Patent DE-102005030400-A1 (DE)
Title: Preparation of (hetero)aryl, ethers or thioether compound, comprises cross-coupling of primary or secondary amines, alcohols or thioalcohol compound with substituted (hetero)aryl compound in the presence of Bronsted-base and catalyst
Inventor: MEUDT ANDREAS
IPC: C07C43/257
Filed: 2005-06-27
Abstract: Preparation of (hetero)aryl, ethers or thioether compound (III) comprises: cross-coupling of primary or secondary amines, alcohols or thioalcohols compound (II) with substituted (hetero)aryl compound (I) in the presence of Bronsted-base and catalyst or pre-catalyst containing a transition metal complex, salt or its compound (such as vanadium, manganese, iron, cobalt, nickel, rhodium, palladium, iridium or platinum) and at least one sulfonated phosphane ligand in a solvent or its mixture. Preparation of (hetero)aryl, ethers or thioether compound of formula (III) comprises: cross-coupling of primary or secondary amines, alcohols or thioalcohols compound (II) of formula (H-X-Ra) with substituted (hetero)aryl compound of formula (I) in the presence of Bronsted-base and catalyst or pre-catalyst containing a transition metal complex, salt or its compound (such as vanadium, manganese, iron, cobalt, nickel, rhodium, palladium, iridium or platinum) and at least one sulfonated phosphane ligand in a solvent or its mixture. Hal : F, Cl, Br, I, alkoxy, trifluoromethanesulfonate, methanesulfonate, 4-toluolsulfonate, nonafluorotrimethyl methanesulfonate, benzolsulfonate, 2-naphthalinsulfonate, 3-nitrobenzolsulfonate, 4-nitrobenzolsulfonate, 4-chlorobenzol-sulfonate, 2,4,6-triisopropylbenzolsulfonate or any other sulfonate; X : O, S or NRb; X 1-X 5carbon; either R 1-R 5H, methyl, primary, secondary, acyclic or cyclic 2-20C atoms (in which one or more hydrogen atoms are replaced by F, Cl or Br), substituted cyclic or acyclic alkyl, hydroxy, alkoxy, amino, alkylamino, dialkylamino, arylamino, diarylamino, alkylarylamino, pentafluorosulfuranyl, phenyl, substituted phenyl, heteroaryl, substituted heteroaryl, thio, alkylthio, arylthio, diarylphosphino, dialkylphosphino, alkylarylphosphino, optionally substituted aminocarbonyl, CO 2, alkyl- or aryloxycarbonyl, hydroxyalkyl, alkoxyalkyl, F, Cl, NO 2, CN, aryl- or alkylsulfone or aryl- or alkylsulfonyl; or (R 1-R 5)+(R 1-R 5) : aromatic, heteroaromatic or aliphatic condensed ring; either Ra : H, methyl, 1-20C alkyl or cyclic alkyl, or optionally substituted aryl- or heteroaryl (when X is O or S); and Rb : H, methyl, 1-20C alkyl or cyclic alkyl, or optionally substituted aryl- or heteroaryl (when X is NRb); or RaRb : a ring; and X iR i(sic) : nitrogen, where two adjacent X iR i(connected over a double bond) are O (furan), S (thiophene), NH or NR i(pyrrole). Independent claims are included for: (1) a sulfonated ligand structure of formula (A); (2) a complex, mixture, salts or formulation comprising the ligand and the metal; and (3) a procedure for the manufacture of sulfonated 2-hydroxy-2'-phosphinobiphenyl from 2-hydroxy-2'-phosphinobiphenyl comprising either sulfonating electrophilically or reacting metal and subsequently quenching with sulfonating agent. Either R 2-R 10sulfonic acid- containing sulfonate (substituted by H, CH 3or 2-20C-alkyl, where H are substituted by F, Cl, Br, alkyl, OH, alkoxy, (alkyl)amino, dialkylamino, arylamino, diarylamino, alkylarylamino, phenyl, heteroaryl, thio, alkylthio, arylthiodialkylphosphino, alkylarylphosphino, optionally substituted aminocarbonyl, CO 2->, alkyl- or aryloxycarbonyl, hydroxyalkyl, alkoxyalkyl, NO 2, CN, aryl- or alkylsulfone, aryl- or alkylsulfonyl); or 2(R 1-5) : forms a ring; and either Ra, Rb : H, CH 3, alkyl, phenyl, norbromyl or admantyl; or Ra+Rb : a ring or bonded with alkylene. [Image] [Image].