Ruthenium-based metathesis catalysts, precursors for their preparation and their use

Abstract

The invention is directed to ruthenium-based metathesis catalysts of the Grubbs-Hoveyda type. The new 2-aryloxy-substituted ruthenium catalysts described herein reveal rapid initiation behavior. Further, the corresponding styrene-based precursor compounds are disclosed. The catalysts are prepared in a cross-metathesis reaction starting from styrene-based precursors which can be prepared in a cost-effective manner. The new Grubbs-Hoveyda type catalysts are suitable to catalyze ring-closing metathesis (RCM), cross metathesis (CM) and ring-opening metathesis polymerization (ROMP). Low catalyst loadings are necessary to convert a wide range of substrates including more complex and critical substrates via metathesis reactions at low to moderate temperatures in high yields within short reaction times.

1 .- 20 . (canceled) 
     
     
         21 . A compound of formula (I) for the preparation of ruthenium-based catalysts 
       
         
           
           
               
               
           
         
         wherein
 a, b, c and d are, independently from each other, selected from hydrogen, straight chain or branched alkyl groups including C 1 -C 10 -alkyl, C 1 -C 10 -alkylthio, C 1 -C 10 -silyloxy, C 1 -C 10 -alkylamino, optionally substituted C 6 -C 14 -aryl, optionally substituted C 6 -C 14 -aryloxy, optionally substituted C 6 -C 14 -heteroaryl or electron-withdrawing groups (EWG); 
 R 1  is hydrogen, straight chain or branched C 1 -C 10 -alkyl, C 1 -C 10 -alkoxy, C 1 -C 10 -alkylthio, C 1 -C 10 -silyloxy, C 1 -C 10 -alkylamino, C 1 -C 10 -dialkylamino, C 6 -C 14 -aryl, C 6 -C 14 -aryloxy, C 6 -C 14 -heterocyclic or electron-withdrawing groups (EWG); 
 R 2  is hydrogen, straight chain or branched C 1 -C 10 -alkyl groups. 
 
       
     
     
         22 . The compound according to  claim 21 , wherein the electron-withdrawing groups are halogen atoms, trifluormethyl (—CF 3 ), nitro (—NO 2 ), sulfinyl (—SO—), sulfonyl (—SO 2 —), formyl (—CHO), C 1 -C 10 -carbonyl, C 1 -C 10 -carboxyl, C 1 -C 10 -alkylamido, C 1 -C 10 -aminocarbonyl, nitrile (—CN) or C 1 -C 10 -sulfonamide. 
     
     
         23 . The compound according to  claim 21 , wherein
 b, c and d each are hydrogen;   R 1  is dimethylamino (NMe 2 -), nitro (NO 2 ) or chlorine (Cl); and   R 2  is hydrogen, methyl, ethyl, n-propyl, iso-propyl, n-butyl or iso-butyl.   
     
     
         24 . The compound according to  claim 23 , having the formula (Ia) 
       
         
           
           
               
               
           
         
       
     
     
         25 . The compound according to  claim 21 , having the formula (Ib) 
       
         
           
           
               
               
           
         
       
     
     
         26 . A ruthenium-based catalyst of formula (II) 
       
         
           
           
               
               
           
         
         wherein
 L is a neutral two-electron donor ligand, 
 a, b, c and d are, independently from each other, selected from hydrogen, straight chain or branched C 1 -C 10 -alkyl, C 1 -C 10 -alkoxy, C 1 -C 10 -alkylthio, C 1 -C 10 -silyloxy, C 1 -C 10 -alkylamino, optionally substituted C 6 -C 14 -aryl, optionally substituted C 6 -C 14 -aryloxy, optionally substituted C 6 -C 14 -heteroaryl or electron-withdrawing groups (EWG); 
 R 1  is hydrogen, straight chain or branched alkyl groups including C 1 -C 10 -alkyl, C 1 -C 10 -alkoxy, C 1 -C 10 -alkylthio, C 1 -C 10 -silyloxy, C 1 -C 10 -alkylamino, C 6 -C 14 -aryl, C 6 -C 14 -aryloxy, C 6 -C 14 -heterocyclic or electron-withdrawing groups (EWG); 
 X is an anionic ligand independently selected from the group of halogen anions (Cl − , Br − , I − ), tetrafluoroborate (BF 4   − ) or acetate (CH 3 COO − ). 
 
       
     
     
         27 . The catalyst according to  claim 26 , wherein the electron-withdrawing groups are halogen atoms, trifluormethyl (—CF 3 ), nitro (—NO 2 ), sulfinyl (—SO—), sulfonyl (—SO 2 —), formyl (—CHO), C 1 -C 10 -carbonyl, C 1 -C 10 -carboxyl, C 1 -C 10 -alkylamido, C 1 -C 10 -aminocarbonyl, nitrile (—CN) or C 1 -C 10 -sulfonamide. 
     
     
         28 . The catalyst according to  claim 26 , wherein L is a N-heterocyclic carbene (NHC) ligand. 
     
     
         29 . The catalyst according to  claim 26 , wherein L is a N-heterocyclic carbene ligand having the formula (III) or (IV) 
       
         
           
           
               
               
           
         
         wherein
 R 3  is selected from the group of 2,4,6-trimethylphenyl, 2,6-di-isopropylphenyl, 3,5-di-tert.-butylphenyl, 2-methylphenyl and combinations thereof. 
 
       
     
     
         30 . The catalyst according to  claim 26 , wherein
   L is a NHC ligand selected from the group of 1,3-bis-(2,4,6-trimethylphenyl)-imidazolidine-2-ylidene (“SIMes”), 1,3-bis-(2,6-di-isopropylphenyl)-imidazolidine-2-ylidene (“SIPr”) or 1,3-bis-(2,6-di-isopropylphenyl)-imidazoline-2-ylidene (“IPr”);   X is Cl − ;   a, b, c and d each are hydrogen;   R 1  is hydrogen, dimethylamino (NMe 2 ), nitro (NO 2 ) or chlorine (Cl).     
     
     
         31 . The catalyst according to  claim 26 , wherein L is a phosphine ligand selected from the group of tri-isopropylphosphine, tricyclohexylphosphine (PCy 3 ), tricyclopentylphosphine and phospha-bicycloalkane compounds selected from the group of 9-cyclohexyl-9-phospha-bicyclo-[3.3.1]-nonane (“cyclohexylphobane”), 9-(2,2,4-trimethylpentyl)-9-phospha-bicyclo-[3.3.1]-nonane (“2,2,4-trimethylpentyl phobane”) and 9-isobutyl-9-phospha-bicyclo-[3.3.1]-nonane (“isobutylphobane”). 
     
     
         32 . The catalyst according to  claim 30 , having the formula (IIa) 
       
         
           
           
               
               
           
         
       
     
     
         33 . The catalyst according to  claim 30 , having the formula (IIb) 
       
         
           
           
               
               
           
         
       
     
     
         34 . The catalyst according to  claim 30 , having the formula (IIe) 
       
         
           
           
               
               
           
         
       
     
     
         35 . The catalyst according to  claim 30 , having the formula (IIf) 
       
         
           
           
               
               
           
         
       
     
     
         36 . A method for preparing the catalyst according to  claim 26 , comprising reacting a compound of formula (I) 
       
         
           
           
               
               
           
         
         wherein
 a, b, c and d are, independently from each other, selected from hydrogen, straight chain or branched alkyl groups including C 1 -C 10 -alkyl, C 1 -C 10 -alkoxy, C 1 -C 10 -alkylthio, C 1 -C 10 -silyloxy, C 1 -C 10 -alkylamino, optionally substituted C 6 -C 14 -aryl, optionally substituted C 6 -C 14 -aryloxy, optionally substituted C 6 -C 14 -heteroaryl or electron-withdrawing groups (EWG); 
 R 1  is hydrogen, straight chain or branched C 1 -C 10 -alkyl, C 1 -C 10 -alkoxy, C 1 -C 10 -alkylthio, C 1 -C 10 -silyloxy, C 1 -C 10 -alkylamino, C 1 -C 10 -dialkylamino, C 6 -C 14 -aryl, C 6 -C 14 -aryloxy, C 6 -C 14 -heterocyclic or electron-withdrawing groups (EWG); 
 R 2  is hydrogen, straight chain or branched C 1 -C 10 -alkyl groups 
 
         with a Ru-starting compound having the formula (V): 
       
       
         
           
           
               
               
           
         
         in a cross metathesis reaction, 
         wherein
 L is a phosphine ligand selected from the group of tri-iso-propyl-phosphine, tricyclohexylphosphine (PCy 3 ), tricyclopentylphosphine, cyclohexylphobane, 2,2,4-trimethylpentylphobane or isobutyl-phobane or a NHC ligand selected from the group of 1,3-bis-(2,4,6-trimethylphenyl)-imidazolidine-2-ylidene (“SIMes”), 1,3-bis-(2,6-di-isopropylphenyl)-imidazolidine-2-ylidene (“SIPr”) or 1,3-bis-(2,6-di-isopropylphenyl)-imidazoline-2-ylidene (“IPr”) and 
 L′ is a leaving ligand from the group of tri-iso-propylphosphine, tricyclohexylphosphine (PCy 3 ), tricyclopentylphosphine, cyclo-hexylphobane, 2,2,4-trimethylpentyl-phobane, isobutylphobane or substituted or unsubstituted pyridine ligands; 
 X is an anionic ligand selected from the group of halogen anions (Cl − , Br − , I − ). 
 
       
     
     
         37 . The method for preparing the catalysts according to  claim 36 ,
 wherein
 L is a NHC ligand selected from the group of 1,3-bis-(2,4,6-trimethylphenyl)-imidazolidine-2-ylidene (“SIMes”), 1,3-bis-(2,6-di-isopropylphenyl)-imidazolidine-2-ylidene (“SIPr”) or 1,3-bis-(2,6-di-isopropylphenyl)-imidazoline-2-ylidene (“IPr”), 
 L′ is pyridine, 
 X is Cl − . 
   
     
     
         38 . An olefin metathesis reaction which comprises utilizing the catalyst according to  claim 26 . 
     
     
         39 . The metathesis reaction as claimed in  claim 38 , wherein the reaction is a ring-closing metathesis (RCM), cross metathesis (CM) or ring-opening metathesis polymerization (ROMP). 
     
     
         40 . The metathesis reaction as claimed in  claim 38 , wherein the olefin metathesis is carried out at temperatures <55° C. with catalyst loadings <0.1 mol-%. 
     
     
         41 . The metathesis reaction as claimed in  claim 38 , wherein reaction is a ring-closing metathesis (RCM), wherein the activity of the catalyst in the reaction (turn-over frequency, TOF) is >1 x 10 4  h −1 . 
     
     
         42 . A ruthenium-based compound of formula (II) 
       
         
           
           
               
               
           
         
         wherein
 L is a neutral two-electron donor ligand, 
 a, b, c and d are, independently from each other, selected from hydrogen, straight chain or branched C 1 -C 10 -alkyl, C 1 -C 10 -alkoxy, C 1 -C 10 -alkylthio, C 1 -C 10 -silyloxy, C 1 -C 10 -alkylamino, optionally substituted C 6 -C 14 -aryl, optionally substituted C 6 -C 14 -aryloxy, optionally substituted C 6 -C 14 -heteroaryl or electron-withdrawing groups (EWG); 
 R 1  is hydrogen, straight chain or branched alkyl groups including C 1 -C 10 -alkyl, C 1 -C 10 -alkoxy, C 1 -C 10 -alkylthio, C 1 -C 10 -silyloxy, C 1 -C 10 -alkylamino, C 6 -C 14 -aryl, C 6 -C 14 -aryloxy, C 6 -C 14 -heterocyclic or electron-withdrawing groups (EWG); 
 X is an anionic ligand independently selected from the group of halogen anions (Cl − , Br − , I − ), tetrafluoroborate (BF 4   − ) or acetate (CH 3 COO − ).