Method for forming a carbon-carbon or carbon-heteroatom linkage

Abstract

The present invention concerns a process for creating a carbon-carbon or carbon-heteroatom bond by reacting an unsaturated compound carrying a leaving group with a nucleophilic compound. The invention also concerns the creation of a carbon-nitrogen bond using a process for arylating organic nitrogen-containing derivatives. The process of the invention is a process for creating a carbon-carbon or carbon-heteroatom bond by reacting an unsaturated compound carrying a leaving group with a nucleophilic compound carrying a carbon atom or a heteroatom (HE) that can substitute for the leaving group, creating a C—C or C-HE bond, characterized in that the reaction takes place in the presence of an effective quantity of a catalyst based on a metallic element M selected from group (VIII), (IB) and (IIB) of the periodic table and at least one at least bidentate ligand comprising at least two chelation atoms, namely at least one oxygen atom and at least one nitrogen atom.

1 - 46 . (Canceled)  
     
     
         47 . A process for creating a carbon-carbon or carbon-heteroatom bond by reacting an unsaturated compound carrying a leaving group with a nucleophilic compound carrying a carbon atom or a heteroatom (HE) that can substitute for the leaving group, creating a C—C or C-HE bond, wherein the reaction takes place in the presence of an effective quantity of a catalyst based on a metallic element M selected from group (VIII), (IB) and (IIB) of the periodic table and at least one bidentate ligand comprising at least two chelation atoms.  
     
     
         48 . The process according to  claim 47 , wherein the ligand is oxime, dioxime or hydrazone.  
     
     
         49 . The process according to  claim 48 , wherein the ligand employed has the following formulae:  
       
         
           
           
               
               
           
         
         wherein:  
         at least one of groups R a  and R b  has at least one atom of oxygen or a group comprising an oxygen atom;  
         R a  and R b  independently represent a hydrocarbon group containing 1 to 20 carbon atoms, linear or branched, saturated or unsaturated acyclic aliphatic group; a monocyclic or polycyclic, saturated, unsaturated or aromatic, carbocyclic or heterocyclic group; or a concatenation of said groups; or  
         R a  and R b  are optionally bonded to constitute, with the carbon atoms carrying them, a monocyclic or polycyclic, saturated or unsaturated carbocyclic or heterocyclic group containing 3 to 20 atoms;  
         at most one of groups R a  and R b  represents a hydrogen atom;  
         R c  represents a hydrogen atom, an alkyl group, an alkenyl or alkynyl group, a cycloalkyl group,; or an aryl or arylalkyl group.  
       
     
     
         50 . The process according to  claim 49 , wherein the ligand has formula (Ia 1 ) in which R c  represents a hydrogen atom and R a  represents one of the following groups:  
       
         
           
           
               
               
           
         
         Wherein R s  represents an alkyl or alkoxy group, or an amino group optionally substituted with an alkyl group.  
       
     
     
         51 . The process according to  claim 48 , wherein the ligand employed has the following formula:  
       
         
           
           
               
               
           
         
         wherein:  
         R a ′ and R b ′, which are identical or different, have the meanings given in formulae (Ia 1 ) or (Ia 2 ) with the exception of an oxygen atom the presence of which is not obligatory;  
         R a  or R b  represents a hydrogen atom;  
         R a ′ and R b ′ optionally form a carbocyclic or heterocyclic cycle optionally substituted, containing 5 or 6 atoms;  
         R c  represents a hydrogen atom, an alkyl group; an alkenyl or alkynyl group; a cycloalkyl group; or an aryl or arylalkyl group;  
         R d , R e , are identical or different, represent: 
 a hydrogen atom;  
 a linear or branched alkyl group containing 1 to 12 carbon atoms, optionally carrying a halogen atom;  
 a halogen atom; and  
 m equals 0, 1, 2 or 3.  
 
       
     
     
         52 . The process according to  claim 51 , wherein the ligand has formula (Ib 1 ) whwerein R c  represents a hydrogen atom, m equals 0 and R a ′ and R b ′ represent a methyl group or form a cyclohexane cycle.  
     
     
         53 . The process according to  claim 48 , wherein the ligand employed has the following formulae:  
       
         
           
           
               
               
           
         
         wherein:  
         R a  and R b , which are identical or different, have the meanings given in formulae (Ia 1 ) and (Ia 2 );  
         at least one of groups R a  and R b  has at least one oxygen atom or a group containing an oxygen atom;  
         R a  or R b  optionally represent a hydrogen atom; and  
         R c , which are be identical or different, represents a hydrogen atom, has the meanings given in formulas (Ia 1 ) and (Ia 2 ) and further represents a —CO—NH 2  group.  
       
     
     
         54 . The process according to  claim 53 , wherein the ligand has formulae (Ic 1 ) or (Ic 2 ) in which groups R c , which are identical or different, represent a hydrogen atom or a methyl group, and R a  represents one of the following groups:  
       
         
           
           
               
               
           
         
         in which R s  represents an alkyl, alkoxy, or an amino group optionally substituted with an alkyl group.  
       
     
     
         55 . The process according to  claim 47 , wherein the ligand employed has the following formulae:  
       
         
           
           
               
               
           
         
         wherein:  
         R AA  represents the residue of an amino acid, a linear or branched C 1  to C 12  alkyl group optionally carrying a functional group, or a C 6  to C 12  aryl group or arylalkyl group;  
         R a  or R b  optionally represents a hydrogen atom; and  
         R a  and R b , which are identical or different, have the meanings given in formulae (Ia 1 ) and (Ia 2 ).  
       
     
     
         56 . The process according to  claim 55 , wherein the ligand has formulae (Id 1 ) and (Id 2 ), in which R AA  represents an alkyl group that carry a functional group.  
     
     
         57 . The process according to  claim 55 , wherein the ligand has formulae (Id 1 ) or (Id 2 ) in which R AA  represents a hydrogen atom or a methyl group and R a  represents one of the following groups:  
       
         
           
           
               
               
           
         
       
       wherein R s  represents an alkyl, alkoxy group, or an amino group optinally substituted with alkyl groups.  
     
     
         58 . The process according to  claim 49 , wherein the ligand employed has the following formulae:  
       
         
           
           
               
               
           
         
         wherein:  
         R a , which are identical or different, have the meanings given in formulae (Ia 1 ) and (Ia 2 );  
         R b , which are identical or different, have the meanings given in formulae (Ia 1 ) and (Ia 2 );  
         R a  and/or R b  represent a hydrogen atom;  
         Ψ represents a —HN—CO—NH— group or a skeleton with general formula (F 2 ) or (F 3 ):  
         
           
             
             
                 
                 
             
           
           in which formulae (F 2 ) and (F 3 ):  
           R f  and R g  independently represent a hydrogen atom, hydrocarbon group containing 1 to 20 carbon atoms, which are a linear or branched, saturated or unsaturated acyclic aliphatic group; a monocyclic or polycyclic, saturated, unsaturated or aromatic carbocyclic or heterocyclic group; or  
           R f  and R g  are bonded together to constitute, with the carbon atoms carrying them, a carbocyclic or heterocyclic group containing 3 to 20 atoms, said group being saturated, unsaturated, monocyclic or polycyclic;  
           Ar 1  and Ar 2  independently represent two substituted or non substituted aromatic, carbocyclic or heterocyclic cycles optionally condensed roatoms; and  
           x and y respectively represent the two bonds between the skeleton shown as ψ, and the imine groups.  
         
       
     
     
         59 . The process according to  claim 58 , wherein the ligand has formula (Ie 1 ) or (Ie 2 ) in which R b  represents a hydrogen atom and R a  represents one of the following groups:  
       
         
           
           
               
               
           
         
         wherein R s  represents an alkyl or alkoxy group, or an amino group optionally substituted with alkyl groups.  
       
     
     
         60 . The process according to  claim 58 , wherein the ligand has formula (Ie 1 ) or (Ie 2 ) in which Ψ represents the following cyclic groups:  
       
         
           
           
               
               
           
         
       
     
     
         61 . The process according to  claim 47 , wherein the ligand is selected from: Salox, Salox-Me, 5-MeO-Salox, Aldox, 3-Py-Aldox, 4-Net 2 -Salox, Bz-Phenox, Benzophenoxime, DMG, Nioxime, Salzone, Me-Salzone, Py-Semizone, Me 2 -Salzone, Sal-gly, Sal-glu, Trans-Chxn-Salen, Carbosalzone and Salen.  
     
     
         62 . The process according to  claim 47 , wherein the ligand is employed in a ratio between the number of moles of ligand and the number of moles of metal being in the range 2 to 1.  
     
     
         63 . The process according to  claim 47 , wherein the nucleophilic substrate is an organic hydrocarbon compound acyclic or cyclic comprising at least one atom carrying a free electron pair optionally carrying a charge or having a carbon atom that is capable of donating its electron pair.  
     
     
         64 . The process according to  claim 47 , wherein the nucleophilic substrate presents at least one of the following atoms or groups:  
       
         
           
           
               
               
           
         
       
     
     
         65 . The process according to  claim 47 , wherein the nucleophilic substrate has at least one nitrogen atom carrying a free electron pair included in a saturated, unsaturated or aromatic cycle: the cycle comprising 3 to 8 atoms.  
     
     
         66 . The process according to  claim 63 , wherein the nucleophilic substrate is a primary or secondary amine; a hydrazine or hydrazone derivative; an amide; a sulphoamide; a urea derivative; or a heterocyclic derivative, optionally nitrogen- or sulphur-containing.  
     
     
         67 . The process according to  claim 63 , wherein the nucleophilic substrate has the following formula:  
       
         
           
           
               
               
           
         
         wherein:  
         A represents the residue of a cycle forming all or a portion of a monocyclic or polycyclic, aromatic or non aromatic heterocyclic system wherein one of the carbon atoms is replaced by at least one nucleophilic atom;  
         R 12 , identical or different, represent substituents on the cycle; and  
         n represents the number of substituents on the cycle.  
       
     
     
         68 . The process according to  claim 67 , wherein A represents a imidazole, pyrazole, triazole, pyrazine, oxadiazole, oxazole, tetrazole, indole, pyrole, phthalazine, pyridazine or oxazolidine cycle.  
     
     
         69 . The process according to  claim 63 , wherein the nucleophilic substrate is an alcohol, a thiol or a thioaromatic compound.  
     
     
         70 . The process according to  claim 69 , wherein the nucleophilic substrate has the following formula:  
       
         
           
           
               
               
           
         
         wherein:  
         B represents the residue of a monocyclic or polycyclic, aromatic carbocyclic group or a divalent group constituted by a concatenation of two or more monocyclic aromatic carbocyclic groups;  
         R 14  represents one or more substituents, which are identical or different;  
         Z represents a hydroxyl or thiol group; and  
         n′ is 5 or less.  
       
     
     
         71 . The process according to  claim 63 , wherein the nucleophilic substrate is a hydrocarbon compound containing a nucleophilic carbon, or a nucleophilic compound comprising a carbanion the counter-ion of which is a metal.  
     
     
         72 . The process according to  claim 63 , wherein the nucleophilic substrate is a phosphide, phosphine, phosphonium diazaylide, phosphonium azaylide, or boronic acid.  
     
     
         73 . The process according to  claim 72 , wherein the nucleophilic substrate is a boronic acid or a derivative with the following formula:  
       
         
           
           
               
               
           
         
         wherein:  
         R 25  represents a monocyclic or polycyclic, aromatic, carbocyclic or heterocyclic group; and  
         Q 1 , Q 2 , identical or different, represent a hydrogen atom, a linear or branched, saturated or unsaturated aliphatic group containing 1 to 20 carbon atoms, or a R 25  group.  
       
     
     
         74 . The process according to  claim 73 , wherein the arylboronic acid has formula (IIIu) in which R 25  represents an aromatic carbocyclic or heterocyclic group.  
     
     
         75 . The process according to  claim 73 , wherein the arylboronic acid has formula (IIIu) in which Q 1 , Q 2 , identical or different, represent a hydrogen atom or a linear or branched acyclic aliphatic group containing 1 to 20 carbon atoms saturated or having one or more unsaturated bonds in the chain, or a group R 25 , optionally a phenyl group.  
     
     
         76 . The process according to  claim 47 , wherein the compound carrying a leaving group Y is represented by formula (IV):  
         R 0 -Y (IV)  wherein R 0  represents a hydrocarbon group having 2 to 20 carbon atoms and has a double bond or a triple bond located in the position a to the leaving group Y, or a monocyclic or polycyclic, aromatic, carbocyclic or heterocyclic group.    
     
     
         77 . The process according to  claim 76 , wherein: 
 R 0  represents an aliphatic hydrocarbon group having a double bond or a triple bond in the position a to the leaving group or a cyclic hydrocarbon group containing an unsaturated bond carrying a leaving group;    R 0  represents a monocyclic or polycyclic, aromatic, carbocyclic and/or heterocyclic group; and    Y represents a leaving group, a halogen atom or a sulphonic ester group with formula —OSO 2 —R e , in which R e  is a hydrocarbon group.    
     
     
         78 . The process according to  claim 77 , wherein the compound carrying a leaving group has formula (IV) in which Y represents a bromine or chlorine atom or a sulphonic ester with formula —OSO 2 —R e , in which R e  is a methyl or ethyl, a phenyl or tolyl group or a trifluoromethyl group.  
     
     
         79 . The process according to one of claims  76 , wherein the compound carrying a leaving group has formula (IV) and is selected from the group consisting of: 
 (1) aliphatic type compounds, carrying a double bond of formula (IVa):                           wherein: 
 R 26 , R 27  and R 28 , which may be identical or different, represent a hydrogen atom or a hydrocarbon group containing 1 to 20 carbon atoms, which are a linear or branched, saturated or unsaturated aliphatic group; a monocyclic or polycyclic, saturated, unsaturated or aromatic carbocyclic or heterocyclic group; or a concatenation of aliphatic or carbocyclic or heterocyclic groups; and  
 Y represents the leaving group, as defined above;  
   (2) aliphatic type compounds carrying a triple bond, represented by formula (IVb):      R 26 —C≡C—Y  (IVb)     wherein: 
 R 26  has the meaning given in formula (IVa);  
 Y represents a leaving group as defined above; and  
   (3) aromatic compounds of formula (IVc):                           wherein: 
 D represents the residue of a cycle forming all or a portion of a monocyclic or polycyclic, aromatic, carbocyclic and/or heterocyclic system;  
 R 29 , identical or different, represent substituents on the cycle;  
 Y represents a leaving group as defined above; and  
 n″ represents the number of substituents on the cycle.  
   
     
     
         80 . The process according to  claim 79 , wherein the compound carrying a leaving group with formula (IV) is: vinyl chloride, vinyl bromide, bromoalkyne, iodoalkyne, β-bromostyrene, β-chlorostyrene, p-chlorotoluene, p-bromoanisole or p-bromotrifluorobenzene.  
     
     
         81 . The process according to one  claim 47 , wherein the catalyst comprises at least one of the following metallic elements M: copper, silver, palladium, cobalt, nickel, iron or zinc.  
     
     
         82 . The process according to  claim 81 , wherein the catalyst is a copper catalyst, preferably a copper halide.  
     
     
         83 . The process according to 47, wherein the reaction is carried out further in the presence of a base.  
     
     
         84 . The process according to  claim 83 , wherein the base is selected from: the group consisting of alkali metal carbonates, bicarbonates; alkali metal alcoholates, and tertiary amines.  
     
     
         85 . The process according to  claim 47 , wherein the reaction is carried out further in the presence of an organic solvent.  
     
     
         86 . The process according to  claim 85 , wherein the organic solvent is: linear or cyclic carboxamides; dimethylsulphoxide (DMSO); hexamethylphosphotriamide (HMPT); tetramethylurea; nitro compounds; aliphatic or aromatic nitrites, tetramethylene sulphone; organic carbonates; alkyl esters; halogenated aromatic hydrocarbons, toluene; nitrogen-containing heterocycles, pyridine, picoline or quinolines.  
     
     
         87 . The process according to  claim 47 , wherein the reaction is carried out at a temperature in the range 0° C. to 120° C.  
     
     
         88 . The process according to  claim 47 , wherein the ligand is addeded concomitantly with the compound supplying the catalytic metallic element M.  
     
     
         89 . The process according to  claim 47 , wherein the catalyst is an extemporaneously prepared metallic complex, by reacting a compound supplying the catalytic metallic element M with the ligand.  
     
     
         90 . The process according to  claim 47 , wherein the metallic complex is prepared at the start of the reaction from a ligand and a compound supplying the metallic element M.  
     
     
         91 . The process according to  claim 89 , wherein the metallic element M is copper.  
     
     
         92 . The process according to  claim 89 , wherein the ligand is an oxime.