Method for coupling a first compound to a second compound

A method for coupling a first compound A1 a second compound A2, as illustrated in Equation 1, comprising:

• providing the first compound A1 having a hydroxyl substituent, sulfuryl fluoride and a base to a reaction mixture, the first compound A1 comprising an aryl group or a heteroaryl group;
• providing a catalyst comprising a group 10 atom and the second compound A2 to the reaction mixture, the second compound A2 as defined in Equation 4:
• the second compound A2 comprising an amine wherein each of R1 and R2 are independently Hydrogen, an aryl group, a heteroaryl group, an alkyl group, a cycloalkyl group, a nitro group, a halide, a nitrogen, a cyano group, a carboxyester group, an acetoxy group, a substituted alkyl, aryl, heteroaryl or cycloalkyl group, or R1 and R2 are constituent parts of a ring system;
• reacting the first compound and the second compound under conditions effective to couple the first compound to the second compound.

A method comprising:

• providing to a first mixture, said first mixture comprising ethyl-4-hydroxybenzoate, sulfuryl fluoride, a base and a solvent,
• wherein said base is selected from the group consisting of lithium carbonate, lithium hydrogen carbonate, sodium carbonate, sodium hydrogen carbonate, potassium carbonate, potassium hydrogen carbonate, rubidium carbonate, rubidium hydrogen carbonate, cesium carbonate, cesium hydrogen carbonate, ammonium carbonate, and ammonium hydrogen carbonate, and
• wherein said solvent is selected from the group consisting of 1,4-dioxane, tetrahydrofuran, 2-methyltetrahydrofuran, diethylether, cyclopenyl methyl ether, 2-butyl ethyl ether, dimethoxyethane, polyethyleneglycol, and mixtures thereof;
• reacting said first mixture to provide a second mixture comprising ethyl 4-((fluorosulfonyl)oxy)benzoate;
• providing a phosphine ligand to said second mixture, wherein said phosphine ligand is selected from the group consisting of triphenylphosphine, tri(o-tolyl)phosphine, tris(4-methoxyphenyl)phosphine, tris(pentafluorophenyl)phosphine, 9,9-dimethyl-4,5-bis(diphenylphosphino)xanthene, (R)-(−)-1-[(S)-2-(diphenylphosphino)ferrocenyl]ethyldicyclohexylphosphine, and 1,1′-bis(diisopropylphosphino)ferrocene;
• removing sulfuryl fluoride if present, from said second mixture;
• providing aniline and a precatalyst to said second mixture, wherein said precatalyst is selected from the group consisting of palladium(II) acetate, palladium(II) chloride, dichlorobis(acetonitrile)palladium(II), dichlorobis(benzonitrile)palladium(II), palladium(II) acetylacetonate, dichloro(1,5-cyclooctadiene)palladium(II), dichloro(norbomadiene)palladium(II), tris(dibenzylideneacetone)dipalladium(0), palladium(II) hexafluoroacetylacetonate, cis-dichloro(N,N,N′,N′-tetramethylethylenediamine)palladium(II), and cyclopentadienyl[(1,2,3-n)-1-phenyl-2-propenyl]palladium(II);
• and
• reacting said second mixture comprising ethyl 4-((fluorosulfonyl)oxy)benzoate, aniline, said base, said solvent, said ligand, and said precatalyst under conditions effective to couple ethyl 4-((fluorosulfonyl)oxy)benzoate to aniline to provide ethyl 4-(phenylamino)benzoate.