Recyclable ruthenium catalysts for metathesis reactions
AssigneeZheng-Yun James Zhan
InventorZheng-Yun James Zhan
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Abstract
The invention relates to novel carbene ligands and their incorporated monomeric and resin/polymer linked ruthenium catalysts, which are recyclable and highly active for olefin metathesis reactions. It is disclosed that significant electronic effect of different substituted 2-alkoxybenzylidene ligands on the catalytic activity and stability of corresponding carbene ruthenium complexes, some of novel ruthenium complexes in the invention can be broadly used as catalysts highly efficient for olefin metathesis reactions, particularly in ring-closing (RCM), ring-opening (ROM), ring-opening metathesis polymerization (ROMP) and cross metathesis (CM) in high yield. The invention also relates to preparation of new ruthenium complexes and the use in metathesis.
Claims28
A composition comprising a recyclable ruthenium catalyst having a ligand chemically bonded to a support material and which is represented by formula IIIa, IIIb, or IIIc:
- wherein
- G is a support material selected from the group consisting of resins, polymers, PEGs, and silica gel, wherein the support material has amino, hydroxy, alkylthio, haloalkyl, or carboxylic group on the surface or terminal thereof;
- X1 and X2 are the same or different and each are electron-withdrawing anionic ligands, wherein X1 and X2 may be linked to each other via carbon-carbon and/or carbon-heteroatom bonds;
- Y is a neutral two-electron donor selected from the group consisting of oxygen, sulfur, nitrogen and phosphorus;
- R is H, halogen atom, alkyl, alkoxy, aryl, aryloxy, alkylcarbonyl, arylcarbonyl, alkoxycarbonyl, aryloxycarbonyl, heteroaryl, carboxyl, (RCO2—), cyano, nitro, amido, amino, aminosulfonyl, N-heteroarylsulfonyl, alkylsulfonyl, arylsulfonyl, alkylsulfinyl, arylsulfinyl, alkylthio, arylthio, or sulfonamido group;
- R1 and R2 are each H, Br, I, alkyl, alkoxy, aryl, aryloxy, alkylcarbonyl, alkoxycarbonyl, aryloxycarbonyl, carboxyl, amido, amino, heteroaryl, alkylthio, arylthio, or sulfonamido group;
- R3 is an alkyl, aryl, heteroaryl, alkylcarbonyl, arylcarbonyl, thiocarbonyl, or aminocarbonyl group;
- EWG is an electron withdrawing group selected from the group consisting of aminosulfonyl, amidosulfonyl, N-heteroarylsulfonyl, arylsulfonyl, arylsulfinyl, arylcarbonyl, alkylcarbonyl, aryloxycarbonyl, aminocarbonyl, amido, sulfonamido, chloro, fluoro, and haloalkyl group;
- and
- L is an electron donating ligand, which may be linked to X1 via carbon-carbon and/or carbon-heteroatom bonds.
A process for preparing a Ru complex represented by the formula VI:
- wherein
- X1 and X2 are the same or different and each are electron-withdrawing anionic ligands, wherein X1 and X2 may be linked to each other via carbon-carbon and/or carbon-heteroatom bonds;
- Y is a neutral two-electron donor selected from the group consisting of oxygen, sulfur, nitrogen and phosphorus;
- R is H, halogen atom, alkyl, alkoxy, aryl, aryloxy, alkylcarbonyl, arylcarbonyl, alkoxycarbonyl, aryloxycarbonyl, heteroaryl, carboxyl, (RCO2—), cyano, nitro, amido, amino, aminosulfonyl, N-heteroarylsulfonyl, alkylsulfonyl, arylsulfonyl, alkylsulfinyl, arylsulfinyl, alkylthio, arylthio, or sulfonamido group;
- R1 and R2 are each H, Br, I, alkyl, aryl, aryloxy, alkylcarbonyl, arylcarbonyl, alkoxycarbonyl, aryloxycarbonyl, carboxyl, amido, amino, heteroaryl, alkylthio, arylthio, or sulfonamido group;
- R3 is an alkyl, heteroaryl, alkylcarbonyl, arylcarbonyl, thiocarbonyl, or aminocarbonyl group;
- and
- EWG is an electron withdrawing group selected from the group consisting of aminosufonyl, amidosulfonyl, N-heteroarylsulfonyl, arylsulfonyl, arylsulfinyl, arylcarbonyl, alkylcarbonyl, aryloxycarbonyl, aminocarbonyl, amido, sulfonamido, chloro, fluoro, haloalkyl group and nitro group;
- comprising:
- forming an alkoxybenzylidene carbene of a compound represented by formula V:
- wherein
- Z is O, CH2, or a TsNHN group;
- and
- X1, X2, Y, R, R1, R2, R3 and EWG are as defined above, in the presence of NaOEt or NaOMe when Z is TsNHN, followed by reacting with RuCl2(PPh3)3 to produce the Ru complex represented by formula VI.
A process for preparing a Ru complex represented by the formula VII:
- wherein
- X1 and X2 are the same or different and are each electron-withdrawing anionic ligands, wherein X1 and X2 may be linked to each other via carbon-carbon and/or carbon-heteroatom bonds;
- Y is a neutral two-electron donor selected from the group consisting of oxygen, sulfur, nitrogen and phosphorus;
- R is H, halogen atom, alkyl, alkoxy, aryl, aryloxy, alkylcarbonyl, arylcarbonyl, alkoxycarbonyl, aryloxycarbonyl, heteroaryl, carboxyl, (RCO2—), cyano, nitro, amido, amino, aminosulfonyl, N-heteroarylsulfonyl, alkylsulfonyl, arylsulfonyl, alkylsulfinyl, arylsulfinyl, alkylthio, arylthio, or sulfonamido group;
- R1 and R2 are each H, Br, I, alkyl, aryl, aryloxy, alkylcarbonyl, arylcarbonyl, alkoxycarbonyl, aryloxycarbonyl, carboxyl, amido, amino, heteroaryl, alkylthio, arylthio, or sulfonamido group;
- R3 is an alkyl, heteroaryl, alkylcarbonyl, arylcarbonyl, thiocarbonyl, or aminocarbonyl group;
- and
- EWG is an electron withdrawing group selected from the group consisting of aminosufonyl, amidosulfonyl, N-heteroarylsulfonyl, arylsulfonyl, arylsulfinyl, arylcarbonyl, alkylcarbonyl, aryloxycarbonyl, aminocarbonyl, amido, sulfonamido, chloro, fluoro, haloalkyl group and nitro group;
- comprising:
- reacting a compound represented by the formula VI:
- wherein X1, X2, Y, R, R1, R2, R3 and EWG are as defined above above,
- with a ligand represented by the formula Pcy3, wherein Cy represents a cyclohexyl group, to produce the complex represented by formula VII.
Dependencies are inferred from the claim text.