Processes of enantioselectively forming an aminoxy compound and an 1,2-oxazine compound

Abstract

Disclosed is a process of enantioselectively forming an aminoxy compound of Formula (3) In formula (3) R 1 is one of an aliphatic group and an alicyclic group. R 2 is one of hydrogen, an aliphatic group, an alicyclic group, an aromatic group, an arylaliphatic group and an arylalicyclic group. R 3 is one of hydrogen, halogen, hydroxyl, and an aliphatic group with a main chain having 1 to about 10 carbon atoms. The respective aliphatic, alicyclic, aromatic, arylaliphatic or arylalicyclic groups of R 1 , R 2 , and R 3 comprise 0 to about 3 heteroatoms independently selected from the group consisting of N, O, S, Se and Si. The process includes contacting a carbonyl compound of Formula (1) and a nitroso compound of Formula (2) in the presence of a chiral catalyst. The chiral catalyst is a compound of Formula (IX)

1 - 12 . (canceled) 
     
     
         13 . A process of enantioselectively forming an 1,2-oxazine compound of Formula (13) 
       
         
           
           
               
               
           
         
         wherein R 2  is one of hydrogen, an aliphatic group, and an alicyclic group, comprising 0 to about 3 heteroatoms independently selected from the group consisting of N, O, S, Se and Si, 
         R 3  is one of hydrogen, halogen, OR 6 , an aliphatic group with a main chain having 1 to about 10 carbon atoms and 0 to about 3 heteroatoms independently selected from the group consisting of N, O, S, Se and Si, and 
         R 8  is one of hydrogen, NO 2 , CN, C(R 40 )O, COOR 40 , and CONR 40 R 41 , an aliphatic group, an alicyclic group, an aromatic group, an arylaliphatic group and an arylalicyclic group, comprising 0 to about 3 heteroatoms independently selected from the group consisting of N, O, S, Se and Si, 
         wherein R 40  and R 41  are independent from one another one of hydrogen, an aliphatic group, an alicyclic group, an aromatic group, an arylaliphatic group and an arylalicyclic group, comprising 0 to about 3 heteroatoms independently selected from the group consisting of N, O, S, Se and Si, and 
         Z is one of NO 2 , CN, C(R 42 )O, COOR 42 , and CONR 42 R 43 , wherein R 42  and R 43  are independent from one another one of hydrogen, an aliphatic group, an alicyclic group, an aromatic group, an arylaliphatic group and an arylalicyclic group, comprising 0 to about 3 heteroatoms independently selected from the group consisting of N, O, S, Se and Si, 
         the process comprising contacting a carbonyl compound of Formula (11) 
       
       
         
           
           
               
               
           
         
         and a nitroso compound of Formula (2) 
       
       
         
           
           
               
               
           
         
         in the presence of a chiral catalyst, the catalyst being a compound of Formula (IX) 
       
       
         
           
           
               
               
           
         
         wherein R 4  and R 5  are independently one of COOH and 
       
       
         
           
           
               
               
           
         
         Y is one of CHOH, O, S, Se, CH 2 , CHOH, CHSH and CHSeH, 
         thereby forming a reaction mixture, and 
         allowing the carbonyl compound of Formula (1) and the nitroso compound of Formula (2) to react in the reaction mixture, thereby allowing the formation of the 1,2-oxazine compound of Formula (13). 
       
     
     
         14 . The process of  claim 13 , wherein the carbonyl compound of Formula (1) and the nitroso compound of Formula (2) are allowed to react at a temperature below 25° C. 
     
     
         15 . The process of  claim 14 , wherein the temperature is selected in the range from about −80° C. to about 0° C. 
     
     
         16 . The process of  claim 13 , wherein the carbonyl compound of Formula (1) and the nitroso compound of Formula (II) are allowed to react for a period of time selected in the range from about 15 minutes to about 48 hours. 
     
     
         17 . The process of  claim 13 , wherein the reaction mixture is formed in a dipolar aprotic solvent.