N-heterocyclic carbene metallacycle catalysts and methods

Abstract

The present invention generally relates to materials and methods for catalytic reactions, including transition metal-catalyzed cross-coupling reactions. The materials may be stable metal complexes that do not require special handling or processing conditions. In some cases, materials of the invention advantageously may be synthesized in one synthetic step without the need for isolation of intermediate compounds. Also, materials of the invention may be synthesized from inexpensive and readily available starting materials, under relatively mild reaction conditions that do not require the exclusion of air, water, and the like. In some embodiments, the material is a N-heterocyclic carbene metallacycle complex. Such materials and methods may be useful in the production of fine chemicals, advanced materials and specialty polymers.

What is claimed: 
     
         1 . A method for synthesizing a transition metal-containing precatalyst, comprising:
 reacting at least three components all contained together in a single reaction chamber to form a transition metal-containing precatalyst having one of the following structures,   
       
         
           
           
               
               
           
         
         wherein M is Pd, Pt, or Ru; each R 1-8  is independently absent, hydrogen, alkyl, cycloalkyl, heteroalkyl, cycloheteroalkyl, aryl, heteroaryl, or a substituted derivative thereof, or wherein any two of R 1-8  are joined to form a cycloalkyl, cycloheteroalkyl, aryl, heteroaryl, or substituted derivative thereof; A is carbon or a heteroatom; B is a heteroatom; C is alkyl or aryl; D is a heteroatom; X 1  is halide, sulfonate, or carboxylate; X 2  is a neutral ligand; Y is a counterion;   is alkyl, heteroalkyl, aryl, heteroaryl, or a substituted derivative thereof;   is a single bond or double bond; and n is an integer between 1 and 3. 
       
     
     
         2 . A method as in  claim 1 , wherein each R 1-8  is independently hydrogen, alkyl, cycloalkyl, alkoxy, amino, aryl, heteroaryl, or substituted derivatives thereof; A is carbon, nitrogen, phosphorus, oxygen, or sulfur; C is nitrogen, phosphorus, oxygen, or sulfur; D is nitrogen, phosphorus, arsenic, antimony, oxygen, sulfur, selenium, or tellurium; and n is an integer between 1 and 3. 
     
     
         3 - 11 . (canceled) 
     
     
         12 . A method as in  claim 1 , wherein one of the three components is a palladium-containing compound. 
     
     
         13 .- 14 . (canceled) 
     
     
         15 . A method as in  claim 1 , wherein one of the three components is an N-heterocyclic carbene ligand precursor. 
     
     
         16 . A method as in  claim 1 , wherein the N-heterocyclic carbene ligand precursor has the structure, 
       
         
           
           
               
               
           
         
       
       each R 1-4  is independently absent, hydrogen, alkyl, cycloalkyl, heteroalkyl, cycloheteroalkyl, aryl, heteroaryl, or a substituted derivative thereof, or wherein any two of R 1-4  are joined to form a cycloalkyl, cycloheteroalkyl, aryl, heteroaryl, or substituted derivative thereof; A is carbon or a heteroatom; B is a heteroatom;   is a single bond or double bond; n is an integer between 1 and 3; and Z is halide, sulfonate, carboxylate, BF 4 , PF 6 , or Ar 4 B, wherein Ar is aryl. 
     
     
         17 . A method as in  claim 16 , wherein the N-heterocyclic carbene ligand precursor has the structure, 
       
         
           
           
               
               
           
         
       
     
     
         18 . A method as in  claim 16 , wherein the N-heterocyclic carbene ligand precursor has the structure, 
       
         
           
           
               
               
           
         
       
     
     
         19 . A method as in  claim 1 , wherein one of the three components is a compound having the structure, 
       
         
           
           
               
               
           
         
       
       wherein each R 5-8  is independently absent, hydrogen, alkyl, cycloalkyl, heteroalkyl, cycloheteroalkyl, aryl, heteroaryl, or a substituted derivative thereof, or wherein any two of R 5-8  are joined to form a cycloalkyl, cycloheteroalkyl, aryl, heteroaryl, or substituted derivative thereof; C is alkyl or aryl; D is a heteroatom; X is halide or carboxylate;   is alkyl, heteroalkyl, aryl, heteroaryl, or a substituted derivative thereof. 
     
     
         20 - 29 . (canceled) 
     
     
         30 . A method as in  claim 1 , wherein the at least three components are a palladium-containing compound, an N-heterocyclic carbene ligand precursor, and a compound having the structure, 
       
         
           
           
               
               
           
         
       
       wherein each R 5-8  is independently absent, hydrogen, alkyl, cycloalkyl, heteroalkyl, cycloheteroalkyl, aryl, heteroaryl, or a substituted derivative thereof, or wherein any two of R 5-8  are joined to form a cycloalkyl, cycloheteroalkyl, aryl, heteroaryl, or substituted derivative thereof; C is alkyl or aryl; D is a heteroatom; X is halide, sulfonate, or carboxylate;   is alkyl, heteroalkyl, aryl, heteroaryl, or a substituted derivative thereof. 
     
     
         31 . A method as in  claim 1 , wherein the at least three components are not joined by a bond prior to the reacting. 
     
     
         32 . A method as in  claim 1 , wherein the method is represented by Scheme 1, 
       
         
           
           
               
               
           
         
       
     
     
         33 . A composition of matter, comprising a compound having one of the following structures, 
       
         
           
           
               
               
           
         
         wherein M is Pd, Pt, or Ru; each R 1-8  is independently absent, hydrogen, alkyl, cycloalkyl, heteroalkyl, cycloheteroalkyl, aryl, heteroaryl, or a substituted derivative thereof, or wherein any two of R 1-8  are joined to form a cycloalkyl, cycloheteroalkyl, aryl, heteroaryl, or substituted derivative thereof; A is carbon or a heteroatom; B is a heteroatom; C is alkyl or aryl; D is a heteroatom; X 1  is halide, sulfonate, or carboxylate; X 2  is a neutral ligand; Y is a counterion;   is alkyl, heteroalkyl, aryl, heteroaryl, or a substituted derivative thereof;   is a single bond or double bond; and n is an integer between 1 and 3; 
         wherein the compound does not have the following structure, 
       
       
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
       
     
     
         34 . A composition as in  claim 33 , wherein each R 1-8  is independently hydrogen, alkyl, cycloalkyl, alkoxy, amino, aryl, heteroaryl, or substituted derivatives thereof; A is carbon, nitrogen, phosphorus, oxygen, or sulfur; B is nitrogen, phosphorus, oxygen, or sulfur; D is nitrogen, phosphorus, arsenic, antimony, oxygen, sulfur, selenium, or tellurium; and n is an integer between 1 and 3. 
     
     
         35 . A composition as in  claim 33 , wherein A and B are nitrogen; D is nitrogen, phosphorus, or sulfur; R 1  and R 2  are aromatic rings optionally substituted with methyl, ethyl, isopropyl, t-butyl, methoxy, isopropoxy, trifluoromethyl, or phenyl; R 3  and R 4  are phenyl, t-butyl, or are joined together to form a six-membered ring; R 5  and R 6  are hydrogen, t-butyl, methoxy, trifluoromethyl, or are joined together to form an aryl ring; R 7  and R 8  are methyl, isopropyl, t-butyl, phenyl, phenoxy, hydroxyl, R 7  and R 8  are joined together to form a ring; or at least one of R 7  and R 8  is joined to a portion of   to form a ring. 
     
     
         36 - 44 . (canceled) 
     
     
         45 . A composition as in  claim 33 , wherein the compound has the following structure, 
       
         
           
           
               
               
           
         
       
     
     
         46 . A composition as in  claim 33 , wherein the compound has the following structure, 
       
         
           
           
               
               
           
         
       
     
     
         47 - 51 . (canceled) 
     
     
         52 . A composition of matter, comprising a compound having the following structure, 
       
         
           
           
               
               
           
         
       
       wherein   is a single bond or double bond. 
     
     
         53 . (canceled) 
     
     
         54 . A composition as in  claim 33 , wherein D is nitrogen, phosphorous, arsenic, or antimony. 
     
     
         55 . A composition as in  claim 33 , wherein D is oxygen, sulfur, selenium, or tellurium.