6,6'-Bis-(1-Phosphanorbornadiene) diphosphines, their preparation and their uses

Abstract

A subject of the present invention is new 6,6′-bis-(1-phosphanorbornadiene) diphosphines, their preparation process and their use in asymmetrical catalysis. The new diphosphines correspond to general formula (I): in which R 1 , R 2 , R 3 , R 4 , R 5 are as defined in claim 1.

1 . 6,6′-bis-(1-phosphanorbornadiene) diphosphine corresponding to the following formula:  
       
         
           
           
               
               
           
         
       
       in said formula (I): 
 R 1 , R 2 , R 3 , R 4 , R 5 , identical or different, represent a hydrogen atom or hydrocarbon radical optionally substituted, having from 1 to 40 carbon atoms, which can be a linear or branched, saturated or unsaturated acyclic aliphatic radical; a monocyclic or polycyclic, saturated, unsaturated or aromatic, carbocyclic or heterocyclic radical; a linear or branched, saturated or unsaturated aliphatic radical, carrying a cyclic substituent,  
 R 2  and R 3  together with the carbon atoms which carry them can form a saturated or unsaturated ring,  
 R 5  can represent a radical of  
                     
  type, in which R 1 ′, R 2 ′ and R 3 ′ have the same meaning as that given for R 1 , R 2  and R 3 ,  
 R 4  and R 5  cannot simultaneously represent a phenyl group.  
 
     
     
         2 . Optically active 6,6′-bis-(1-phosphanorbornadiene) diphosphine according to  claim 1  corresponding to the following formula:  
       
         
           
           
               
               
           
         
         in formula (Ia), R 1  to R 5  have the meanings given in  claim 1 .  
       
     
     
         3 . Optically active 6,6′-bis-(1-phosphanorbornadiene) diphosphine according to  claim 1  corresponding to the following formula:  
       
         
           
           
               
               
           
         
       
       in formula (Ib), R 1  to R 5  have the meanings given in  claim 1 .  
     
     
         4 . 6,6′-bis-(1-phosphanorbornadiene) diphosphine according to  claim 1  in meso form corresponding to the following formula:  
       
         
           
           
               
               
           
         
       
       in formula (Im), R 1  to R 5  have the same meanings given in  claim 1 .  
     
     
         5 . 6,6′-bis-(1-phosphanorbornadiene) diphosphine according to  claim 1  in racemic form corresponding to the following formula:  
       
         
           
           
               
               
           
         
       
       in formulae (Ir), R 1  and R 5  have the meanings given in  claim 1 .  
     
     
         6 . Diphosphine according to one of  claims 1  to  5  characterized in that it corresponds to formulae (I), (Ia), (Ib), (Im), (Ir) in which R 1 , R 2 , R 3 , R 4 , R 5  identical or different, represent: 
 a linear or branched, saturated or unsaturated acylic aliphatic radical, preferably having 1 to 12 carbon atoms: the hydrocarbon chain being optionally interrupted by a heteroatom and/or optionally carrying substituents,  
 a linear or branched, saturated or unsaturated acylic aliphatic radical carrying an optionally substituted cyclic substituent,  
 a carbocylic radical which is saturated or comprises 1 or 2 unsaturations in the ring, generally having 3 to 8 carbon atoms, preferably 6 carbon atoms in the ring; said ring can be substituted,  
 a saturated or unsaturated polycyclic carbocylic radical, preferably bicylic, the number of carbon atoms in each ring varying preferably between 3 and 6: said ring can be substituted,  
 a polycyclic aromatic hydrocarbon radical; the rings can together form ortho-condensed, ortho- and peri-condensed systems; said rings being optionally substituted,  
 a saturated, unsaturated or aromatic heterocyclic radical, in particular comprising 5 or 6 atoms in the rings including 1 or 2 heteroatoms such as nitrogen, sulphur and oxygen atoms; the carbon atoms of the heterocycle being optionally substituted,  
 a polycyclic heterocyclic radical defined as being either a radical constituted by at least 2 aromatic or non-aromatic heterocycles containing at least one heteroatom in each ring and together forming ortho- or ortho- and peri-condensed systems or a radical constituted by at least one aromatic or non-aromatic hydrocarbon ring and at least one aromatic or non-aromatic heterocycle together forming ortho- or ortho- and peri-condensed systems; the carbon atoms of said rings being optionally substituted.  
 
     
     
         7 . Diphosphine according to one of  claims 1  to  6  characterized in that it corresponds to the formulae (I), (Ia), (Ib), (Im), (Ir) in which R 1 , R 2 , R 3 , R 4 , R 5  identical or different, represent an aromatic hydrocarbon radical, and in particular a benzene radical corresponding to general formula (II):  
       
         
           
           
               
               
           
         
       
       in said formula (II): 
 n is an integer from 0 to 5, preferably from 0 to 3,  
 Q represents R 0 , one of the following groups or functions: 
 a linear or branched alkyl radical having from 1 to 6 carbon atoms, preferably from 1 to 4 carbon atoms, such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl,  
 a linear or branched alkenyl radical having from 2 to 6 carbon atoms, preferably from 2 to 4 carbon atoms, such as vinyl, allyl,  
 a linear or branched alkoxy radical having from 1 to 6 carbon atoms, preferably from 1 to 4 carbon atoms such as methoxy, ethoxy, propoxy, isopropoxy, butoxy radicals,  
 an acyl group having from 2 to 6 carbon atoms,  
 a radical of formula: 
 —R 6 —OH  
 —R 6 —COOR 7    
 —R 6 —CHO  
 —R 6 —NO 2    
 —R 6 —CN  
 —R 6 —N(R 7 ) 2    
 —R 6 —CO—N(R 7 ) 2    
 —R 6 —SH  
 —R 6 —X  
 —R 6 —CF 3    
 —O—CF 3    
 
 in said formulae, R 6  represents a valency bond or a saturated or unsaturated, linear or branched, divalent hydrocarbon radical having from 1 to 6 carbon atoms such as, for example, methylene, ethylene, propylene, isopropylene, isopropylidene; the R 7  radicals, identical or different, represent a hydrogen atom or a linear or branched alkyl radical having from 1 to 6 carbon atoms; X symbolizes a halogen atom, preferably a chlorine, bromine or fluorine atom.  
 
 Q represents R 0 ′, one of the following more complex radicals:  
                     
 in which:  
 m is an integer from 0 and 5, preferably from 0 to 3,  
 R 0  has the meaning indicated previously,  
 R 8  represents a valency bond; a saturated or unsaturated, linear or branched divalent hydrocarbon group having from 1 to 6 carbon atoms such as for example methylene, ethylene, propylene, isopropylene, isopropylidene or one of the following. groups called Z: 
 —O—; —CO—; COO—; —NR 7 —; —CO—NR 7 —; —S—; —SO 2 —; —NR 7 —CO—; 
 in said formulae, R 7  represents a hydrogen atom, a linear or branched alkyl group having from 1 to 6 carbon atoms, preferably a methyl or ethyl radical.  
 when n is greater than 1, the Q radicals can be identical or different and 2 successive carbon atoms of the benzene ring can be joined together by a ketal bridge such as the extranuclear methylene dioxy or ethylene dioxy radicals.  
 
     
     
         8 . Diphospine according to one of  claims 1  to  7  characterized in that it corresponds to formulae (I), (Ia), (Ib), (Im), (Ir) in which the R 2  and R 3  radicals can together with the carbon atoms which carry them form a saturated or unsaturated ring preferably having from 5 to 7 carbon atoms and more preferentially 6 carbon atoms.  
     
     
         9 . Diphosphine according to one of  claims 1  to  8  characterized in that it correspnds to formulae (I), (Ia), (Ib), (Im), (Ir), in which the different radicals represent: 
 for R 1  and R 2  radicals, 
 a hydrogen atom,  
 a linear or branched alkyl radical having from 1 to 4 carbon atoms,  
 
 for the R 3  radical, 
 a radical other than a hydrogen atom, preferably a linear or branched alkyl radical having from 1 to 4carbon atoms, a phenyl radical,  
 
 and for R 4  and R 5  radicals, 
 a hydrogen atom,  
 a linear or branched alkyl radical having from 1 to 4 carbon atoms, 
 a phenyl radical or a phenyl radical carrying one or more substituents, preferably 1 to 3 linear or branched alkyl or alkoxy radicals having 1 to 4 carbon atoms, a naphthyl radical.  
 
 
 
     
     
         10 . 6,6′-bis-(1-phosphanorbornadiene) diphosphine according to  claim 1  corresponding to the following formula:  
       
         
           
           
               
               
           
         
       
       in said formula (I′): 
 R 1 , R 2 , R 3 , R 4 , identical or different, represent a hydrogen atom or a hydrocarbon radical, optionally substituted, having from 1 to 40 carbon atoms, which can be a saturated or unsaturated, linear or branched acyclic aliphatic radical; a saturated, unsaturated or aromatic, monocyclic or polycyclic carbocyclic or heterocyclic radical; a saturated or unsaturated, linear or branched aliphatic radical carrying a cyclic substituent,  
 R 2  and R 3  can form together with the carbon atoms which carry them a saturated or unsaturated ring,  
 R 5  represents a sterically hindered group  
 R 4  and R 5  cannot simultaneously represent a phenyl group.  
 
     
     
         11 . Diphospine according to  claim 10  characterized in that it corresponds to formula (I′) in which the R 5  radical represents: 
 a branched, saturated or unsaturated aliphatic radical the characteristic of which is having a tertiary radical located in b position with respect to the phosphorus atom, preferably, a tert-butyl radical;  
 a phenyl radical carrying at least one substituent, preferably, one or more alkyl or alkoxy radicals having from 1 to 4 carbon atoms or a naphthyl radical,  
 
     
     
         12 . Diphosphine according to one of claims  10  and  11  characterized in that it corresponds to formula (I′) in which the R 1 , R 2 , R 3 , R 4  radicals have the meaning given in  claims 6  to  9 .  
     
     
         13 . Diphosphine according to one of  claims 1  to  12  characterized in that it corresponds to one of the formulae:  
       
         
           
           
               
               
           
         
       
     
     
         14 . 6,6′-bis-(1-phosphanorbornadiene) diphosphine dioxide or disulphide according to one of  claims 1  to  13  corresponding to the following formulae:  
       
         
           
           
               
               
           
         
       
       in formulae (IX) and (IX′), R 1  to R 5  have the meanings given in  claims 1  to  13 .  
     
     
         15 . 6,6′-bis-(1-phosphanorbornadiene) diphosphine dioxode according to  claim 14  in optically active form corresponding to the following formulae:  
       
         
           
           
               
               
           
         
       
       in formulae (IXa), (IXb), (IXm) and (IXr), R 1  to R 5  have the meanings given in  claims 1  to  13 .  
     
     
         16 . 6,6′-bis-(1-phosphanorbornadiene) diphosphine disulphide according to  claim 14  in optically active form corresponding to the following formulae:  
       
         
           
           
               
               
           
         
       
       in the formulae (IXa′), (IX′b), (IX′m) and (IX′r), R 1  to R 5  have the meanings given in  claims 1  to  13 .  
     
     
         17 . Preparation process for a diphosphine of formula (I) or (I′) described in one of claims  1 ,  6  to  13  characterized in that it consists in reacting: 
 a diphosphole of formula (III) originating from the rearrangement of the diphosphole of formula (IV):  
                     
 in said formulae (III) and (IV), R 1 , R 2  and R 3  have the meaning indicated previously,  
 and an acetylenic compound of formula (V):  
                     
 in said formula (V), R4 and R5 have the meaning given previously.  
 
     
     
         18 . Process according to  claim 17  characterized in that the diphosphole of formula (III) is obtained from a diphosphole of formula (IV) by thermal treatment carried out at a temerature comprised between 100° C. and 200° C., preferably between 130° C. and 150° C.  
     
     
         19 . Process according to one of claims  17  and  18  characterized in that the diphosphole of formula (IV) is: 
 1,1′-bis-(3,4-dimethylphosphole),  
 1,1′-bis-(3-methylphosphole),  
 1,1′-bis-(phosphole).  
 
     
     
         20 . Process according to one of  claims 17  to  19  characterized in that the acetylenic compound of formula (V) is 
 acetylene,  
 methylacetylene,  
 tert-butylacetylene,  
 phenylacetylene,  
 phenylmethylacetylene,  
 o-tolylacetylene,  
 bis-(o-tolylacetylene),  
 phenyl-tert-butylacetylene,  
 phenylmesitylacetylene,  
 bis-(mesityl)acetylene.  
 
     
     
         21 . Process according to one of  claims 17  to  20  characterized in that the diphosphole of formula (IV) is obtained by reaction: 
 of a compound of formula (VI):  
                     
 in formula (VI), R 1 , R 2 , R 3  have the meanings indicated previously, and Y represents any group, preferably, an aromatic carbocyclic radical, and more preferentially, a phenyl radical or an aromatic heterocyclic radical,  
 with an alkali metal, leading to a compound of formula (VII):  
                     
 in formula (VII), R 1 , R 2 , R 3  have the meanings indicated previously, and M represents an alkali metal, preferably lithium or sodium.  
 dimerizing the compound of formula (VII) into a compound of formula (IV).  
 
     
     
         22 . Process according to  claim 21  characterized in that, at the end of the reaction between the compound of formula (VI) and the alkali metal, a Lewis acid is used, preferably AlCl 3  and optionally a tertiary alkyl halide, preferably tert-butyl chloride.  
     
     
         23 . Process according to  claim 21  characterized in that the dimerization of the compound of formula (VII) is carried out using iodine.  
     
     
         24 . Process according to  claim 21  characterized in that the phosphole of formula (IV) is obtained by reacting a diene of formula (VIII) with a dihalogenarylphosphine:  
       
         
           
           
               
               
           
         
       
       in formula (VIII), R 1 , R 2 , R 3  have the meanings given previously.  
     
     
         25 . Process according to  claim 24  characterized in that the dihalogenarylphosphine used is dichlorophenylphosphine, dibromophenylphosphine or their mixtures preferably comprising equimolar quantities of each of the dihalogenphosphines.  
     
     
         26 . Proces according to  claim 25  characterized in that a base, preferably a tertiary amine is added at the end of the reaction of the compound (VIII) and dihalogenarylphosphine.  
     
     
         27 . Process according to  claim 26  characterized in that a neuralisation stage is carried out.  
     
     
         28 . Process according to one of  claims 24  to  27  characterized in that the phosphole of formula (VI) is separated by extraction.  
     
     
         29 . Preparation process for a disphosphine dioxide of formula (IX) described in  claim 14  characterized in that it consists of oxidizing a diphosphine of formula (I) using an oxidizing agent.  
     
     
         30 . Preparation process for a diphosphine dioxide in meso form or in racemic form described in  claim 15  characterized in that it consists of oxidizing a diphosphine in meso form (Im) and in racemic form (Ir), then separating the two diasteroisomers of the diphosphine dioxides.  
     
     
         31 . Process according to  claim 30  characterized in that the diphosphine in meso form (Im) and in racemic form (Ir) is obtained according to one of  claims 17  to  20 .  
     
     
         32 . Process according to one of  claim 30  to  31  characterized in that the oxidizing agent is a hydrogen peroxide solution.  
     
     
         33 . Process according to one of  claims 30  to  32  characterized in that the two diastereoisomers (IXm) and (IXr) are separated by liquid column chromatography, preferably with a silica support allowing firstly the diphosphine dioxide to be obtained in meso form (IXm) and the diphosphine dioxide to be obtained in racemic form (IXr).  
     
     
         34 . Preparation process for an optically active diphosphine of formula (Ia) or (Ib) described in one of the claims  2 ,  3 ,  6  to  13  characterized in that it consists of: 
 carrying out the resolution of diphosphine dioxide in racemic form (IXr),  
 then separately carrying out the reduction of the diphosphine dioxide enantiomers (IXa) or (IXb)  
 
     
     
         35 . Process according to  claim 34  characterized in that the resolution of (IXr) is carried out by chiral liquid chromatography.  
     
     
         36 . Preparation process for an optically active diphosphine of formula (Ia) or (Ib) described in one of the claims  2 ,  3 ,  6  to  13  characterized in that it consists of: 
 carrying out the reduction of diphosphine dioxide in racemic form (IXr), leading to the diphosphine in racemic form (Ir),  
 carrying out the resolution of the diphosphine in racemic form (Ir).  
 
     
     
         37 . Process according to one of claims  34  and  36  characterized in that the reduction is carried out by trichlorosilane, hexachlorodisilazane, phenyltrisilane, a hydride in particular LiAlH 4  or NaBH 4 .  
     
     
         38 . Process according to  claim 37  characterized in that a base is added, preferably a tertiary amine, more preferentially a picoline, pyridine, 2-ethylpyridine, 4-ethylpyridine, 2-methylpyridine, 4-methylpyridine, 2,6-dimethylpyridine, imidazole, 1-methylimidazole, TMEDA (tetramethylenediamine), N-methylpyrrolidine, 4-methylmorpholine, triethylamine, DBU (1,8-diazabicyclo[5.4;0.]undecene-7).  
     
     
         39 . Process for the resolution of a 6,6′-bis-(1-phosphanorbornadiene) diphosphine in racemic form correpsonding to formula (Ir) described in  claim 5  characterized in that it consists in reacting it with a palladium and/or platinum complex as chiral auxiliary, in an organic solvent thus forming diastereoisomeric complexes, then resolving said optically pure complexes.  
     
     
         40 . Process according to  claim 39  characterized in that the chiral auxiliary corresponds to the general formula:  
       
         
           
           
               
               
           
         
       
       in said formula: 
 M represents palladium and/or platinum, 
 R 1 , R 2 , R 3  and R 4  represent a hydrogen atom or an alkyl radical having from 1 to 10 carbon atoms or a cycloalkyl radical having from 3 to 10 carbon atoms,  
 R 3  and R 4  are different and at least one of the two represents a hydrogen atom,  
 R has the meaning given for R 1 , R 2 , R 3  and R 4 ,  
 X represents a halogen atom,  
 n is an integer from 0 to 4,  
 when n is greater than 1, the two R radicals and the 2 successive atoms of the benzene ring can together form a ring having from 5 to 7 carbon atoms.  
 
 
     
     
         41 . Process according to one of  claims 39  to  40  characterized in that the chiral auxiliary corresponds to general formula (X) in which R 1 , R 2 , R 3  and R 4  represent a hydrogen atom or a methyl radical, X represents a chlorine atom and n is equal to 0.  
     
     
         42 . Process according to one of  claims 39  to  41  characterized in that the chiral auxiliary corresponds to general formula (X) in which R 1 , R 2 , R 3  and R 4  represent a hydrogen atom or a methyl radical, X represents a chlorine atom when n is equal to 2, the two R radicals form a benzene ring.  
     
     
         43 . Process according to one of  claims 39  to  42  characterized in that the chiral auxiliary corresponds to general formula (XI):  
       
         
           
           
               
               
           
         
       
     
     
         44 . Process according to one of  claims 39  to  43  characterized in that the separation of the two enantiomers is carried out by liquid column chromatography, preferably with a silica support.  
     
     
         45 . Process according to  claim 39  characterized in that the two pure diphosphine enantiomers are recovered by solubilizing complexes in an organic solvent such as, for example, dichloromethane, then decomplexing using a hydrocyanic acid salt, preferably an alkaline salt and even more preferentially sodium.  
     
     
         46 . Preparation process for a diphosphine disulphide of formula (IX′) described in  claim 14  characterized in that it consists of reacting a diphosphine of formula (I) with sulphur.  
     
     
         47 . Preparation process for a diphosphine disulphide in meso form or in racemic form described in  claim 15  characterized in that it consists of reacting the mixture of diastereoisomers (Im) and (Ir) with sulphur, thus converting them into diphosphine disulphides (IX′m) and (IX′r), then separating the two diastereoisomers of the diphosphine disulphides.  
     
     
         48 . Process according to  claim 47  characterized in that the diphosphine in meso form (Im) and in racemic form (Ir) is obtained according to one of  claims 17  to  20 .  
     
     
         49 . Preparation process for an optically active diphosphine of formula (Ia) or (Ib) described in one of claims  2 ,  3 ,  6  to  13  characterized in that it consists in carrying out the resolution of the racemic mixture of diphosphine disulphides (IX′r) preferably on a chiral column, the reducing the enantiomers of the diphosphine disulphides (IX′a) and (IX′b) to diphosphine enantiomers (Ia) and (Ib).  
     
     
         50 . Preparation process for an optically active diphosphine of formula (Ia) or (Ib) described in one of the claims  2 ,  3 ,  6  to  13  characterized in that it consists of reducing the racemic mixture of diphosphine disulphides (IX′r) to a racemic mixture of diphosphines (Ir) then carrying out the resolution of the racemic mixture of diphosphines into enantiomers (Ia) and (Ib).  
     
     
         51 . Process according to one of claims  49  and  50  characterized in that the diphosphine disulphides are reduced by reaction with a phosphorated reagent of, PBu 3  or P(CH 2 CH 2 CN) 3  type.  
     
     
         52 . Preparation process for an optically active diphosphine of formula (Ia) or (Ib) described in one of claims  2 ,  3 ,  6  to  13  characterized in that it consists of converting the racemic mixture of diphosphine disulphides (IX′r) into a racemic mixture of diphosphine dioxides (IXr) then obtaining the optically active diphosphines (Ia) and (Ib) according to one of  claims 34  to  45 .  
     
     
         53 . Process according to  claim 52  characterized in that the convertion of the diphosphine disulphides into diphosphine dioxides is carried out by reacting the diphospine disulphides with cyclohexene oxide, in trifluoroacetic acid and in an organic solvent medium.  
     
     
         54 . Complex containing an optically active diphosphine described in one of claims  2 ,  3 ,  6  to  13  and a chiral auxiliary characterized in that it corresponds to one of the following formulae:  
       
         
           
           
               
               
           
         
       
       in said formulae, M represents palladium or platinum, X a halogen atom, preferably chlorine and A represents the remainder of a chrial metallic complex corresponding to one of formulae (X) and preferentially (XI).  
     
     
         55 . Complex containing an optically active diphosphine described in one of claims  2 ,  3 ,  6  and  13  and a transition metal characterized in that the ligand corresponds to one of the following formuale:  
       
         
           
           
               
               
           
         
       
       in formula (Ia) and (Ib), R 1  to R 5  have the meanings given in  claims 1  to  13 .  
     
     
         56 . Complex according to  claim 55  characterized in that the transisiton metal is chosen from: rhodium, ruthenium, rhenium, iridium, cobalt, nickel, platinum, palladium.  
     
     
         57 . Complex containing an optically active diphosphine and of rhodium and/or iridium according to one of claims  55  and  56  characterized in that it is represented by the following formulae: 
       [M L 2 (P*P)]Y  (XIVa)[M L 2 (P*P)]Y  (XIVb) 
       in said formulae: 
 (P*P) in formula (XIVa) represents the diphosphine of formula (Ia) and in formula (XIVb) represents the diphosphine of formula (Ib),  
 M represents rhodium or iridium,  
 Y represents a coordinating anionic ligand,  
 L represents a neutral ligand.  
 
     
     
         58 . Complex according to  claim 57  characterized in that it corresponds to formula (XVIa) or (XVIb) in which: 
 L represents an olefine having from 2 to 12 carbon atoms and two ligands L can be linked together to form a polyunsaturated, linear or cyclic hydrocarbon chain; L preferably representing 1,5-cyclooctadiene, norbornadiene, ethylene,  
 Y represents a PF 6   − , PCl 6   − , BF 4   − , BCl 4   − , SbF 6   − , SbCl 6   − , BPh 4   − , ClO 4   − , CN − , CF 3 SO 3   −  anion, preferably halogen, Cl −  or Br − , a 1,3-diketonate, alkylcarbonate, haloalkylcarboxylate anion with a lower alkyl; radical, a phenylcarboxylate or phenolate anion the benzene ring of which can be substituted by lower alkyl radicals and/or halogen atoms.  
 
     
     
         59 . Complex containing an optically active diphosphine and iridium according to one of claims  55  and  56  characterized in that it is represented by the following formulae: 
       [Ir L(P*P)]Y  (XVa)[Ir L(P*P)]Y  (XVb) 
       in said formulae, (P*P), L and Y have the meanings given for formulae (XIVa) and (XIVb).  
     
     
         60 . Complex containing an optically active diphosphine and ruthenium according to one of claims  55  and  56  characterized in that it is represented by the following formulae: 
       [RuY 1 Y 2 (P*P)]  (XVIa)[RuY 1 Y 2 (P*P)]  (XVIb) 
       in said formulae: 
 (P*P) in formula (XVIa) represents the diphosphine of formula (Ia) and in formula (XVIb) represents the diphosphine of formula (Ib),  
 Y 1  and Y 2 , identical or different, preferably represent a PF 6   − , PCl 6   − , BF 4   − , BCl 4   − , SbF 6   − , SbCl 6   − , BPh 4   − , ClO 4   − , CF 3 SO 3   −  anion, a halogen atom, more particularly chlorine or bromine or a carboxylate anion, preferentially acetate, trifluoroacetate.  
 
     
     
         61 . Complex containing an optically active diphosphine and ruthenium according to one of claims  55  and  56  characterized in that it is represented by the following formulae: 
       [RuY 1 Ar(P*P)Y 2 ]  (XVIc)[RuY 1 Ar(P*P)Y 2 ]  (XVId) 
       in said formulae: 
 (P*P) in formula (XVIc) represents the diphosphine of formula (Ia) and in formula (XVId) represents the diphosphine of formula (Ib),  
 Ar represents benzene, p-methylisopropylbenzene, hexamethylbenzene,  
 Y 1  represents a halogen atom, preferably chlorine or bromine,  
 Y 2  represents an anion, preferably a PF 6   − , PCl 6   − , BF 4   − , BCl 4   − , SbF 6   − , SbCl 6   − , BPh 4   − , ClO 4   − , CF 3 SO 3   − .  
 
     
     
         62 . Preparation process for a complex according to one of  claims 55  to  61  characterized in that it consists of reacting a diphosphine of formula (Ia) Pr (Ib) with the transition metal compound, in an appropriate organic solvent.  
     
     
         63 . Complex containing a diphosphine of formula (Ia) or (Ib) described in one of claims  2 ,  3 ,  6  to  13  and a palladium precursor, preferably [Pd(allyl)Cl] 2 .  
     
     
         64 . Use of an optically active diphosphine described in one of claims  2 ,  3 ,  6  to  13  for the preparation of catalytic metallic complex coordinates to selectively carry out asymmetrical synthesis in organic chemistry.  
     
     
         65 . Use of an optically active diphosphine described in one of claims  2 ,  3 ,  6  to  13  for the preparation of catalytic metallic complex coordinates to selectively carry out asymmetrical hydrogenation.  
     
     
         66 . Use of metallic complexes described in one of  claims 55  to  61  to carry out asymmetrical hydrogenation of an a,b-unsaturated carboxylic acid and/or its derivatives.  
     
     
         67 . Use according to one of  claims 65  to  66  characterized in that the a,b-unsaturated carboxylic acid and/or its derivatives correspond more particularly to the following general formula:  
       
         
           
           
               
               
           
         
       
       in said formula (XVII): 
 R 1 , R 2 , R 3  and R 4  represent a hydrogen atom and any hydrocarbon group, provided that: 
 if R 1  is different from R 2  and different from a hydrogen atom, then R 3  can be any hydrocarbon or functional group designated by R.  
 if R 1  or R 2  represents a hydrogen atom and if R 1  is different from R 2 , then R 3  is different from a hydrogen atom and different from —COOR 4 ,  
 if R 1  is identical to R 2  and represents any hydrocarbon or functional group designated by R then R 3  is different from —CH—(R) 2  and different from —COOR 4 ,  
 
 one of groups R 1 , R 2  and R 3  can represent a functional group.  
 
     
     
         68 . Process according to  claim 67  characterized in that a,b-unsaturated carboxylic acid and/or its derivative correspond to formula (XVII) in which the R 1  to R 4  radicals identical or different represent an optionally substituted hydrocarbon radical having from 1 to 20 carbon atoms, which can be a saturated or unsaturated, linear or branched acyclic aliphatic radical; a saturated, unsaturated or aromatic, monocyclic or polycyclic carbocyclic or heterocyclic radical; a saturated or unsaturated, linear or branched aliphatic radical carrying a cyclic substituent.  
     
     
         69 . Process according to  claim 68  characterized in that the carboxylic acid used is a substituted acrylic acid which is a precursor of an amino acid, itaconic acid and/or a derivative, an arylpropionic acid and/or a derivative.  
     
     
         70 . Use of an optically active diphosphine described in one of claims  2 ,  3 ,  6  to  13  for the preparation of catalytic metallic complex coordinates to carry out an allylic substitution reaction.  
     
     
         71 . Use of metallic complexes described in  claim 64  for carrying out an allylic substituion reaction.  
     
     
         72 . Use according to one of claims  70  and  71  characterized in that esters, preferably 1,3-diphenyl-3-acetoxypropene, are reacted with malonic acid alkyl esters, preferably dimethyl or diethyl malonate.  
     
     
         73 . Use according to  claim 72  characterized in that the malonic acid ester which is reacted can be in the form of an anion.