Method for preparation of ruthenium-based metathesis catalysts with chelating alkylidene ligands

摘要

The invention relates to a method for preparation of ruthenium-based carbene catalysts with a chelating alkylidene ligand (“Hoveyda-type catalysts”) by reacting a penta coordinated ruthenium (II)-alkylidene complex of the type (L) (Py)X1X2Ru(alkylidene) with a suitable olefin derivative in a cross metathesis reaction. The method delivers high yields and is conducted preferably in aromatic hydrocarbon solvents. The use of phosphine-containing Ru carbene complexes as starting materials can be avoided. Catalyst products with high purity, particularly with low Cu content, can be obtained.

主权项

1. Method for the preparation of a ruthenium-based carbene catalyst with a chelating alkylidene ligand comprising the reaction of a ruthenium (II)-alkylidene complex with an olefin derivative according to the equation: wherein L is a substituted or unsubstituted imidazole or imidazolidine ring, X1 and X2 are, independently from each other, inorganic or organic anionic ligands selected from halide anions, pseudohalide anions, hydroxides, acetates, trifluoracetates or carboxylates, Y1 and Y2 are, independently from each other, hydrogen, C1-C6-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, C1-C6-alkylthio, aryl, arylthio, C1-C6-alkylsulfonyl or C1-C6-alkylsulfinyl, or Y1 and Y2 are taken together to form a ring of the indenylidene type according to the formula wherein in said formula R3 is hydrogen or a substituted or unsubstituted aryl group, Py is an N-heterocyclic two-electron donor ligand selected from the group consisting of pyridine, 3-bromo-pyridine, 4-methyl-pyridine, quinolone, and piperidine, R0 and R1 are, independently from each other, hydrogen, C1-C10-alkyl, C2-C10-alkenyl, C2-C10-alkynyl, or a substituted or unsubstituted aryl group, a, b, c and d are, independently from each other, hydrogen, C1-C10-alkyl, C2-C10-alkenyl, C2-C10-alkynyl, or aryl group, or an electron withdrawing group (“EWG”), with the provision that two of a, b, c or d can form a ring, Z is a heterodonor atom selected from the group consisting of oxygen (O), sulphur (S), and nitrogen (N), or a group comprising a heterodonor atom, R2 is a substituted or unsubstituted hydrocarbon group selected from alkyl, alkenyl, alkynyl, aryl, alkylamino, alkylthio, a hydrocarbon containing a substituted or unsubstituted keto group, a hydrocarbon containing a substituted or unsubstituted ester group and wherein R2 and/or Z may form a quinolone, a quinoxaline, or an indol ring system with d.