Chelating carbene ligand precursors and their use in the synthesis of metathesis catalysts

Abstract

Chelating ligand precursors for the preparation of olefin metathesis catalysts are disclosed. The resulting catalysts are air stable monomeric species capable of promoting various metathesis reactions efficiently, which can be recovered from the reaction mixture and reused. Internal olefin compounds, specifically beta-substituted styrenes, are used as ligand precursors. Compared to terminal olefin compounds such as unsubstituted styrenes, the beta-substituted styrenes are easier and less costly to prepare, and more stable since they are less prone to spontaneous polymerization. Methods of preparing chelating-carbene metathesis catalysts without the use of CuCl are disclosed. This eliminates the need for CuCl by replacing it with organic acids, mineral acids, mild oxidants or even water, resulting in high yields of Hoveyda-type metathesis catalysts. The invention provides an efficient method for preparing chelating-carbene metathesis catalysts by reacting a suitable ruthenium complex in high concentrations of the ligand precursors followed by crystallization from an organic solvent.

1 . (canceled)  
     
     
         2 . A chelating carbene complex of the formula:  
       
         
           
           
               
               
           
         
       
       wherein 
 X 1  and X 2  are each, independently, any anionic ligand;  
 L 1  is any neutral electron donor, and wherein any of two or three of X 1 , X 2 , and L 1  may form a multidentate ligand;  
 M is ruthenium or osmium;  
 R 5 , R 6 , R 7 , and R 8  are each, independently, selected from the group consisting of hydrogen, halogen, alkyl, alkenyl, alkynyl, aryl, heteroaryl, alkoxy, alkenyloxy, aryloxy, alkoxycarbonyl, carbonyl, alkylamino, alkylthio, alkylsulfonyl, nitrile, nitro, alkylsulfinyl, trihaloalkyl, perfluoroalkyl, carboxylic acid, ketone, aldehyde, nitrate, cyano, isocyanate, hydroxyl, ester, ether, amine, imine, amide, sulfide, disulfide, sulfonate, carbamate, silane, siloxane, phosphine, phosphate, and borate, wherein any two of R 5 , R 6 , R 7 , and R 8  may be independently connected through hydrocarbon or functionalized hydrocarbon groups forming an aliphatic or aromatic ring;  
 Y is a heteroatom selected from oxygen (O), sulfur (S), nitrogen (N), or phosphorus (P); and  
 Z is selected from the group consisting of hydrogen, alkyl, aryl, functionalized alkyl, and functionalized aryl where the functional group(s) may independently be one or more or the following: alkoxy, aryloxy, halogen, carboxylic acid, ketone, aldehyde, nitrate, cyano, isocyanate, hydroxyl, ester, ether, amine, imine, amide, sulfide, disulfide, carbamate, silane, siloxane, phosphine, phosphate, and borate; and  
 wherein the chelating carbene complex is prepared by a method comprising contacting a metathesis-active metal carbene complex with a beta-substituted styrene ligand precursor.  
 
     
     
         3 . The chelating carbene complex of  claim 2 , wherein the metathesis-active metal carbene complex is of the formula X 1 X 2 L 1 M 2 =CR 1 R 2 , wherein 
 X 1 , X 1 , L 2 , and M 1  are as defined in  claim 2;     L 2  is any neutral electron donor, and wherein any of two or three of X 1 , X 2 , L 1 , and L 2  may form a multidentate ligand; and    R 1  and R 2  are each, independently, selected from hydrogen or a substituent selected from the group consisting of alkyl, alkenyl, alkynyl, aryl, alkylcarboxylate, arylcarboxylate, alkoxy, alkenyloxy, alkynyloxy, aryloxy, alkoxycarbonyl, alkylthio, alkylsulfonyl, alkylsulfinyl, or trialkylsilyl, wherein each of the substituents is substituted or unsubstituted, and wherein R 1  and R 2  may be linked to form a substituted or unsubstituted cyclic group.    
     
     
         4 . The chelating carbene complex of  claim 2 , wherein the ligand precursor is of the formula  
       
         
           
           
               
               
           
         
       
       wherein 
 Y, Z, n, R 5 , R 6 , R 7 , and R 8  are as defined in  claim 2;   
 n is 1, in the case of a divalent heteroatom, or 2, in the case of a trivalent heteroatom; and  
 R 3  and R 4  are each, independently, selected from hydrogen or a substituent selected from the group consisting of alkyl, aryl, alkoxy, aryloxy, C 2 -C 20  alkoxycarbonyl, or C 1 -C 20  trialkylsilyl, wherein each of the substituents is substituted or unsubstituted.  
 
     
     
         5 . A method of preparing a metathesis-active metal chelating carbene complex comprising a chelating carbene ligand, the method comprising contacting a metathesis-active metal carbene complex with a beta-substituted styrene ligand precursor to form the metathesis-active metal chelating carbene complex.  
     
     
         6 . The method of  claim 5 , wherein the metathesis-active metal carbene complex is of the formula X 1 X 2 L 1 L 2 M=CR 1 R 2 , wherein 
 X 1  and X 2  are each, independently, any anionic ligand;    L 1  and L 2  are each, independently, any neutral electron donor, and wherein any of two or three of X 1 , X 2 , L 1  and L 2  may form a multidentate ligand;    M is ruthenium or osmium;    R 1  and R 2  are each, independently, selected from hydrogen or a substituent selected from the group consisting of alkyl, alkenyl, alkynyl, aryl, alkylcarboxylate, arylcarboxylate, alkoxy, alkenyloxy, alkynyloxy, aryloxy, alkoxycarbonyl, alkylthio, alkylsulfonyl, alkylsulfinyl, or trialkylsilyl, wherein each of the substituents is substituted or unsubstituted, and wherein R 1  and R 2  may be linked to form a substituted or unsubstituted cyclic group.    
     
     
         7 . The method of  claim 5 , wherein the ligand precursor is of the formula  
       
         
           
           
               
               
           
         
       
       wherein 
 Y is a heteroatom selected from oxygen (O), sulfur (S), nitrogen (N), or phosphorus (P);  
 Z is selected from hydrogen, alkyl, aryl, functionalized alkyl, or functionalized aryl where the functional group(s) may independently be one or more or the following: alkoxy, aryloxy, halogen, carboxylic acid, ketone, aldehyde, nitrate, cyano, isocyanate, hydroxyl, ester, ether, amine, imine, amide, sulfide, disulfide, carbamate, silane, siloxane, phosphine, phosphate, or borate;  
 n is 1, in the case of a divalent heteroatom, or 2, in the case of a trivalent heteroatom;  
 R 3  and R 4  are each, independently, selected from hydrogen or a substituent selected from the group consisting of alkyl, aryl, alkoxy, aryloxy, C 2 -C 20  alkoxycarbonyl, or C 1 -C 20  trialkylsilyl, wherein each of the substituents is substituted or unsubstituted; and  
 R 5 , R 6 , R 7 , and R 8  are each, independently, selected from the group consisting of hydrogen, halogen, alkyl, alkenyl, alkynyl, aryl, heteroaryl, alkoxy, alkenyloxy, aryloxy, alkoxycarbonyl, carbonyl, alkylamino, alkylthio, alkylsulfonyl, nitrile, nitro, alkylsulfinyl, trihaloalkyl, perfluoroalkyl, carboxylic acid, ketone, aldehyde, nitrate, cyano, isocyanate, hydroxyl, ester, ether, amine, imine, amide, sulfide, disulfide, sulfonate, carbamate, silane, siloxane, phosphine, phosphate, and borate, wherein any two of R 5 , R 6 , R 7 , and R 8  may be independently connected through hydrocarbon or functionalized hydrocarbon groups forming an aliphatic or aromatic ring.