Process for preparing organic compounds by a transition metal-catalysed cross-coupling reaction of an aryl-x, heteroaryl-x, cycloalkenyl-x or alkenyl-x compound with an alkyl, alkenyl, cycloalkyl or cycloalkenyl halide

Abstract

This invention relates to a process for preparing functionalized aryl, heteroaryl, cycloalkenyl, or alkenyl compounds, by a transition-metal-catalyzed cross-coupling reaction of a substituted or unsubstituted aryl-X, heteroaryl-X, cycloalkenyl-X or alkenyl-X compound with an alkyl, alkenyl, cycloalkyl or cycloalkenyl halide, where X is a halide, diazonium, tosylate (p-toluenesulphonate), mesylate (methanesulphonate) or triflate (trifluoromethanesulphonate) leaving group.

What is claimed is: 
     
         1 . Process for preparing organic compounds of the general formula (I)
   R—R′  (I),
   where   R is a substituted or unsubstituted aromatic radical selected from the group consisting of phenyl, naphtyl, tolyl, cresol, aniline, and benzoic acid, and   R′ is a cycloalkylic radical,   by reacting a corresponding compound of the general formula (II) where
   R—X  (II)
 
   X is chlorine, bromine, iodine, diazonium, mesylate (methanesulphonate), tosylate (p-toluenesulphonate) or triflate (trifluoromethanesulphonate) and   R is as defined for formula (I),   with a corresponding compound of the general formula (III)
   R′—Y  (III),
 
   where   Y is chlorine, bromine or iodine and   R′ is as defined for formula (I),   wherein the reaction is carried out in the presence of   a) stoichiometric amounts of elemental magnesium, based on the compound of the general formula (II), and   b) amounts of an iron or cobalt compound from 0.01 to 50 mole percent of, based on the compound of the general formula (II), and,   c) in the presence of a nitrogen-, oxygen- and/or phosphorus-containing additive in a catalytic or stoichiometric amount of from 0 to 200 mole percent, based on the compound of the general formula (II), and   wherein the reaction is carried out as a one-pot process in which the organomagnesium compound (Grignard compound) formed in situ as intermediate is not isolated.   
     
     
         2 . Process according to  claim 1 , wherein the cycloalkylic radical R′ comprises one or more substituents which can be, independently of one another, (C 1 -C 12 )-alkyl, (C 1 -C 12 )-cycloalkyl, (C 1 -C 12 )-alkenyl, (C 1 -C 12 )-cycloalkenyl, (C 1 -C 12 )-alkynyl, (C 1 -C 12 )-aryl, O—[(C 1 -C 12 )-alkyl], O—[(C 1 -C 12 )-aryl], O—Si[(C 1 -C 12 )-alkyl] n [C 1 -C 12 )-aryl] 3-n , OC(O)—[(C 1 -C 12 )-alkyl], OC(O)—[(C 1 -C 12 )-aryl], NH 2 , NH[(C 1 -C 12 )-alkyl], N[(C 1 -C 12 )-alkyl] 2 , NH[(C 1 -C 12 )-aryl], N[(C 1 -C 12 )-aryl] 2 , NHC(O)—[(C 1 -C 12 )-alkyl], N[(C 1 -C 12 )-alkyl]C(O)—[(C 1 -C 12 )-alkyl], NHC(O)—[(C 1 -C 12 )-aryl], N[(C 1 -C 12 )-alkyl]C(O)—[(C 1 -C 12 )-aryl], NO 2 , NO, S—[(C 1 -C 12 )-aryl], S—[(C 1 -C 12 )-alkyl], fluorine, chlorine, bromine, CF 3 , CN, COOM, COO—[(C 1 -C 12 )-alkyl], COO—[(C 1 -C 12 )-aryl], C(O)NH—[(C 1 -C 12 )-alkyl], C(O)NH—[(C 1 -C 12 )-aryl], C(O)N—[(C 1 -C 12 )-alkyl] 2 , C(O)N—[(C 1 -C 12 )-aryl] 2 , CHO, SO 2 —[(C 1 -C 12 )-alkyl], SO—[(C 1 -C 12 )-alkyl], SO 2 —[(C 1 -C 12 )-aryl], SO—[(C 1 -C 12 )-aryl], OSO 2 —[(C 1 -C 12 )-alkyl], OSO 2 —[(C 1 -C 12 )-aryl], PO—[(C 1 -C 12 )-alkyl] 2 , PO—[(C 1 -C 12 )-aryl] 2 , SO 3 M, SO 3 —[(C 1 -C 12 )-alkyl], SO 3 —[(C 1 -C 12 )-aryl] or Si[(C 1 -C 12 )-alkyl] n [C 1 -C 12 )-aryl] 3-n , where M is an alkali metal or alkaline earth metal atom and n is a natural number in the range from 0 to 3. 
     
     
         3 . Process according to  claim 1 , wherein iron(II) chloride, iron(III) chloride, iron(II) acetylacetonate, iron(III) acetylacetonate, iron(II) acetate, iron(III) acetate, iron(II) bromide, iron(III) bromide, iron(II) fluoride, iron(III) fluoride, iron(II) iodide, iron(III) iodide, iron(II) sulphate, iron(III) chloride-TMEDA complex or iron carbonyl complexes is/are used as iron compound. 
     
     
         4 . Process according to  claim 1 , wherein a cobalt compound is used as transition metal compound. 
     
     
         5 . Process according to  claim 1 , wherein cobalt(II) chloride, cobalt(III) chloride, cobalt(II) acetylacetonate, cobalt(III) acetylacetonate, cobalt(II) acetate, cobalt(III) acetate, cobalt(II) bromide, cobalt(III) bromide, cobalt(II) fluoride, cobalt(III) fluoride, cobalt(II) iodide, cobalt(III) iodide, cobalt(II) sulphate, cobalt(III) sulphate, cobalt(II) cyanide, cobalt(III) cyanide, cobalt(II) oxide, cobalt(III) oxide, cobaltcarbonyl complexes, bis(cyclopentadienyl)cobalt(II), bis(cyclopentadienyl)cobalt(III) salts, dichlorobis(ethylenediamine)cobalt(III) salts, tris(ethylenediamine)cobalt(III) salts, chlorotris(triphenylphosphine)cobalt(I), dichlorobis(triphenylphosphine)cobalt(II), [1,1′-bis(diphenylphosphino)ferrocene]dichlorocobalt(II), (R,R)-(−)-N,N′-bis(3,5-di-tert-butylsalicylidene)-1,2-cyclohexanediaminecobalt(II), N,N′-bis(salicylidene)ethylene-diaminecobalt(II) or [1,2-bis(diphenylphosphino)ethane]dichlorocobalt(II) is used as cobalt compound. 
     
     
         6 . Process according to  claim 1 , wherein substituted or unsubstituted alkylamines, N-containing heterocycles, alkylamides, cyclic alkylamides, cycloalkylamines, cycloalkyldiamines, alkylimines, cycloalkylimines, aniline, aniline derivatives, nitrogen-containing heteroaromatics, dialkyl ethers, alkyl aryl ethers, diaryl ethers, cyclic ethers, oligoethers, polyethers, triarylphosphanes, trialkylphosphanes, aryldialkylphosphanes, alkyldiarylphosphanes and bridged bisphosphanes are used as a nitrogen-, oxygen- and/or phosphorus-containing additive having one or more nitrogen, oxygen and/or phosphorus atoms which may be added. 
     
     
         7 . Process according to  claim 1 , wherein the nitrogen-, oxygen- and/or phosphorus-containing additive is preferably used in an amount of from 0 to 200 mol %, based on the compound of the general formula (II).