Hydroamination of Alkenes

Abstract

A method includes reacting an amino group, a composition including rhodium and an organic ligand, and a substrate having structural formula (I) in a reaction mixture. R 1 is an organic group including a sp 3 carbon atom bonded to C A . R 2 is selected from the group consisting of hydrogen, methyl, and an organic group including a sp 3 carbon atom bonded to C A . R 3 and R 4 independently are selected from the group consisting of hydrogen, methyl, and an organic group including a sp 3 carbon atom bonded to C B . The method further includes forming a hydroaminated product in the reaction mixture.

1 . A method, comprising:
 reacting an amino group, a composition comprising rhodium and an organic ligand, and a substrate having structural formula (I) in a reaction mixture;   
       
         
           
           
               
               
           
         
         where R 1  is an organic group comprising a sp 3  carbon atom bonded to C A , 
         R 2  is selected from the group consisting of hydrogen, methyl, and an organic group comprising a sp 3  carbon atom bonded to C A , and 
         R 3  and R 4  independently are selected from the group consisting of hydrogen, methyl, and an organic group comprising a sp 3  carbon atom bonded to C B ; and 
         forming a hydroaminated product in the reaction mixture. 
       
     
     
         2 . The method of  claim 1 , where the amino group is a substituent group of the substrate. 
     
     
         3 . The method of  claim 2 , where the hydroaminated product comprises a heterocyclic ring comprising a nitrogen from the amino group and at least one of C A  and C B . 
     
     
         4 . The method of  claim 1 , where the amino group is a substituent group of a compound separate from the substrate. 
     
     
         5 . The method of  claim 1 , where the amino group is a primary amino group. 
     
     
         6 . The method of  claim 1 , where the amino group is a secondary amino group. 
     
     
         7 . The method of  claim 1 , where the substrate comprises at least one functional group. 
     
     
         8 . The method of  claim 7 , where the at least one functional group is selected from the group consisting of hydroxyl, ether, ester, cyano, and halogen. 
     
     
         9 . The method of  claim 1 , where R 2  is methyl or an organic group comprising a sp 3  carbon atom bonded to C A . 
     
     
         10 . The method of  claim 1 , where at least one of R 3  and R 4  is methyl or an organic group comprising a sp 3  carbon atom bonded to C B . 
     
     
         11 . The method of  claim 1 , where the organic ligand is selected from the group consisting of DPPF, t-BuXantphos, 4,5-(bis[bis-diethylamido]-phosphonito)-9,9-dimethylxanthene, 2-dicyclohexyl-phosphino-2′-(N,N-dimethylamino)biphenyl and substituted derivatives thereof. 
     
     
         12 . The method of  claim 1 , where the mole ratio of ligand to rhodium is from 0.8 to 2. 
     
     
         13 . The method of  claim 1 , where the mole ratio of ligand to rhodium is from 0.9 to 1.5. 
     
     
         14 . The method of  claim 1 , where the mole ratio of ligand to rhodium is from 1 to 1.2. 
     
     
         15 . The method of  claim 1 , where
 when the catalyst is present in the reaction mixture in an amount providing 2.5 mol % rhodium relative to the amino group, and   the reaction mixture is heated at 70° C. for 7 h,   the yield of the hydroaminated product in the reaction mixture is at least 65%.   
     
     
         16 . The method of  claim 15 , where the yield of the hydroaminated product in the reaction mixture is at least 70%. 
     
     
         17 . The method of  claim 15 , where the yield of the hydroaminated product in the reaction mixture is at least 75%. 
     
     
         18 . The method of  claim 15 , where the yield of the hydroaminated product in the reaction mixture is at least 80%. 
     
     
         19 . The method of  claim 15 , where the yield of the hydroaminated product in the reaction mixture is at least 90%.