Refined routes to chlorin building blocks

Abstract

A method of making chlorins comprises the steps of reacting (e.g. condensing) a dipyrrin western half intermediate with an eastern half intermediate to form a tetrahydrobilene, and then cyclizing the tetrahydrobilene to form a chlorin. Intermediates including tetrahydrobilenes useful in such reactions are also described.

1 .- 36 . (canceled) 
     
     
         37 . A method of making a compound of Formula WH: 
       
         
           
           
               
               
           
         
       
       wherein:
 K 1  is selected from the group consisting of N, O, S, Se, Te, and CH; 
 S 1 , S 2 , S 7 , S 8 , S 9 , S 12 , S 13 , and S 14  are independently selected from the group consisting of H, aryl, phenyl, cycloalkyl, alkyl, alkenyl, alkynyl, halogen, alkoxy, alkylthio, perfluoroalkyl, perfluoroaryl, pyridyl, cyano, thiocyanato, nitro, amino, alkylamino, acyl, sulfoxyl, sulfonyl, imido, amido, and carbamoyl; 
 and wherein from one to two of S 1 , S 2 , S 7 , S 8 , S 9 , S 12 , S 13 , and S 14  may optionally be independently selected linking groups Q, wherein said linking groups Q are of the formula: 
 
       
         
           
           
               
               
           
         
       
       wherein:
 n is from 0 to 10; 
 R 3  may be present or absent; 
 R 1 , R 2 , and R 3  are each independently selected from the group consisting of ethene, ethyne, aryl, and heteroaryl groups, which aryl and heteroaryl groups may be unsubstituted or substituted one or more times with H, aryl, phenyl, cycloalkyl, alkyl, alkenyl, alkynyl, halogen, alkoxy, alkylthio, perfluoroalkyl, perfluoroaryl, pyridyl, cyano, thiocyanato, nitro, amino, alkylamino, acyl, sulfoxyl, sulfonyl, imido, amido, and carbamoyl; 
 Y is a protected or unprotected reactive substituent selected from the group consisting of hydroxy, thio, seleno, telluro, ester, carboxylic acid, boronic acid, phenol, silane, sulfonic acid, phosphonic acid, alkylthiol, formyl, halo, alkenyl, alkynyl, haloalkyl, alkyl phosphonate, alkyl sulfonate, alkyl carboxylate, and alkyl boronate groups; 
 said method comprising reacting a compound of Formula III 
 
       
         
           
           
               
               
           
         
       
       in an organic solvent in the presence of Ti(0) to form the compound of Formula WH. 
     
     
         38 . A compound according to Formula III: 
       
         
           
           
               
               
           
         
       
       wherein:
 K 1  is selected from the group consisting of N, O, S, Se, Te, and CH; 
 S 1 , S 2 , S 7 , S 8 , S 9 , S 12 , S 13 , and S 14  are independently selected from the group consisting of H, aryl, phenyl, cycloalkyl, alkyl, alkenyl, alkynyl, halogen, alkoxy, alkylthio, perfluoroalkyl, perfluoroaryl, pyridyl, cyano, thiocyanato, nitro, amino, alkylamino, acyl, sulfoxyl, sulfonyl, imido, amido, and carbamoyl; 
 and wherein from one to two of S 1 , S 2 , S 7 , S 8 , S 9 , S 12 , S 13 , and S 14  may optionally be independently selected linking groups Q, wherein said linking groups Q are of the formula: 
 
       
         
           
           
               
               
           
         
       
       wherein:
 n is from 0 to 10; 
 R 3  may be present or absent; 
 R 1 , R 2 , and R 3  are each independently selected from the group consisting of ethene, ethyne, aryl, and heteroaryl groups, which aryl and heteroaryl groups may be unsubstituted or substituted one or more times with H, aryl, phenyl, cycloalkyl, alkyl, alkenyl, alkynyl, halogen, alkoxy, alkylthio, perfluoroalkyl, perfluoroaryl, pyridyl, cyano, thiocyanato, nitro, amino, alkylamino, acyl, sulfoxyl, sulfonyl, imido, amido, and carbamoyl; and 
 Y is a protected or unprotected reactive substituent selected from the group consisting of hydroxy, thio, seleno, telluro, ester, carboxylic acid, boronic acid, phenol, silane, sulfonic acid, phosphonic acid, alkylthiol, formyl, halo, alkenyl, alkynyl, haloalkyl, alkyl phosphonate, alkyl sulfonate, alkyl carboxylate, and alkyl boronate groups. 
 
     
     
         39 . A method of making a compound of Formula III: 
       
         
           
           
               
               
           
         
       
       wherein:
 K 1  is selected from the group consisting of N, O, S, Se, Te, and CH; 
 S 1 , S 2 , S 7 , S 8 , S 9 , S 12 , S 13 , and S 14  are independently selected from the group consisting of H, aryl, phenyl, cycloalkyl, alkyl, alkenyl, alkynyl, halogen, alkoxy, alkylthio, perfluoroalkyl, perfluoroaryl, pyridyl, cyano, thiocyanato, nitro, amino, alkylamino, acyl, sulfoxyl, sulfonyl, imido, amido, and carbamoyl; 
 and wherein from one to two of S 1 , S 2 , S 7 , S 8 , S 9 , S 12 , S 13 , and S 14  may optionally be independently selected linking groups Q, wherein said linking groups Q are of the formula: 
 
       
         
           
           
               
               
           
         
       
       wherein:
 n is from 0 to 10; 
 R 3  may be present or absent; 
 R 1 , R 2 , and R 3  are each independently selected from the group consisting of ethene, ethyne, aryl, and heteroaryl groups, which aryl and heteroaryl groups may be unsubstituted or substituted one or more times with H, aryl, phenyl, cycloalkyl, alkyl, alkenyl, alkynyl, halogen, alkoxy, alkylthio, perfluoroalkyl, perfluoroaryl, pyridyl, cyano, thiocyanato, nitro, amino, alkylamino, acyl, sulfoxyl, sulfonyl, imido, amido, and carbamoyl; and 
 Y is a protected or unprotected reactive substituent selected from the group consisting of hydroxy, thio, seleno, telluro, ester, carboxylic acid, boronic acid, phenol, silane, sulfonic acid, phosphonic acid, alkylthiol, formyl, halo, alkenyl, alkynyl, haloalkyl, alkyl phosphonate, alkyl sulfonate, alkyl carboxylate, and alkyl boronate groups; 
 comprising cyclizing a compound of Formula II: 
 
       
         
           
           
               
               
           
         
         in an organic solvent under reducing conditions to produce a compound of Formula III. 
       
     
     
         40 . A compound of Formula II: 
       
         
           
           
               
               
           
         
       
       wherein:
 K 1  is selected from the group consisting of N, O, S, Se, Te, and CH; 
 S 1 , S 2 , S 7 , S 8 , S 9 , S 12 , S 13 , and S 14  are independently selected from the group consisting of H, aryl, phenyl, cycloalkyl, alkyl, alkenyl, alkynyl, halogen, alkoxy, alkylthio, perfluoroalkyl, perfluoroaryl, pyridyl, cyano, thiocyanato, nitro, amino, alkylamino, acyl, sulfoxyl, sulfonyl, imido, amido, and carbamoyl; 
 and wherein from one to two of S 1 , S 2 , S 7 , S 8 , S 9 , S 12 , S 13 , and S 14  may optionally be independently selected linking groups Q, wherein said linking groups Q are of the formula: 
 
       
         
           
           
               
               
           
         
       
       wherein:
 n is from 0 to 10; 
 R 3  may be present or absent; 
 R 1 , R 2 , and R 3  are each independently selected from the group consisting of ethene, ethyne, aryl, and heteroaryl groups, which aryl and heteroaryl groups may be unsubstituted or substituted one or more times with H, aryl, phenyl, cycloalkyl, alkyl, alkenyl, alkynyl, halogen, alkoxy, alkylthio, perfluoroalkyl, perfluoroaryl, pyridyl, cyano, thiocyanato, nitro, amino, alkylamino, acyl, sulfoxyl, sulfonyl, imido, amido, and carbamoyl; and 
 Y is a protected or unprotected reactive substituent selected from the group consisting of hydroxy, thio, seleno, telluro, ester, carboxylic acid, boronic acid, phenol, silane, sulfonic acid, phosphonic acid, alkylthiol, formyl, halo, alkenyl, alkynyl, haloalkyl, alkyl phosphonate, alkyl sulfonate, alkyl carboxylate, and alkyl boronate groups. 
 
     
     
         41 . A compound of Formula X: 
       
         
           
           
               
               
           
         
       
       wherein:
 M is a metal selected from the group consisting of Cu, Zn, Mg, Pt, Pd, Sn and Al, or M is absent; 
 K 1 , K 2  and K 4  are hetero atoms independently selected from the group consisting of N, O, S, Se, Te, and CH; 
 K 3  is N; 
 S 1 , S 2 , S 3 , S 4 , S 5 , S 6 , S 8 , S 9 , S 10 , S 11 , S 12 , and S 14  are independently selected from the group consisting of H, aryl, phenyl, cycloalkyl, alkyl, alkenyl, alkynyl, halogen, alkoxy, alkylthio, perfluoroalkyl, perfluoroaryl, pyridyl, cyano, thiocyanato, nitro, amino, alkylamino, acyl, sulfoxyl, sulfonyl, imido, amido, and carbamoyl; 
 S 7  and S 13  are together ═O; 
 and wherein from one to four of S 1 , S 2 , S 3 , S 4 , S 5 , S 6 , S 7 , S 8 , S 9 , S 10 , S 11 , S 12 , S 13 , and S 14  are independently selected linking groups Q, wherein said linking groups Q are of the formula: 
 
       
         
           
           
               
               
           
         
       
       wherein:
 n is from 0 to 10; 
 R 3  may be present or absent; 
 R 1 , R 2 , and R 3  are each independently selected from the group consisting of ethene, ethyne, aryl, and heteroaryl groups, which aryl and heteroaryl groups may be unsubstituted or substituted one or more times with H, aryl, phenyl, cycloalkyl, alkyl, alkenyl, alkynyl, halogen, alkoxy, alkylthio, perfluoroalkyl, perfluoroaryl, pyridyl, cyano, thiocyanato, nitro, amino, alkylamino, acyl, sulfoxyl, sulfonyl, imido, amido, and carbamoyl; and 
 Y is a protected or unprotected reactive substituent selected from the group consisting of hydroxy, thio, seleno, telluro, ester, carboxylic acid, boronic acid, phenol, silane, sulfonic acid, phosphoric acid, alkylthiol, formyl, halo, alkenyl, alkynyl, haloalkyl, alkyl phosphonate, alkyl sulfonate, alkyl carboxylate, and alkyl boronate groups. 
 
     
     
         42 . The compound according to  claim 41 , wherein S 1  is a linking group Q. 
     
     
         43 . The compound according to  claim 41 , wherein S 1  is iodo.