Method for the preparation of phosphine butadiene ligands, complexes thereof with copper and use thereof in catalysis

Abstract

The present invention relates to a method for preparing phosphine butadiene-type ligands, and their use, particularly as catalytic metal ligands used in the reactions leading to the formation of carbon-carbon and carbon-heteroatom bonds.

1 . A process for the preparation of a butadienylphosphine of formula (1): 
     
       
         
         
             
             
         
       
     
     in which:
 R a  and R b , which are identical or different, each represent a radical chosen independently from alkyl, aryl, heteroaryl, monoalkylamino, dialkylamino, alkoxy, aryloxy and heteroaryloxy; 
 R 1 , R 2 , R 3 , R 4  and R 5 , which are identical or different, are chosen independently from hydrogen, a hydrocarbon radical, an aryl radical and a heteroaryl radical; 
 said process comprising the stages of: 
 a) bringing a phosphonium halide of formula (2) into contact with a strong base in a polar aprotic solvent at low temperature, to result in the phosphonium diylide (3): 
 
     
       
         
         
             
             
         
       
     
     where R 1  is as defined above, Z and Z′ have definitions identical to those of R a  and R b  defined above and X represents a halogen atom chosen from fluorine, chlorine, bromine and iodine;
 b) which diylide (3) is reacted, in the polar aprotic solvent medium, at a temperature generally of between −70° C. and +10° C., with a halophosphine (4): 
 
     
       
         
         
             
             
         
       
     
     where R a  and R b  are as defined above and X′ represents a halogen atom chosen from fluorine, chlorine, bromine and iodine; 
     to result in the phosphonium ylide (5a), which undergoes a prototropic rearrangement to give the phosphonium ylide (5b): 
     
       
         
         
             
             
         
       
     
     where R a , R b , R 1 , Z and Z′ are as defined above;
 c) the ylide (5b) then being brought together with an α,β-unsaturated carbonyl derivative of formula (6): 
 
     
       
         
         
             
             
         
       
     
     in which R 2 , R 3 , R 4  and R 5  are as defined above, 
     to result, after removal of the solvent and optional purification, in the butadienylphosphine (1). 
   
   
       2 . The process as claimed in  claim 1 , in which the R a  and R b  substituents of the butadienylphosphine of formula (1) are identical and each represent a radical chosen independently from alkyl, aryl, heteroaryl, monoalkylamino, dialkylamino, alkoxy, aryloxy and heteroaryloxy. 
   
   
       3 . The process as claimed in  claim 1 , in which the R 4  and/or R 5  substituents can be connected so as to form, with the carbon atom which carries them, a carbocyclic or heterocyclic group having from 3 to 20 carbon atoms which is saturated, unsaturated, monocyclic or polycyclic, in the latter case comprising two or three rings, it being possible for the adjacent rings to be aromatic in nature. 
   
   
       4 . The process as claimed in  claim 1 , in which the strong base is butyllithium. 
   
   
       5 . The process as claimed in  claim 1 , in which the polar aprotic solvent is tetrahydrofuran. 
   
   
       6 . The process as claimed in  claim 1 , in which the butadienylphosphine of formula (1) obtained is of Z configuration or of E configuration or is in the form of a mixture in all proportions of the Z and E configurations. 
   
   
       7 . The process as claimed in  claim 1 , in which the butadienylphosphine of formula (1) obtained exhibits the following characteristics:
 R a  and R b  are identical and each represent a radical chosen from methyl, ethyl, propyl, butyl, phenyl, naphthyl, pyridyl or quinolyl;   R 1  represents hydrogen, methyl, ethyl or propyl;   R 2 , R 3  and R 4 , which are identical or different, are chosen independently from hydrogen, methyl, ethyl and propyl;   R 5  is chosen from hydrogen, methyl, ethyl, propyl, butyl, pentyl, phenyl, naphthyl, pyridyl and quinolyl.   
   
   
       8 . The process according to  claim 1 , in which the butadienylphosphine of formula (1) obtained exhibits the following characteristics:
 R a  and R b  each represent phenyl;   R 1  represents hydrogen;   R 2 , R 3  and R 4 , which are identical or different, are chosen independently from hydrogen, methyl, ethyl and propyl;   R 5  is chosen from methyl, ethyl, propyl, phenyl, naphthyl, pyridyl and quinolyl.   
   
   
       9 . The process as claimed in  claim 1 , in which the butadienylphosphine obtained is (Z)-Ph(C 4 H 4 )PPh 2 , (E)-Ph(C 4 H 4 )PPh 2 , (Z)—CH 3 (C 4 H 4 )PPh 2  or (E)-CH 3 Ph(C 4 H 4 )PPh 2 , where Ph represents phenyl. 
   
   
       10 . A complex comprising copper and at least one butadienylphosphine of formula (1): 
     
       
         
         
             
             
         
       
     
     in which:
 R a  and R b , which are identical or different, each represent a radical chosen independently from alkyl, aryl, heteroaryl, monoalkylamino, dialkylamino, alkoxy, aryloxy and heteroaryloxy; 
 R 1 , R 2 , R 3 , R 4  and R 5 , which are identical or different, are chosen independently from hydrogen, a hydrocarbon radical, an aryl radical and a heteroaryl radical. 
 
   
   
       11 . The complex as claimed in  claim 10 , in which the R a  and R b  substituents of the butadienylphosphine of formula (1) are identical and each represent a radical chosen independently from alkyl, aryl, heteroaryl, monoalkylamino, dialkylamino, alkoxy, aryloxy and heteroaryloxy. 
   
   
       12 . The complex as claimed in  claim 10 , in which the butadienylphosphine of formula (1) is of Z configuration or of E configuration or is in the form of a mixture in all proportions of the Z and E configurations. 
   
   
       13 . The complex as claimed in  claim 10 , in which the butadienylphosphine of formula (1) exhibits the following characteristics:
 R a  and R b  are identical and each represent a radical chosen from methyl, ethyl, propyl, butyl, phenyl, naphthyl, pyridyl or quinolyl;   R 1  represents hydrogen, methyl, ethyl or propyl;   R 2 , R 3  and R 4 , which are identical or different, are chosen independently from hydrogen, methyl, ethyl and propyl;   R 5  is chosen from hydrogen, methyl, ethyl, propyl, butyl, pentyl, phenyl, naphthyl, pyridyl and quinolyl.   
   
   
       14 . The complex as claimed in  claim 10 , in which the butadienylphosphine of formula (1) exhibits the following characteristics:
 R a  and R b  each represent phenyl;   R 1  represents hydrogen;   R 2 , R 3  and R 4 , which are identical or different, are chosen independently from hydrogen, methyl, ethyl and propyl;   R 5  is chosen from methyl, ethyl, propyl, phenyl, naphthyl, pyridyl and quinolyl.   
   
   
       15 . The complex as claimed in  claim 10 , in which the butadienylphosphine of formula (1) is (Z)-Ph(C 4 H 4 )PPh 2 , (E)-Ph(C 4 H 4 )PPh 2 , (Z)—CH 3 (C 4 H 4 )PPh 2  or (E)-CH 3 Ph(C 4 H 4 )PPh 2 , where Ph represents phenyl. 
   
   
       16 . The complex as claimed in  claim 10 , which is the phenylbutadienyldiphenylphosphine/copper iodide monomer complex [Ph-CH═CH—CH═CH—PPh 2 ] 2 CuI (iododi{η-[(4-phenyl-1,3-butadienyl)diphenylphosphine]}copper complex), where Ph represents the phenyl radical. 
   
   
       17 . The complex as claimed in  claim 10 , which is the methylbutadienyldiphenylphosphine/copper iodide monomer complex [CH 3 —CH═CH—CH═CH—PPh 2 ] 2 CuI (iododi{η-[(4-methyl-1,3-butadienyl)diphenylphosphine]}copper complex), where Ph represents the phenyl radical. 
   
   
       18 . A process for the creation of a carbon-carbon (C—C) bond or of a carbon-heteroatom (C-HE) bond by reacting a compound carrying a leaving group with a nucleophilic compound carrying a carbon atom or a heteroatom (HE) capable of replacing the leaving group, thus creating a C—C or C-HE bond, in which process the reaction is carried out in the presence of an effective amount of a catalytic system comprising at least one copper/butadienylphosphine complex. 
   
   
       19 . The process as claimed in  claim 18 , in which the copper/butadienylphosphine is a complex of the formula (1): 
     
       
         
         
             
             
         
       
     
     in which:
 R a  and R b , which are identical or different, each represent a radical chosen independently from alkyl, aryl, heteroaryl, monoalkylamino, dialkylamino, alkoxy, aryloxy and heteroaryloxy; 
 R 1 , R 2 , R 3 , R 4  and R 5 , which are identical or different, are chosen independently from hydrogen, a hydrocarbon radical, an aryl radical and a heteroaryl radical. 
 
   
   
       20 . The process as claimed in  claim 19 , in which the compound carrying a leaving group is a compound comprising a double bond or a triple bond in the α position with respect to said leaving group or an aromatic compound. 
   
   
       21 . The process as claimed in  claim 19 , in which the nucleophilic compound is an acyclic, cyclic or polycyclic hydrocarbon organic compound comprising at least one atom carrying a free doublet, which may or may not comprise a charge, and or comprise a carbon atom which can donate its electron pair. 
   
   
       22 . The process as claimed in  claim 19 , in which the ratio between the number of moles of the compound carrying the leaving group to the number of moles of the nucleophilic compound generally varies between 0.1 and 2.0. 
   
   
       23 . The process as claimed in  claim 19 , in which the total amount of copper/butadienylphosphine complex catalyst, expressed by the molar ratio of the number of moles of complex, expressed as copper, to the number of moles of compound carrying a leaving group, generally varies between 0.001 and 0.5. 
   
   
       24 . The process as claimed in  claim 19 , in which a base having a pKa of between 4 and 30 is involved. 
   
   
       25 . The process as claimed in  claim 19 , in which a base chosen from carbonates, hydrogencarbonates, phosphates or hydroxides of alkali metals or of alkaline earth metals, alkali metal hydrides, alkali metal alkoxides and tertiary amines is involved. 
   
   
       26 . The process as claimed in  claim 19 , which is carried out in the presence of a polar organic solvent. 
   
   
       27 . The process as claimed in  claim 19 , in which the nucleophilic compound and/or the compound carrying the leaving group is (are) used as solvent(s) for the reaction. 
   
   
       28 . The process as claimed in  claim 19 , in which the copper/butadienylphosphine complex is prepared in situ.