaOH in 600 ml of ice water and 200 ml of diethyl ether. After a few minutes of stirring, then decantation, the aqueous phase was extracted with 2x200 ml of diethyl ether. The combined organic phases were dried over potassium carbonate. After filtration and evaporation of the solvent, the product was distilled under reduced pressure.
La [bis (diméthylamino) ] -o-tolylphosphine a été obtenue avec un rendement de 78% sous forme d'une huile incolore. Ses caractéristiques sont les suivantes.The [bis (dimethylamino)] -o-tolylphosphine was obtained with a yield of 78% in the form of a colorless oil. Its characteristics are as follows.
Figure imgf000012_0001
Figure imgf000012_0001
Eb : 80°C (10 Pa) RMN XH (CDC13) (200 MHz; δ = 2,31 (s, 3H) ; 2,69 (d, JPH = 35,5 Hz, 6H) ; 2,72Bp: 80 ° C (10 Pa) X H NMR (CDC1 3) (200 MHz; δ = 2.31 (s, 3H); 2.69 (d, J PH = 35.5 Hz, 6H); 2, 72
(d, JPH = 35,5 Hz, 6H) ; 7,17-7,46 (m, 4H) . RMN 13C (CDCI3) (50 MHz) : δ = 36,3 (d, JPC = 16 Hz) ; 41,0 (s) ; 41,3 (s) ;(d, J PH = 35.5 Hz, 6H); 7.17-7.46 (m, 4H). 13 C NMR (CDCI 3 ) (50 MHz): δ = 36.3 (d, J PC = 16 Hz); 41.0 (s); 41.3 (s);
125,1 (s) ; 127,6 (s) ; 130,4 (s) ; 131,4 (s) ; 138,5125.1 (s); 127.6 (s); 130.4 (s); 131.4 (s); 138.5
(s) ; 140,0 (d, JPC = 43, 6 Hz) . RMN 31P (CDCI3) (40,54 MHz) : δ = 96,6.(s); 140.0 (d, J PC = 43.6 Hz). 31 P NMR (CDCI 3 ) (40.54 MHz): δ = 96.6.
Exemple 2Example 2
Synthèse de la Bispyrrolidino-o-tolylphosphineBispyrrolidino-o-tolylphosphine synthesis
Dans un ballon bicol de 25 ml muni d'une entrée d'argon et d'un réfrigérant surmonté d'un bulleur à huile, on a placéIn a 25 ml two-necked flask provided with an argon inlet and a cooler surmounted by an oil bubbler,
0,71 g (10,0 mmole) de pyrrolidine et 1,03 g (5,0 mmole) de0.71 g (10.0 mmol) of pyrrolidine and 1.03 g (5.0 mmol) of
[bis (diméthylamino) ] -o-tolylphosphine dans 6 ml de toluène anhydre et dégazé. On a porté à reflux du toluène et on a suivi la réaction par RMN du 31P . La reaction a été totale après 2 heures. Le solvant a été chassé sous vide et le résidu distillé sur four tubulaire. La bispyrrolidino-o-tolyl- phosphine a été obtenue sous forme d'une huile incolore avec un rendement de 76%. Ses caractéristiques sont les suivantes. [bis (dimethylamino)] -o-tolylphosphine in 6 ml of anhydrous and degassed toluene. Toluene was refluxed and the reaction was followed by 31 P NMR. The reaction was complete after 2 hours. The solvent was removed in vacuo and the residue distilled on a tube oven. Bispyrrolidino-o-tolylphosphine was obtained in the form of a colorless oil with a yield of 76%. Its characteristics are as follows.
Figure imgf000013_0001
Figure imgf000013_0001
Eb : 95°C (3 Pa)Eb: 95 ° C (3 Pa)
RMN 1H (CDC13) (200 MHz) : δ = 1,76 (m, 8H) ; 2,41 (s, 3H) ; 3,01 (m, 8H) ; 6,63- 1 H NMR (CDC1 3 ) (200 MHz): δ = 1.76 (m, 8H); 2.41 (s, 3H); 3.01 (m, 8H); 6,63-
7,48 (m, 4H) . RMN 13C (CDCI3) (50 MHz) : δ = 26,4 (d, JPC = 4,8 Hz) ; 36,4 (d, JPC = 14,0 Hz) ;7.48 (m, 4H). 13 C NMR (CDCI 3 ) (50 MHz): δ = 26.4 (d, J PC = 4.8 Hz); 36.4 (d, J PC = 14.0 Hz);
49,9 (d, JPC = 13,5 Hz), 125,3 (s) ; 127,7 (s) ; 128,749.9 (d, J PC = 13.5 Hz), 125.3 (s); 127.7 (s); 128.7
(s) ; 129,8 (d, JPC = 5,0 Hz) ; 130,5 (s) ; 143,3 (d,(s); 129.8 (d, J PC = 5.0 Hz); 130.5 (s); 143.3 (d,
JPC = 42, 0 Hz) . RMN 31P (CDCI3) (40,54 MHz) : δ = 89, 1.J PC = 42.0 Hz). 31 P NMR (CDCI 3 ) (40.54 MHz): δ = 89.1.
Exemple 3Example 3
Synthèse de la Bispipéridino-o-tolylphosphine Dans un ballon bicol de 25 ml muni d'une entrée d'argon et d'un réfrigérant surmonté d'un bulleur à huile, on a placé 0,85 g (10,0 mmole) de pipéridine et 1,03 g (5,0 mmole) de [bis (diméthylamino) ] -o-tolylphosphine dans 6 ml de toluène anhydre et dégazé. On a porté à reflux du toluène et on aSynthesis of Bispiperidino-o-tolylphosphine 0.85 g (10.0 mmol) was placed in a 25 ml two-necked flask provided with an argon inlet and a cooler surmounted by an oil bubbler. piperidine and 1.03 g (5.0 mmol) of [bis (dimethylamino)] -o-tolylphosphine in 6 ml of anhydrous and degassed toluene. We brought toluene to reflux and we
31 suivi la réaction par RMN du P. La réaction a été totale au bout de 2 heures. Le solvant a été chassé sous vide et le résidu distillé sur four tubulaire. Le produit qui se présente sous forme d'une huile incolore, a été obtenu avec un rendement de 58%. Ses caractéristiques sont les suivantes.31 followed the reaction by P NMR. The reaction was complete after 2 hours. The solvent was removed in vacuo and the residue distilled on a tube oven. The product, which is in the form of a colorless oil, was obtained with a yield of 58%. Its characteristics are as follows.
Figure imgf000013_0002
Figure imgf000013_0002
Eb 130°C (2 Pa) RMN λH (CDC13) (200 MHz) : δ = 1,49 (m, 12H) ; 2,46 (s, 3H) ; 3,0 (m, 8H) ; 7,0-Eb 130 ° C (2 Pa) Λ H NMR (CDC1 3 ) (200 MHz): δ = 1.49 (m, 12H); 2.46 (s, 3H); 3.0 (m, 8H); 7,0-
7, 42 (m, 4H) . RMN 13C (CDCI3) (50 MHz) : δ = 25,5 (d, JPC = 4,5 Hz) ; 41,2 (d, JPC = 35,0 Hz) ;7.42 (m, 4H). 13 C NMR (CDCI 3 ) (50 MHz): δ = 25.5 (d, J PC = 4.5 Hz); 41.2 (d, J PC = 35.0 Hz);
46,2 (s) ; 50,4 (d, JPC = 15,0 Hz) , 125,1 (s) ; 128,646.2 (s); 50.4 (d, J PC = 15.0 Hz), 125.1 (s); 128.6
(s) ; 127,7 (s) ; 129,2 (s) ; 130,7 (s) ; 141,2 (d, JPC (s); 127.7 (s); 129.2 (s); 130.7 (s); 141.2 (d, J PC
= 41, 0 Hz) . RMN 31P (CDCI3) (40,54 MHz) : δ = 91,2= 41.0 Hz). 31 P NMR (CDCI 3 ) (40.54 MHz): δ = 91.2
Exemple 4Example 4
Synthèse du (2R, 5S) -2-o-Tolyl-3-phényl-diazaphosphabicyclo-Synthesis of (2R, 5S) -2-o-Tolyl-3-phenyl-diazaphosphabicyclo-
[3.3.0] -octane[3.3.0] -octane
Dans un ballon bicol de 25 ml muni d'une entrée d'argon et d'un réfrigérant surmonté d'un bulleur à huile, on a placéIn a 25 ml two-necked flask provided with an argon inlet and a cooler surmounted by an oil bubbler,
1,0 g (5,0 mmole) de ( S) -2-anilinométhylpyrrolidine et 1,03 g1.0 g (5.0 mmol) of (S) -2-anilinomethylpyrrolidine and 1.03 g
(5,0 mmole) de [bis (diméthylamino) ] -o-tolylphosphine dans(5.0 mmol) of [bis (dimethylamino)] -o-tolylphosphine in
6 ml de toluène anhydre et dégazé. On a porté à reflux du toluène et on a suivi la réaction par RMJSI du P. La réaction a été totale au bout de 2 heures. Le solvant a été chassé sous vide et le résidu distillé sur four tubulaire. Le produit a été obtenu avec un rendement de 79%. Il se présente sous la forme d'une huile incolore qui solidifie après quelques heures. Ses caractéristiques sont les suivantes.6 ml of anhydrous and degassed toluene. Toluene was refluxed and the reaction was followed by RMJSI of P. The reaction was complete after 2 hours. The solvent was removed in vacuo and the residue distilled on a tube oven. The product was obtained with a yield of 79%. It is in the form of a colorless oil which solidifies after a few hours. Its characteristics are as follows.
Figure imgf000014_0001
Figure imgf000014_0001
Eb 140°C (2 Pa;Bp 140 ° C (2 Pa;
Pf : 45°CMp: 45 ° C
RMN XH (CDCI3) (200 MHz; δ = 2,29 (m, 4H) 3,16 (s, 3H) ; 3,47-3,6É (m, 4H; X NMR H (CDCl 3) (200 MHz; δ = 2.29 (m, 4H) 3.16 (s, 3H); 3,47-3,6É (m, 4H;
3,93-397 m, IH; 7, 17-7, 8e (m, 9H) .
Figure imgf000014_0002
δ = 25,5 (d, JPC = 4,5 Hz) ; 30,43 (s) ; 36,4 (d, JPC = 15 Hz) ; 46,4 (d, JPC = 100,0 Hz) , 51,8 (d, JPC = 27,5 Hz) ; 57,6 (s) ; 113,0 (s) ; 114,9 (d, JPC =15 Hz) ; 117,3 (d, JPC = 25 Hz) ; 125,4 (s) ; 128,6 (s) ; 128,7 (s) ; 129,0 (s) ; 129,3 (s) ; 130,7 (d, JPC = 3Hz) ;3.93-397 m, 1H; 7, 17-7, 8th (m, 9H).
Figure imgf000014_0002
δ = 25.5 (d, J PC = 4.5 Hz); 30.43 (s); 36.4 (d, J PC = 15 Hz); 46.4 (d, J PC = 100.0 Hz), 51.8 (d, J PC = 27.5 Hz); 57.6 (s); 113.0 (s); 114.9 (d, J PC = 15 Hz); 117.3 (d, J PC = 25 Hz); 125.4 (s); 128.6 (s); 128.7 (s); 129.0 (s); 129.3 (s); 130.7 (d, J PC = 3Hz);
140,1 (s) ; 147,3 (d, JPC = 65 Hz) . RMN 31P (CDC13) (40,54 MHz) : δ = 97,1140.1 (s); 147.3 (d, J PC = 65 Hz). 31 P NMR (CDC1 3 ) (40.54 MHz): δ = 97.1
Exemple 5 Hydroarylation du norborneneEXAMPLE 5 Noraryene Hydroarylation
Le complexe catalyseur a été préparé selon le schéma réactionnel suivant :The catalyst complex was prepared according to the following reaction scheme:
Figure imgf000015_0001
X = Br. Cl. I. OTf
Figure imgf000015_0001
X = Br. Cl. I. OTf
Dans un ballon bicol, on a placé sous argon 2,5 mg (llxlO-6 mol) de Pd(OAc)2 et 4,8 mg (23xl0~6 mol) de [Bis (diméthylamino) ] -o-tolylphosphine (indiqué par "phosphine" dans le schéma réactionnel) dans 5 ml de DMSO. Le complexe a été obtenu par chauffage à 60 °C durant 5 minutes. On a ensuite additionné 459 mg (2,3x10 mol) d' iodobenzèneIn a two-necked flask, 2.5 mg (11 × 10 -6 mol) of Pd (OAc) 2 and 4.8 mg (23 × 10 −6 mol) of [Bis (dimethylamino)] -o-tolylphosphine were placed under argon. by "phosphine" in the reaction scheme) in 5 ml of DMSO. The complex was obtained by heating at 60 ° C for 5 minutes. 459 mg (2.3x10 mol) of iodobenzene were then added.
_3 et 700 mg (7,4x10 mol) de norbornene. On a également ajouté 0,76 g de NEt3 (7,5xl0~3 mol) et 280 mg d'acide formique (6x10" mol). On a laissé sous agitation à 100°C durant 15 heures. Après refroidissement, on a additionné 15 ml d'eau et on a extrait avec du pentane (3x30 ml) . Les phases organiques ont été réunies et séchées sur MgS04. Après evaporation des solvants, le résidu a été distillé sur four tubulaire pour conduire à 392 mg de phénylnorbornane ._3 and 700 mg (7.4x10 mol) of norbornene. 0.76 g of NEt 3 was also added (7,5xl0 -3 mol) and 280 mg of formic acid (6x10 "mol). Stirring was allowed at 100 ° C for 15 hours. After cooling, added 15 ml of water and extracted with pentane (3 × 30 ml). The organic phases were combined and dried over MgSO 4. After evaporation of the solvents, the residue was distilled on a tubular oven to yield 392 mg of phenylnorbornane .
Le produit a été obtenu avec un rendement de 99% sous forme d'une huile incolore. Ses caractéristiques sont les suivantes .
Figure imgf000016_0001
The product was obtained with a yield of 99% in the form of a colorless oil. Its characteristics are as follows.
Figure imgf000016_0001
RMN XH (CDC13) (200 MHz) : δ = 1,25-1, 92 (m, 8H) ; 2,44 :s, 2H; 2,83 (q, J = Hz, 1H) ; 7,20-7,41 (m, 5H) . RMN 13C (CDCI3) (50 MHz) : δ = 29,0 (s) ; 30,7 (s) 36,1 (s) 36,9 (s) ; 39,2 X H NMR (CDC1 3) (200 MHz): δ = 1.25 to 1, 92 (m, 8H); 2.44: s, 2H; 2.83 (q, J = Hz, 1H); 7.20-7.41 (m, 5H). 13 C NMR (CDCI 3 ) (50 MHz): δ = 29.0 (s); 30.7 (s) 36.1 (s) 36.9 (s); 39.2
(s) ; 43,0 (s) ; 47,4 (s) 125,4 (s; 127,1 (s, 2C) ;(s); 43.0 (s); 47.4 (s) 125.4 (s; 127.1 (s, 2C);
128,3 (s, 2C) ; 142,7 (s) .128.3 (s, 2C); 142.7 (s).
D'autres essais ont été effectués dans des conditions analogues à celles décrites ci-dessus, en faisant varier l'agent d'arylation, la teneur en catalyseur et/ou le solvant. Les résultats obtenus sont donnés dans le tableau 1 ci-dessous. "Ph" représente un radical phényle, "Ar-X" représente l'agent d'arylation. "Cv" représente le taux de conversion de l'agent d'arylation, "Rdt" représente le rendement en produit final, "TON" représente le nombre de moles de produit obtenu par mole de Pd, "TOF" représente le nombre de moles de produit obtenu par mole de Pd et par heure .Other tests were carried out under conditions similar to those described above, by varying the arylating agent, the catalyst content and / or the solvent. The results obtained are given in Table 1 below. "Ph" represents a phenyl radical, "Ar-X" represents the arylating agent. "Cv" represents the conversion rate of the arylating agent, "Yield" represents the yield of final product, "TON" represents the number of moles of product obtained per mole of Pd, "TOF" represents the number of moles of product obtained per mole of Pd and per hour.
Tableau 1Table 1
ssai Ar-X Catalyseur Solvant Cv (%) Rdt (%) TON (mol TOF (mol prod/mol (mol% Pd) prod/mol Pd) Pd/h)ssai Ar-X Solvent Catalyst Cv (%) Yield (%) TON (mol TOF (mol prod / mol (mol% Pd) prod / mol Pd) Pd / h)
1 Ph-I 0,5 DMSO 100 99 198 131 Ph-I 0.5 DMSO 100 99 198 13
2 Ph-I 5 1O 2 DMSO 100 99 1980 1322 Ph-I 5 1O 2 DMSO 100 99 1980 132
3 Ph-I 5 10-4 DMSO 100 99 198000 13 103 3 Ph-I 5 10- 4 DMSO 100 99 198 000 13 10 3
4 Ph-I 5 10"6 DMSO 100 98 19 106 1 ,3 10e 4 Ph-I 5 10 "6 DMSO 100 98 19 10 6 1, 3 10 e
5 Ph-I 5 10"7 DMSO 100 98 196 106 13 106 5 Ph-I 5 10 "7 DMSO 100 98 196 10 6 13 10 6
6 Ph-I 5 10"9 DMSO 100 79 158 108 10,8 108 6 Ph-I 5 10 "9 DMSO 100 79 158 10 8 10.8 10 8
7 Ph-I 5 10"7 DMF 75 62 124 106 8 106 8 Ph-I 5 10"7 DMAE 50 42 80 10e 6 106 7 Ph-I 5 10 "7 DMF 75 62 124 10 6 8 10 6 8 Ph-I 5 10 "7 DMAE 50 42 80 10 e 6 10 6
9 Ph-CI 0,5 DMSO 100 99 198 139 Ph-CI 0.5 DMSO 100 99 198 13
10 Ph-CI 5 10"3 DMSO 100 - - -10 Ph-CI 5 10 "3 DMSO 100 - - -
11 Ph-OTf 5 10"4 DMSO 100 99 198000 13 103 11 Ph-OTf 5 10 "4 DMSO 100 99 198 000 13 10 3
12 Ph-Br 5 10'4 DMSO 100 98 196000 13 103 12 Ph-Br 5 10 '4 DMSO 100 98 196 000 13 10 3
Des résultats ci-dessus, il apparaît que le complexe catalyseur selon l'invention permet d'obtenir des performances très intéressantes. Un taux de conversion de l' oléfine de 100% peut être atteint lorsque le solvant du milieu réactionnel est le DMSO. En outre, le choix d'un agent arylant du type iodure permet d'obtenir des TON très élevés, supérieurs à 106 avec des rendements de 98 à 99%.From the above results, it appears that the catalyst complex according to the invention makes it possible to obtain very advantageous performances. An olefin conversion rate of 100% can be achieved when the solvent for the reaction medium is DMSO. In addition, the choice of an arylating agent of the iodide type makes it possible to obtain very high TONs, greater than 10 6 with yields of 98 to 99%.
Exemple 6Example 6
Hydroarylation du norbornadiène La réaction a été effectuée selon le schéma réactionnel suivant :Norbornadiene hydroarylation The reaction was carried out according to the following reaction scheme:
Figure imgf000017_0001
Figure imgf000017_0001
4 heures4 hours
Dans un ballon bicol, on a placé sous argon 2,5 mg de Pd(OAc)2 (llxlO-6 mol) et 4,8 mg (23xl0~6 mol) de [bis-In a two-necked flask, 2.5 mg of Pd (OAc) 2 (11 × 10 -6 mol) and 4.8 mg (23 × 10 -6 mol) of [bis-
(diméthylamino) ] -o-tolylphosphine (notée "phosphine" dans le schéma réactionnel) dans 5 ml de DMSO. La formation du complexe a été obtenue par chauffage à 60 °C durant 5 minutes.(dimethylamino)] -o-tolylphosphine (denoted "phosphine" in the reaction scheme) in 5 ml of DMSO. The formation of the complex was obtained by heating at 60 ° C for 5 minutes.
On a ensuite additionné 459 mg d' iodobenzène (2,3x10" mol) et 680 mg de norbornadiène (7,4x10 mol) . On a également ajouté 0,76 g de NEt3 (7,5xl0~3 mol) et 280 mg d'acide formique (6xl0~ mol). On a laissé sous agitation à 100°C durant 15 heures. Après refroidissement, on a additionné459 mg of iodobenzene (2.3x10 " mol) and 680 mg of norbornadiene (7.4x10 mol) were then added. 0.76 g of NEt 3 (7.5 × 10 -3 mol) and 280 mg were also added. formic acid (6xl0 ~ mol). stirring was allowed at 100 ° C for 15 hours. After cooling, it was added
15 ml d'eau et on a extrait avec du pentane (3x30 ni). Les phases organiques ont été réunies et séchées sur MgSO.; . Après evaporation des solvants, le résidu a été distillé sur four tubulaire pour conduire à 387 mg de phénylnorbornène .15 ml of water and extracted with pentane (3x30 µl). The organic phases were combined and dried over MgSO. ; . After evaporation of the solvents, the residue was distilled on a tube furnace to yield 387 mg of phenylnorbornene.
Le produit a été obtenu avec un rendement de 99% sous forme d'une huile incolore. Ses caractéristiques sont les suivantes .The product was obtained with a yield of 99% in the form of a colorless oil. Its characteristics are as follows.
Figure imgf000018_0001
Figure imgf000018_0001
RMN H (CDC13) (200 MHz) : δ = 1,36-1,72 (m, 4H) ; 2,63 (m, 1H) 2,83 (s, 1H) 2,88 (s, 1H) ; 6,10 (m, 2H) ; 7,10-7,23 (m, 5H) . RMN C (CDCI3) (50 MHz) : δ = 33,7 (s) ; 42,4 (s) ; 43,8 (s) ; 45,8 (s) ; 48,3 (s) ; 125,6 (s) ; 127,7 (s, 2C) ; 128,3 (s, 2C) ; 137,4 (s) ; 137,5 (s) ; 147,2 (s) . D'autres essais ont été effectués dans des conditions analogues à celles décrites ci-dessus, en faisant varier la teneur en catalyseur. Les résultats obtenus sont donnés dans le tableau 2 ci-dessous.1 H NMR (CDC1 3 ) (200 MHz): δ = 1.36-1.72 (m, 4H); 2.63 (m, 1H) 2.83 (s, 1H) 2.88 (s, 1H); 6.10 (m, 2H); 7.10-7.23 (m, 5H). NMR C (CDCI 3 ) (50 MHz): δ = 33.7 (s); 42.4 (s); 43.8 (s); 45.8 (s); 48.3 (s); 125.6 (s); 127.7 (s, 2C); 128.3 (s, 2C); 137.4 (s); 137.5 (s); 147.2 (s). Other tests were carried out under conditions similar to those described above, by varying the catalyst content. The results obtained are given in Table 2 below.
Tableau 2Table 2
Entrée Ar-X Catalyseur Solvant Cv (%) Rdt (%) TON (mol prod/mol TOF (mol prod/mol (mol% Pd) Pd] Pd/h)Input Ar-X Catalyst Solvent Cv (%) Yield (%) TON (mol prod / mol TOF (mol prod / mol (mol% Pd) Pd] Pd / h)
1 Ph-I 0.5 DMSO 100 99 198 131 Ph-I 0.5 DMSO 100 99 198 13
2 Ph-I 5.10-4 DMSO 100 99 198000 13 103 2 Ph-I 5.10- 4 DMSO 100 99 198 000 13 10 3
3 Ph-I 5.10"6 DMSO 100 98 19 106 1.3 106 3 Ph-I 5.10 "6 DMSO 100 98 19 10 6 1.3 10 6
4 Ph-I 5.10"7 DMSO 100 98 196 10e 13 10e 4 Ph-I 5.10 "7 DMSO 100 98 196 10 e 13 10 e
Les résultats ci-dessus montrent que des taux de conversion de 100% et des rendements de 98% peuvent être obtenus avec des concentrations en complexe catalyseur selon l'invention aussi faibles que 5.10"7, ce qui permet un TON supérieur à 108. Exemple 7The above results show that conversion rates of 100% and yields of 98% can be obtained with concentrations of catalyst complex according to the invention as low as 5.10 "7 , which allows a TON greater than 10 8 . Example 7
Arylation de l'acrylate de butyle par le p-bromobenzaldéhyde La réaction a été effectuée selon le schéma réactionnel suivant :Arylation of butyl acrylate with p-bromobenzaldehyde The reaction was carried out according to the following reaction scheme:
Figure imgf000019_0001
Figure imgf000019_0001
Dans un ballon bicol, on a introduit sous argon 5xl0~8 mol de Pd(OAc)2 et 10"7 mol de [Bis (diméthylamino) ] -o- tolylphosphine (notée "phosphine" dans le schéma réactionnel) dans 2 ml de DMAE. La formation du complexe s'effectue par chauffage à 60°C durant 5 minutes.In a two-necked flask, 5 × 10 -8 mol of Pd (OAc) 2 and 10 "7 mol of [Bis (dimethylamino)] -o-tolylphosphine (noted" phosphine "in the reaction scheme) were introduced under argon in 2 ml of DMAE The complex is formed by heating at 60 ° C for 5 minutes.
On a introduit parallèlement dans un ballon bicol sous argon équipé d'un réfrigérant surmonté d'un bulleur à huile 100 mmole de bromobenzaldéhyde, 70 mmole d' acrylate de butyle et 110 mmole d'acétate de sodium anhydre dans 10 ml de DMAE. On a chauffé le mélange réactionnel à 100 °C. Lorsque la température s'est stabilisée, on a ajouté le catalyseur préformé sous argon et on a maintenu le chauffage durant 16 heures à 100°C. Après refroidissement, on a hydrolyse le milieu avec 30 ml d'une solution d'acide chlorhydrique (5%) et on extrait avec 3x20 ml de dichlorométhane . Les phases organiques ont été rassemblées et séchées sur MgS04. Après filtration, les solvants ont été chassés sous vide et le résidu distillé sur four tubulaire.Was introduced in parallel into a two-necked flask under argon equipped with a condenser surmounted by an oil bubbler 100 mmol of bromobenzaldehyde, 70 mmol of butyl acrylate and 110 mmol of anhydrous sodium acetate in 10 ml of DMAE. The reaction mixture was heated to 100 ° C. When the temperature stabilized, the preformed catalyst was added under argon and heating was continued for 16 hours at 100 ° C. After cooling, the medium was hydrolyzed with 30 ml of a hydrochloric acid solution (5%) and extracted with 3 × 20 ml of dichloromethane. The organic phases were combined and dried over MgSO 4 . After filtration, the solvents were removed under vacuum and the residue distilled on a tube oven.
Le produit a été obtenu avec une rendement de 99% sous forme d'une huile incolore. Ses caractéristiques sont les suivantes .The product was obtained with a yield of 99% in the form of a colorless oil. Its characteristics are as follows.
Figure imgf000019_0002
Figure imgf000019_0002
Eb : 212°C (10 Pa)Eb: 212 ° C (10 Pa)
RMN H (CDC13) (200 MHz; δ = 0,9-1,1 (t, J =13 Hz, 3H) ; 1,30-1,75 (m, 4H) ; 4,12-4,25 (t, J = 7Hz, 2H) ; 6,4 (s, 1H) ; 6,8 (s, 1H) ; 7,24-7,91 (m, 4H) ; 9,1 (s, 1H) .H NMR (CDC1 3) (200 MHz; δ = 0.9-1.1 (t, J = 13 Hz, 3H); 1.30-1.75 (m, 4H); 4.12-4.25 (t, J = 7 Hz, 2H); 6.4 (s, 1H); 6.8 (s, 1H); 7.24-7.91 (m, 4H); 9.1 (s, 1H).
13, RMN ^C (CDC13) (50 MHz) : δ = 13,7 (s) ; 19,1 (s) ; 30,7 (s) ; 64,7 (s) ; 121,4 (s) ; 128,5 (s, 2C) ; 130,1 (s, 2C) ; 137,4 (s) ; 140,1 (s) ; 142,8 (s) ; 164,3 (s) ; 191,5 (s).13 C NMR (CDC1 3) (50 MHz): δ = 13.7 (s); 19.1 (s); 30.7 (s); 64.7 (s); 121.4 (s); 128.5 (s, 2C); 130.1 (s, 2C); 137.4 (s); 140.1 (s); 142.8 (s); 164.3 (s); 191.5 (s).
Exemple 8Example 8
Comparaison de différents catalyseurs pour une réaction de d'hydroarylation de norborneneComparison of different catalysts for a norbornene hydroarylation reaction
Une réaction d'hydroarylation de norbornene a été mise en œuvre dans les conditions de l'exemple 5, selon le schéma réactionnel suivant, à l'aide de différents complexes catalyseurs utilisés à différentes concentrations. Les résultats sont rassemblés dans le tableau 3 ci-dessous.A hydrobornlation reaction of norbornene was carried out under the conditions of Example 5, according to the following reaction scheme, using different catalyst complexes used at different concentrations. The results are collated in Table 3 below.
Figure imgf000020_0001
Figure imgf000020_0001
Les essais 1 à 3 ont été effectués à l'aide d'un complexe dans lequel le ligand L est la phosphine répondant à la formule 4 ci-dessous, correspondant à la [bis (diméthylamino) ] -o-tolylphosphine.Tests 1 to 3 were carried out using a complex in which the ligand L is phosphine corresponding to formula 4 below, corresponding to [bis (dimethylamino)] -o-tolylphosphine.
Les essais n° 8 à 10 ont été effectués à l'aide d'un complexe dans lequel le ligand L est la phosphine répondant respectivement aux formules 1, 2 et 3.Tests No. 8 to 10 were carried out using a complex in which the ligand L is phosphine corresponding to formulas 1, 2 and 3 respectively.
Figure imgf000020_0002
Figure imgf000021_0001
Figure imgf000020_0002
Figure imgf000021_0001
Les essais n° 4 à 7 sont des exemples comparatifs effectués à l'aide d'un complexe catalyseur dit de Herrmann, répondant à la formule suivante :Tests No. 4 to 7 are comparative examples carried out using a so-called Herrmann catalyst complex, corresponding to the following formula:
Figure imgf000021_0002
Figure imgf000021_0002
Ar = o-tolvlAr = o-tolvl
Tableau 3Table 3
Essais Ar-X Catalyseur Type de Cv (%) Rdt (%) TON (mol (mol% Pd) catalyseur prod/mol Pd)Ar-X tests Catalyst Type of Cv (%) Yield (%) TON (mol (mol% Pd) catalyst prod / mol Pd)
1 Ph-I 5 10"4 4 100 99 1980001 Ph-I 5 10 "4 4 100 99 198 000
2 Ph-I 5 107 4 100 98 196 10e 2 Ph-I 5 10 7 4 100 98 196 10 e
3 Ph-I 5 10"9 4 100 79 158 10θ 3 Ph-I 5 10 "9 4 100 79 158 10 θ
8 Ph-I 5 10'7 1 100 99 198 106 8 Ph-I 5 10 '7 1 100 99 198 10 6
9 Ph-I 5 10-7 2 100 98 196 10e 9 Ph-I 5 10- 7 2 100 98 196 10 e
10 Ph-I 5 10"7 3 100 94 188 10e 10 Ph-I 5 10 "7 3 100 94 188 10 e
4 Ph-I 1 10"2 Herrmann 100 98 98004 Ph-I 1 10 "2 Herrmann 100 98 9800
5 Ph-I 1 10"4 Herrmann 100 79 7900005 Ph-I 1 10 "4 Herrmann 100 79 790 000
6 Ph-I 1 10"5 Herrmann 0 0 -6 Ph-I 1 10 "5 Herrmann 0 0 -
7 Ph-Br 1 10"7 Herrmann 0 0 .7 Ph-Br 1 10 "7 Herrmann 0 0.
On constate que le catalyseur de Herrmann bien que très efficace dans le cas d'une utilisation à une concentration deIt is found that the Herrmann catalyst although very effective in the case of use at a concentration of
10" mol% ne conduit aucune conversion significative lorsque la concentration est abaissée respectivement à 10" et 10~7 mol%, alors que les complexes selon l'invention permettent d'obtenir des rendements élevés à des taux de conversion de 100% pour des concentrations de complexe catalyseur aussi faible que 5.10-7. 10 " mol% does not lead to any significant conversion when the concentration is lowered respectively to 10 " and 10 ~ 7 mol%, while the complexes according to the invention make it possible to obtain high yields at conversion rates of 100% for concentrations of catalyst complex as low as 5.10 -7 .

Claims

Revendications claims
1. Phosphine caractérisée en ce qu'elle comprend un atome de phosphore portant d'une part un groupe o-tolyle portant éventuellement des substituants, et d'autre part deux substituants aminé secondaire ou tertiaire.1. Phosphine characterized in that it comprises a phosphorus atom carrying on the one hand an o-tolyl group optionally carrying substituents, and on the other hand two secondary or tertiary amine substituents.
2. Phosphine selon la revendication 1, caractérisée en ce qu'elle répond à la formule générale (I) :2. Phosphine according to claim 1, characterized in that it corresponds to the general formula (I):
Figure imgf000023_0001
Figure imgf000023_0001
Z3Z3
dans laquelle : - les substituants RI, R2, R3 et R4 représentent indépendamment les uns des autres un atome d'hydrogène, un radical alkyle, un radical alcenyle ou un radical aryle, étant entendu que au plus l'un des substituants RI et R2 est un atome d'hydrogène, et au plus l'un des substituants R3 et R4 est un atome d'hydrogène ; ou bien les substituants RI et R2 d'une part, et/ou les substituants R3 et R4 d'autre part forment ensemble un biradical qui forme un heterocycle aromatique ou non avec l'atome d'azote qui les porte, ou bien l'un des substituants RI ou R2 forme avec les substituants R3 et R4 un radical trivalent qui forme des heterocycles condensés aromatiques ou non avec le segment -N-P-N- ; les substituants Z\ , Z2, Z3 et Z4 représentent indépendamment les uns des autres : * un groupe alkyle, un groupe aryle, un groupe cycloalkyle, un groupe alcenyle ;in which: the substituents RI, R2, R3 and R4 independently of one another represent a hydrogen atom, an alkyl radical, an alkenyl radical or an aryl radical, it being understood that at most one of the substituents RI and R2 is a hydrogen atom, and at most one of the substituents R3 and R4 is a hydrogen atom; either the substituents R1 and R2 on the one hand, and / or the substituents R3 and R4 on the other hand form together a biradical which forms an aromatic heterocycle or not with the nitrogen atom which carries them, or else the one of the substituents RI or R2 forms with the substituents R3 and R4 a trivalent radical which forms heterocycles condensed aromatic or not with the segment -NPN-; the substituents Z 1 , Z 2 , Z 3 and Z 4 represent independently of each other: * an alkyl group, an aryl group, a cycloalkyl group, an alkenyl group;
* un groupe R'O-, dans lequel R' représente H, un radical alkyle, un radical aryle, un radical trialkylsilyle ou un radical triarylsilyle ; * un groupe (R")2N- dans lequel les substituants R" représentent indépendamment les uns des autres H, un radical alkyle ou un radical aryle ;* a group R'O-, in which R 'represents H, an alkyl radical, an aryl radical, a trialkylsilyl radical or a triarylsilyl radical; * a group (R ") 2 N- in which the substituents R" independently of one another represent H, an alkyl radical or an aryl radical;
* un groupe (R'")3Si- dans lequel les substituants R représentent indépendamment les uns des autres H, un radical alkyle, un radical aryle, un radical alkyloxy ou un radical aryloxy ;* a group (R '") 3 Si- in which the substituents R represent, independently of each other, H, an alkyl radical, an aryl radical, an alkyloxy radical or an aryloxy radical;
* un groupe P(R"")2, un groupe P0(R"")2, un groupe PS(R"")2 ou un groupe PSe(R"")2, dans lequel les substituants R "" représentent indépendamment les uns des autres H, un radical alkyle, un radical aryle, un radical alkyloxy ou un radical aryloxy.* a group P (R "") 2 , a group P0 (R "") 2 , a group PS (R "") 2 or a group PSe (R "") 2, in which the substituents R "" independently represent each other H, an alkyl radical, an aryl radical, an alkyloxy radical or an aryloxy radical.
3. Phosphine selon la revendication 1, caractérisée en ce que les substituants Ri et les substituants Z1 représen- tent un radical alkyle ayant de 1 à 18 atomes de carbone, un groupe cycloalkyle ayant de 5 à 18 atomes de carbone ou un groupe aryle ayant de 6 à 14 atomes de carbone.3. Phosphine according to claim 1, characterized in that the substituents R 1 and the substituents Z 1 represent an alkyl radical having from 1 to 18 carbon atoms, a cycloalkyl group having from 5 to 18 carbon atoms or an aryl group having 6 to 14 carbon atoms.
4. Procédé de préparation d'une phosphine selon la revendication 1 dans laquelle les substituants Ri représentent chacun un groupe méthyle, caractérisé en ce qu'il consiste à condenser un halogénure d' o-tolylmagnésium portant les substituants Zx appropriés avec la chloro [bis- (diméthylamino) phosphine .4. Process for the preparation of a phosphine according to claim 1, in which the substituents Ri each represent a methyl group, characterized in that it consists in condensing an o-tolylmagnesium halide carrying the appropriate substituents Z x with chloro [ bis- (dimethylamino) phosphine.
5. Procédé selon la revendication 4, caractérisé en ce qu' il comprend les étapes suivantes : al) addition lente d'un halogénure d' o-tolylmagnésium portant les substituants Z± appropriés à la chloro [bis- (diméthylamino) phosphine à une température entre -78 °C et +30°C, dans un solvant hydrocarboné ou oxygéné, sous atmosphère neutre et anhydre, dans des proportions stœchiométriques ; bl) maintien sous agitation à température ambiante pendant une durée de 8 à 15 heures ; cl) hydrolyse à une température entre -78°C et +30°C à l'aide d'une solution d'ethylene diamine tétracé~ate (EDTA) et d'une base choisie parmi NaOH et KOH et dans un solvant hydrocarboné ou oxygéné ; dl) extraction de la [bis (diméthylamino) ] -o-tolylphosphine à l'aide d'un solvant analogue à celui de l'étape cl) ; el) purification de la [bis (diméthylamino) ] -o-tolylphosphine par distillation sous pression réduite. 5. Method according to claim 4, characterized in that it comprises the following steps: a1) slow addition of an o-tolylmagnesium halide carrying the substituents Z ± suitable for chloro [bis- (dimethylamino) phosphine to a temperature between -78 ° C and + 30 ° C, in a hydrocarbon or oxygenated solvent, under a neutral and anhydrous atmosphere, in stoichiometric proportions; bl) stirring at room temperature for a period of 8 to 15 hours; cl) hydrolysis at a temperature between -78 ° C and + 30 ° C using a solution of ethylene diamine tetrac ~ ate (EDTA) and a base chosen from NaOH and KOH and in a hydrocarbon solvent or oxygenated; dl) extraction of [bis (dimethylamino)] -o-tolylphosphine using a solvent similar to that of step cl); el) purification of [bis (dimethylamino)] -o-tolylphosphine by distillation under reduced pressure.
6. Procédé de préparation d'une phosphine selon la revendication 1 dans laquelle un ou plusieurs substituants Ri ne sont pas des groupes méthyle, caractérisé en ce que l'on fait réagir la [bis (diméthylamino) ] -o-tolylphosphine avec les aminés (R1)(R2)NH et (R3)(R4)NH ou avec une diamine chirale sous reflux d'un solvant aprotique choisi parmi le toluène, le benzène, le xylène et le cyclohexane.6. Process for the preparation of a phosphine according to claim 1, in which one or more substituents R 1 are not methyl groups, characterized in that the [bis (dimethylamino)] -o-tolylphosphine is reacted with the amines (R1) (R2) NH and (R3) (R4) NH or with a chiral diamine under reflux of an aprotic solvent chosen from toluene, benzene, xylene and cyclohexane.
7. Procédé de préparation d'un complexe phosphine / Pd, caractérisé en ce qu' il consiste à faire réagir une source de palladium avec une bis (diamino) o-tolylphosphine selon la revendication 1, à une température comprise entre 20 et 120°C, dans un solvant polaire, en présence d'un sel d'ammonium quaternaire R4X dans lequel les substituants R sont choisis indépendamment les uns des autres parmi les radicaux alkyle ayant de 4 à 10 atomes de carbone, de préférence de 4 à 6 atomes de carbone, et le radical benzyle, et X est un halogène.7. A process for the preparation of a phosphine / Pd complex, characterized in that it consists in reacting a source of palladium with a bis (diamino) o-tolylphosphine according to claim 1, at a temperature between 20 and 120 ° C, in a polar solvent, in the presence of a quaternary ammonium salt R 4 X in which the substituents R are chosen independently of one another from alkyl radicals having from 4 to 10 carbon atoms, preferably from 4 to 6 carbon atoms, and the benzyl radical, and X is a halogen.
8. Complexe phosphine / Pd, caractérisé en ce qu'il répond à la formule (II) :8. Phosphine / Pd complex, characterized in that it corresponds to formula (II):
Figure imgf000025_0001
Figure imgf000025_0001
dans laquelle les substituants Ri, R2, R3 et R4 représentent indépendamment les uns des autres un atome d'hydrogène, un radical alkyle, un radical alcenyle ou un radical aryle, étant entendu que l'un au moins des substituants RI, R2, R3 et R4 est différent d'un atome d'hydrogène ; ou bien les substituants RI et R2, et/ou les substituants R3 et R4 d'autre part forment ensemble un biradical qui forme un heterocycle aromatique ou non avec l'atome d'azote qui les porte, ou bien l'un des substituants RI ou R2 forme avec les substituants R3 et R4 un radical trivalent qui forme des heterocycles condensés aromatiques ou non avec le segment -N-P-N- ; les substituants Zi, Z2, Z3 et Z4 représentent indépendamment les uns des autres : * un groupe alkyle, un groupe aryle, un groupe cycloalkyle, un groupe alcenyle ;in which the substituents Ri, R2, R3 and R4 independently of one another represent a hydrogen atom, an alkyl radical, an alkenyl radical or an aryl radical, it being understood that at least one of the substituents RI, R2, R3 and R4 is different from a hydrogen atom; either the substituents RI and R2, and / or the substituents R3 and R4 on the other hand together form a biradical which forms an aromatic heterocycle or not with the nitrogen atom which carries them, or one of the substituents RI or R2 forms with the substituents R3 and R4 a trivalent radical which forms heterocycles condensed aromatic or not with the segment -NPN-; the substituents Zi, Z 2 , Z 3 and Z 4 represent independently of each other: * an alkyl group, an aryl group, a cycloalkyl group, an alkenyl group;
* un groupe R'O-, dans lequel R' représente H, un radical alkyle, un radical aryle, un radical trialkylsilyle ou un radical triarylsilyle ; * un groupe (R")2N- dans lequel les substituants R" représentent indépendamment les uns des autres H, un radical alkyle ou un radical aryle ;* a group R'O-, in which R 'represents H, an alkyl radical, an aryl radical, a trialkylsilyl radical or a triarylsilyl radical; * a group (R ") 2 N- in which the substituents R" independently of one another represent H, an alkyl radical or an aryl radical;
* un groupe (R'")3Si- dans lequel les substituants R'" représentent indépendamment les uns des autres H, un radical alkyle, un radical aryle, un radical alkyloxy ou un radical aryloxy ;* a group (R '") 3 Si- in which the substituents R'" represent, independently of each other H, an alkyl radical, an aryl radical, an alkyloxy radical or an aryloxy radical;
* un groupe P(R"")2, un groupe P0(R"")2, un groupe PS(R"")2 ou un groupe PSe(R"")2, dans lequel les substituants R"" représentent indépendamment les uns des autres H, un radical alkyle, un radical aryle, un radical alkyloxy ou un radical aryloxy. X représente un atome d'halogène.* a group P (R "") 2 , a group P0 (R "") 2 , a group PS (R "") 2 or a group PSe (R "") 2 , in which the substituents R "" independently represent each other H, an alkyl radical, an aryl radical, an alkyloxy radical or an aryloxy radical. X represents a halogen atom.
9. Utilisation d'un complexe phosphine / Pd selon la revendication 8 comme catalyseur d'une réaction d'hydroarylation d'une oléfine fonctionnalisée ou non.9. Use of a phosphine / Pd complex according to claim 8 as catalyst for a hydroarylation reaction of an olefin functionalized or not.
10. Utilisation d'un complexe phosphine / Pd selon la revendication 8 comme catalyseur d'une réaction d'arylation d'une oléfine fonctionnalisée ou non. 10. Use of a phosphine / Pd complex according to claim 8 as catalyst for an arylation reaction of a functionalized or non-functionalized olefin.
PCT/FR2000/002148 1999-07-26 2000-07-26 Phosphine/palladium complex catalysts for arylation of olefins WO2001007449A1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU70084/00A AU7008400A (en) 1999-07-26 2000-07-26 Phosphine/palladium complex catalysts for arylation of olefins

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR9909671A FR2796951A1 (en) 1999-07-26 1999-07-26 PHOSPHINE / PALLADIUM COMPLEXES, USEFUL AS CATALYSTS, IN PARTICULAR FOR THE ARYLATION OF OLEFINS
FR99/09671 1999-07-26

Publications (1)

Publication Number Publication Date
WO2001007449A1 true WO2001007449A1 (en) 2001-02-01

Family

ID=9548511

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/FR2000/002148 WO2001007449A1 (en) 1999-07-26 2000-07-26 Phosphine/palladium complex catalysts for arylation of olefins

Country Status (3)

Country Link
AU (1) AU7008400A (en)
FR (1) FR2796951A1 (en)
WO (1) WO2001007449A1 (en)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008514682A (en) * 2004-10-01 2008-05-08 ダック ソシエタ ア レスポンサビリタ リミタータ Novel histone deacetylase inhibitors
WO2009017100A1 (en) * 2007-07-30 2009-02-05 Nippon Oil Corporation Method for producing norbornene derivative
JP2009531393A (en) * 2006-03-31 2009-09-03 ダック ソシエタ ア レスポンサビリタ リミタータ N-hydroxy-3- (4- {3-phenyl-S-oxo-propenyl} -phenyl) -acrylamide derivatives and related compounds as histone deacetylase inhibitors for the treatment of cancer
CN109503737A (en) * 2018-11-19 2019-03-22 石家庄学院 A kind of polystyrene-supported chiral diamine class ligand and its preparation method and application

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2934564A (en) * 1957-11-08 1960-04-26 American Potash & Chem Corp Organohalophosphines
GB1037025A (en) * 1962-06-20 1966-07-20 Rohm & Haas Aromatic phosphorus-nitrogen-containing compounds
EP0719758A1 (en) * 1994-12-29 1996-07-03 Hoechst Aktiengesellschaft Process for the production of aromatic olefines

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2934564A (en) * 1957-11-08 1960-04-26 American Potash & Chem Corp Organohalophosphines
GB1037025A (en) * 1962-06-20 1966-07-20 Rohm & Haas Aromatic phosphorus-nitrogen-containing compounds
EP0719758A1 (en) * 1994-12-29 1996-07-03 Hoechst Aktiengesellschaft Process for the production of aromatic olefines

Non-Patent Citations (7)

* Cited by examiner, † Cited by third party
Title
ALAM K. ET AL.: "Reactions of xenon difluoride. Part 6. Some reactions of phosphorus, arsenic and iodine compounds", JOURNAL OF FLUORINE CHEMISTRY., vol. 36, no. 2, 1987, ELSEVIER SEQUOIA. LAUSANNE., CH, pages 179 - 184, XP002136434, ISSN: 0022-1139 *
BRAZIER JEFF ET AL.: "Synthèse de quelques composés organiques du phosphore", COMPTES RENDUS HEBDOMADAIRES DES SEANCES DE L'ACADEMIE DES SCIENCES, SERIE C: SCIENCES CHIMIQUES., vol. 262, no. 18, - 2 May 1966 (1966-05-02), GAUTHIER-VILLARS. MONTREUIL., FR, pages 1393 - 1396, XP000891567 *
BRUNEL J M ET AL: "Highly efficient phosphapalladacyclic catalysts for the hydroarylation of norbornene", ANGEW. CHEM., INT. ED. (ACIEF5,14337851);2000; VOL.39 (11); PP.1946-1949, UMR CNRS 6516 Faculte de St Jerome, ENSSPICAM;Marseille; 13397; Fr. (FR), XP002149351 *
BRUNEL J.M. ET AL.: "Enantioselective palladium catalyzed allylic substitution with new chiral pyridine-phosphine ligands", TETRAHEDRON LETTERS., vol. 38, no. 34, 1997, ELSEVIER SCIENCE PUBLISHERS, AMSTERDAM., NL, pages 5971 - 5973, XP004086548, ISSN: 0040-4039 *
SHEEHAN S.K. ET AL.: "A flexible, highly efficient method for the preparation of homochiral oxazaphospholidine-boranes", TETRAHEDRON., vol. 50, no. 21, 1994, ELSEVIER SCIENCE PUBLISHERS, AMSTERDAM., NL, pages 6155 - 6162, XP002136436, ISSN: 0040-4020 *
TYE H. ET AL.: "Synthesis and applications of a new class of phosphorus donor ligands for asymmetric catalysis", JOURNAL OF THE CHEMICAL SOCIETY, CHEMICAL COMMUNICATIONS., no. 11, - 7 June 1997 (1997-06-07), CHEMICAL SOCIETY. LETCHWORTH., GB, pages 1053 - 1054, XP002136433, ISSN: 0022-4936 *
VAN DER KNAAP TH.A. ET AL.: "Synthesis and structure of aryl-substituted phospha-alkenes", TETRAHEDRON., vol. 40, no. 4, 1984, ELSEVIER SCIENCE PUBLISHERS, AMSTERDAM., NL, pages 765 - 776, XP002136435, ISSN: 0040-4020 *

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008514682A (en) * 2004-10-01 2008-05-08 ダック ソシエタ ア レスポンサビリタ リミタータ Novel histone deacetylase inhibitors
JP2009531393A (en) * 2006-03-31 2009-09-03 ダック ソシエタ ア レスポンサビリタ リミタータ N-hydroxy-3- (4- {3-phenyl-S-oxo-propenyl} -phenyl) -acrylamide derivatives and related compounds as histone deacetylase inhibitors for the treatment of cancer
WO2009017100A1 (en) * 2007-07-30 2009-02-05 Nippon Oil Corporation Method for producing norbornene derivative
CN101778809A (en) * 2007-07-30 2010-07-14 新日本石油株式会社 Method for producing norbornene derivative
US8487136B2 (en) 2007-07-30 2013-07-16 Nippon Oil Corporation Method for producing norbornene derivative
CN101778809B (en) * 2007-07-30 2013-10-16 新日本石油株式会社 Method for producing norbornene derivative
CN109503737A (en) * 2018-11-19 2019-03-22 石家庄学院 A kind of polystyrene-supported chiral diamine class ligand and its preparation method and application
CN109503737B (en) * 2018-11-19 2021-03-05 石家庄学院 Polystyrene-immobilized chiral diamine ligand and preparation method and application thereof

Also Published As

Publication number Publication date
FR2796951A1 (en) 2001-02-02
AU7008400A (en) 2001-02-13

Similar Documents

Publication Publication Date Title
JP4264418B2 (en) Ruthenium complexes as (preliminary) catalysts for metathesis reactions
EP1436304B1 (en) Novel disphospines, their complexes with transition metals and their use in asymmetric synthesis
WO2006136695A2 (en) Novel p-chiral functionalised arylphosphines and derivatives, the preparation and use thereof for asymmetrical catalysis
CN113620901B (en) Crown ether derived chiral 1,1 '-bi-2, 2' -naphthol, preparation method and application thereof
Benaglia et al. Enantioselective catalysis in water: Mukaiyama-aldol condensation promoted by copper complexes of bisoxazolines supported on poly (ethylene glycol)
EP1392708B1 (en) Method for preparing metallic carbene-based catalysts for hydrosilylation of unsaturated compounds and resulting catalysts
WO2001007449A1 (en) Phosphine/palladium complex catalysts for arylation of olefins
FR2789992A1 (en) Dicyano-bis-(phosphino)-binaphthyl or biphenyl preparation in 4 stages from diol, used as ligand in metal complexes useful as asymmetric catalysts e.g. for hydrogenation
EP0571515B1 (en) Chiral phosphinite-boranes, their preparation and use
FR2833957A1 (en) New aminoborane derivatives useful as borylating agents, e.g. for preparing arylboratranes, 2-aryl-5,5-dimethyl-1,3,2-dioxaborinanes, arylboronic acids and B,B-diaryl-aminoboranes
WO2008135386A1 (en) Chiral ligands of the n-heterocyclic carbene type for asymmetrical catalysis
FR2856402A1 (en) PROCESS FOR THE PREPARATION OF HALOGENOALKYLCHLOROSILANE
US20080275274A1 (en) Process for the preparation of enantiomerically enriched compounds
EP1080096B1 (en) Novel furylphosphines and organometallic complexes containing them
EP0189694B1 (en) Process for the preparation of isocyanates and isocyanate derivatives
WO2002012253A1 (en) Use of chiral diphosphines as optically active ligands
FR2816946A1 (en) Chiral diphosphine compounds used for producing metallic diphosphine complexes used as catalysts in asymmetric hydrogenation processes
JP4928798B2 (en) Catalyst for asymmetric synthesis, ligand used therein, and method for producing optically active compound by asymmetric synthesis reaction using them
JP5283984B2 (en) Process for producing transition metal compound
JP2002537400A (en) Chiral diazaphospholidine ligand
WO2012049424A2 (en) Method for synthesizing phosphine
BE1013489A6 (en) Method to prepare aromatic carbamates from nitro-aromatic compounds
CN104926747A (en) Synthetic method and application of cyclohexyl oxazoline ligand with optical activity
FR2775975A1 (en) New 1-phospha-norbornadiene derivatives useful for preparing bis-phosphine ligands for asymmetric synthesis catalysts
EP2200986B1 (en) Chiral tridentate compounds, corresponding organometal complexes, method for preparing same and use of said compounds and complexes as ligands in asymmetrical catalysis

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): AE AG AL AM AT AU AZ BA BB BG BR BY CA CH CN CR CU CZ DE DK DM DZ EE ES FI GB GD GE GH GM HR HU ID IL IN IS JP KE KG KP KR KZ LC LK LR LS LT LU LV MA MD MG MK MN MW MX NO NZ PL PT RO RU SD SE SG SI SK SL TJ TM TR TT TZ UA UG US UZ VN YU ZA ZW

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): GH GM KE LS MW MZ SD SL SZ TZ UG ZW AM AZ BY KG KZ MD RU TJ TM AT BE CH CY DE DK ES FI FR GB GR IE IT LU MC NL PT SE BF BJ CF CG CI CM GA GN GW ML MR NE SN TD TG

121 Ep: the epo has been informed by wipo that ep was designated in this application
DFPE Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101)
REG Reference to national code

Ref country code: DE

Ref legal event code: 8642

122 Ep: pct application non-entry in european phase
NENP Non-entry into the national phase

Ref country code: JP