Intramolecular amidation of sulfamate esters catalyzed by metalloporphyrins

Abstract

The present invention relates to novel intramolecular amidation processes for substrates such as sulfamate esters using chiral and non-chiral metalloporphyrin complexes, which can maximize catalytic activity and enhance efficiency, stereoselectivity and speed of amidation of these substrates. The intramolecular amidation of sulfamate ester exhibits excellent cis-selectivity, affording cyclic sulfamidates with high ee values catalyzed by chiral metalloporphyrin.

What is claimed is:  
     
         1 . A method for synthesizing a cyclic sulfamidate from a sulfamate ester comprising the step of catalyzing the reaction of an oxidant and a base with said sulfamate ester with a catalytic amount of metalloporphyrin as catalyst for producing the cyclic sulfamidate.  
     
     
         2 . The method according to  claim 1  wherein the sulfamate ester is a compound comprising a sulfonylamide functional group.  
     
     
         3 . The method according to  claim 1  wherein the oxidant is selected from the group consisting of PhI(OAc) 2 , PhIO, and NBS.  
     
     
         4 . The method according to  claim 1  further comprising an organic solvent selected from the group consisting of acetonitrile, DMF, CH 2 Cl 2 , and benzene.  
     
     
         5 . The method according to  claim 1  wherein the base is selected from the group consisting of Al 2 O 3 , MgO, ZnO, K 2 CO 3 , and KOH.  
     
     
         6 . The method accoring to  claim 1  wherein the metalloporphyrin is a transition metal metalloporphyrin.  
     
     
         7 . The method according to  claim 6  wherein the transition metal metalloporphyrin is selected from the group consisting of ruthenium, manganese, iron, cobalt, copper and osmium metalloporphyrin.  
     
     
         8 . The method according to  claim 7 , wherein the metalloporphyrin is ruthenium porphyrin.  
     
     
         9 . The method according to  claim 1  wherein the metalloporphyrin catalyst has the structure:  
       
         
           
           
               
               
           
         
       
       wherein M represents a metal.  
     
     
         10 . The method of  claim 9  wherein M is ruthenium.  
     
     
         11 . The method of  claim 9  wherein the catalyst exhibits cis-selectivity.  
     
     
         12 . The method according to  claim 1  wherein the metalloporphyrin catalyst has the structure:  
       
         
           
           
               
               
           
         
       
       wherein M represents a metal.  
     
     
         13 . The method of  claim 12  wherein M is ruthenium.  
     
     
         14 . The method of  claim 12  wherein the catalyst exhibit cis-selectivity.  
     
     
         15 . The method of  claim 12  wherein the catalyst exhibits enantioselctivity and yields corresponding cyclic sulfamidate with high ee value.