Synthesis of metal complexes and uses thereof

Abstract

The present disclosure provides novel methods of making aluminum complexes with utility for promoting epoxide carbonylation reactions. Methods include reacting neutral metal carbonyl compounds with alkylaluminum complexes.

1 . A method for preparing an aluminum-based carbonylation catalyst of formula: 
       
         
           
           
               
               
           
         
         the method comprising a step of contacting a compound of formula I: 
       
       
         
           
           
               
               
           
         
         with a neutral metal carbonyl compound, wherein 
         Q is independently at each occurrence a nitrogen or oxygen atom which is part of a ligand complexed to the aluminum atom, where any two or more Q groups may comprise part of a single ligand; 
         R q  is selected from optionally substituted C 1-12  aliphatic and optionally substituted aryl; 
         M is a metal atom; 
         Q′ is any ligand and need not be present; 
         d is an integer between 0 and 8 inclusive; 
         e is an integer between 1 and 6 inclusive; 
         w is a number such as to provide the stable anionic metal carbonyl complex; and 
         y is the charge of the metal carbonyl anion. 
       
     
     
         2 . A method for preparing an aluminum-based carbonylation catalyst of formula: 
       
         
           
           
               
               
           
         
         the method comprising a step of contacting a compound for formula I′: 
       
       
         
           
           
               
               
           
         
         with a neutral metal carbonyl compound, wherein: 
         Q is independently at each occurrence a nitrogen or oxygen atom which is part of a ligand complexed to the aluminum atom, where any two or more Q groups may comprise part of a single ligand; 
         M is a metal atom; 
         Q′ is any ligand and need not be present; 
         d is an integer between 0 and 8 inclusive; 
         e is an integer between 1 and 6 inclusive; 
         w is a number such as to provide the stable anionic metal carbonyl complex; 
         y is the charge of the metal carbonyl anion; and 
         R q′  is selected from —H, optionally substituted C 1-40  aliphatic and optionally substituted aryl. 
       
     
     
         3 . A method for preparing an aluminum-based carbonylation catalyst of formula: 
       
         
           
           
               
               
           
         
         the method comprising a step of contacting a compound of formula I: 
       
       
         
           
           
               
               
           
         
         with a neutral metal carbonyl compound in the presence of carbon monoxide and an epoxide of formula: 
       
       
         
           
           
               
               
           
         
       
       where
 Q is independently at each occurrence a nitrogen or oxygen atom which is part of a ligand complexed to the aluminum atom, where any two or more Q groups may comprise part of a single ligand; 
 R q  is selected from optionally substituted C 1-12  aliphatic and optionally substituted aryl; 
 M is a metal atom; 
 Q′ is any ligand and need not be present; 
 d is an integer between 0 and 8 inclusive; 
 w is a number such as to provide the stable anionic metal carbonyl complex; 
 R a′  is hydrogen or an optionally substituted group selected from the group consisting of C 1-30  aliphatic; C 1-30  heteroaliphatic having 1-4 heteroatoms independently selected from the group consisting of nitrogen, oxygen, and sulfur; 6- to 10-membered aryl; 5- to 10-membered heteroaryl having 1-4 heteroatoms independently selected from nitrogen, oxygen, and sulfur; and 4- to 7-membered heterocyclic having 1-3 heteroatoms independently selected from the group consisting of nitrogen, oxygen, and sulfur; and 
 each of R b′ , R c′ , and R d′  is independently hydrogen or an optionally substituted group selected from the group consisting of C 1-12  aliphatic; C 1-12  heteroaliphatic having 1-4 heteroatoms independently selected from the group consisting of nitrogen, oxygen, and sulfur; 6- to 10-membered aryl; 5- to 10-membered heteroaryl having 1-4 heteroatoms independently selected from nitrogen, oxygen, and sulfur; and 4- to 7-membered heterocyclic having 1-3 heteroatoms independently selected from the group consisting of nitrogen, oxygen, and sulfur, wherein any of (R b′  and R c′ ), (R c′  and R d′ ), and (R a′  and R b′ ) can be taken together with their intervening atoms to form one or more rings selected from the group consisting of: optionally substituted C 3 -C 14  carbocycle, optionally substituted C 3 -C 14  heterocycle, optionally substituted C 6 -C 10  aryl, and optionally substituted C 5 -C 10  heteroaryl. 
 
     
     
         4 . A method for preparing an aluminum-based carbonylation catalyst of formula: 
       
         
           
           
               
               
           
         
         the method comprising a step of contacting a compound for formula I′: 
       
       
         
           
           
               
               
           
         
         with a neutral metal carbonyl compound in the presence of carbon monoxide and an epoxide of formula: 
       
       
         
           
           
               
               
           
         
         wherein: 
         Q is independently at each occurrence a nitrogen or oxygen atom which is part of a ligand complexed to the aluminum atom, where any two or more Q groups may comprise part of a single ligand; 
         R q′  is selected from —H, optionally substituted C 1-40  aliphatic and optionally substituted aryl; 
         M is a metal atom; 
         Q′ is any ligand and need not be present; 
         d is an integer between 0 and 8 inclusive; 
         w is a number such as to provide the stable anionic metal carbonyl complex; 
         R a′  is hydrogen or an optionally substituted group selected from the group consisting of C 1-30  aliphatic; C 1-30  heteroaliphatic having 1-4 heteroatoms independently selected from the group consisting of nitrogen, oxygen, and sulfur; 6- to 10-membered aryl; 5- to 10-membered heteroaryl having 1-4 heteroatoms independently selected from nitrogen, oxygen, and sulfur; and 4- to 7-membered heterocyclic having 1-3 heteroatoms independently selected from the group consisting of nitrogen, oxygen, and sulfur; and 
         each of R b′ , R c′ , and R d′  is independently hydrogen or an optionally substituted group selected from the group consisting of C 1-12  aliphatic; C 1-12  heteroaliphatic having 1-4 heteroatoms independently selected from the group consisting of nitrogen, oxygen, and sulfur; 6- to 10-membered aryl; 5- to 10-membered heteroaryl having 1-4 heteroatoms independently selected from nitrogen, oxygen, and sulfur; and 4- to 7-membered heterocyclic having 1-3 heteroatoms independently selected from the group consisting of nitrogen, oxygen, and sulfur, wherein any of (R b′  and R c′ ), (R c′  and R d′ ), and (R a′  and R b′ ) can be taken together with their intervening atoms to form one or more rings selected from the group consisting of: optionally substituted C 3 -C 14  carbocycle, optionally substituted C 3 -C 14  heterocycle, optionally substituted C 6 -C 10  aryl, and optionally substituted C 5 -C 10  heteroaryl. 
       
     
     
         5 . A method for providing carbonylation catalysts to an epoxide carbonylation reaction,
 the epoxide carbonylation reaction comprising a reaction zone where an epoxide is contacted with carbon monoxide,   the method comprising the step of feeding the reaction zone with a first catalyst feed stream containing an aluminum complex of formula I and a second catalyst feed stream containing a neutral metal carbonyl compound,   wherein the aluminum complex of formula I has a formula:   
       
         
           
           
               
               
           
         
       
       where
 Q is independently at each occurrence a nitrogen or oxygen atom which is part of a ligand complexed to the aluminum atom, where any two or more Q groups may comprise part of a single ligand; and 
 R q  is selected from optionally substituted C 1-12  aliphatic and optionally substituted aryl. 
 
     
     
         6 . A method of synthesizing a symmetrical ketone comprising the step of contacting an aluminum compound of formula I: 
       
         
           
           
               
               
           
         
         with a neutral metal carbonyl compound to provide a product having a formula: 
       
       
         
           
           
               
               
           
         
       
       where
 Q is independently at each occurrence a nitrogen or oxygen atom which is part of a ligand complexed to the aluminum atom, where any two or more Q groups may comprise part of a single ligand; and 
 R q  is selected from optionally substituted C 1-12  aliphatic and optionally substituted aryl. 
 
     
     
         7 . The method of  claim 1 , wherein the moiety 
       
         
           
           
               
               
           
         
       
       comprises an aluminum-porphinato complex. 
     
     
         8 . The method of  claim 7 , wherein the aluminum-porphinato complex has a structure: 
       
         
           
           
               
               
           
         
       
       where
 R d  is independently at each occurrence hydrogen, halogen, —OR 4 , —NR y   2 , —SR, —CN, —NO 2 , —SO 2 R, —SOR y , —SO 2 NR y   2 ; —CNO, —NRSO 2 R, —NCO, —N 3 , —SiR 3 ; or an optionally substituted group selected from the group consisting of C 1-20  aliphatic; C 1-20  heteroaliphatic having 1-4 heteroatoms independently selected from the group consisting of nitrogen, oxygen, and sulfur; 6- to 10-membered aryl; 5- to 10-membered heteroaryl having 1-4 heteroatoms independently selected from nitrogen, oxygen, or sulfur; and 4- to 7-membered heterocyclic having 1-2 heteroatoms independently selected from the group consisting of nitrogen, oxygen, and sulfur, where two or more R d  groups may be taken together to form one or more optionally substituted rings,
 each R y  is independently hydrogen, or an optionally substituted group selected the group consisting of: acyl; carbamoyl, arylalkyl; 6- to 10-membered aryl; C 1-12  aliphatic; C 1-12  heteroaliphatic having 1-2 heteroatoms independently selected from the group consisting of nitrogen, oxygen, and sulfur; 5- to 10-membered heteroaryl having 1-4 heteroatoms independently selected from the group consisting of nitrogen, oxygen, and sulfur; 4- to 7-membered heterocyclic having 1-2 heteroatoms independently selected from the group consisting of nitrogen, oxygen, and sulfur; an oxygen protecting group; and a nitrogen protecting group; where two R y  on the same nitrogen atom may be taken with the nitrogen atom to form an optionally substituted 4- to 7-membered heterocyclic ring having 0-2 additional heteroatoms independently selected from the group consisting of nitrogen, oxygen, and sulfur, 
 R 4  is a hydroxyl protecting group or R y , and 
 R is independently at each occurrence optionally substituted C 1-12  aliphatic or optionally substituted aryl. 
 
 
     
     
         9 . The method of  claim 8 , wherein the aluminum-porphinato complex has a structure selected from the group consisting of: 
       
         
           
           
               
               
           
         
       
     
     
         10 . The method of  claim 7 , wherein the aluminum-porphinato complex has the structure: 
       
         
           
           
               
               
           
         
       
     
     
         11 . The method of  claim 10 , wherein the aluminum-porphinato complex has the structure: 
       
         
           
           
               
               
           
         
       
     
     
         12 . The method of  claim 10 , wherein the aluminum-porphinato complex has a structure selected from the group consisting of: 
       
         
           
           
               
               
           
         
         
           
           
               
               
           
         
       
     
     
         13 . The method of  claim 1 , wherein the neutral metal carbonyl compound is selected from the group consisting of: Ti(CO) 7 , V 2 (CO) 12 , Cr(CO) 6 , Mo(CO) 6 , W(CO) 6 , Mn 2 (CO) 10 , Tc 2 (CO) 10 , Re 2 (CO) 10 , Fe(CO) 5 , Ru(CO) 5 , Os(CO) 5 , Ru 3 (CO) 12 , Os 3 (CO) 12 , Fe 3 (CO) 12 , Fe 2 (CO) 9 , Co 4 (CO) 12 , Rh 4 (CO) 12 , Rh 6 (CO) 16 , Ir 4 (CO) 12 , Co 2 (CO) 8 , and Ni(CO) 4 . 
     
     
         14 . The method of  claim 1 ,
 wherein the neutral carbonyl compound comprises a cobalt carbonyl compound.   
     
     
         15 . The method of  claim 14 , wherein the cobalt carbonyl compound comprises dicobalt octacarbonyl. 
     
     
         16 . The method of  claim 1 , wherein the composition of catalysts thus formed have halide or alkali metal salts in an amount less than about 200 ppm, less than about 150 ppm, less than about 100 ppm, less than about 50 ppm, less than about 40 ppm, less than about 30 ppm, less than about 20 ppm, less than about 10 ppm, less than about 5 ppm, less than about 2 ppm, or less than about 1 ppm.