Selective Aliphatic C-H Oxidation

Abstract

A composition including a complex of a metal, a tetradentate ligand, at least one ancillary ligand, and a counterion may be used for selective sp 3 C—H bond oxidation. The tetradentate ligand may include a N-heterocyclic-N,N′-bis(pyridyl)-ethane-1,2-diamine group or a N,N′-bis(heterocyclic)-N,N′-bis(pyridyl)-ethane-1,2-diamine group. The composition can be used in combination with H 2 O 2 to effect highly selective oxidations of unactivated sp 3 C—H bonds over a broad range of substrates. The site of oxidation can be predicted, based on the electronic and/or steric environment of the C—H bond. In addition, the oxidation reaction does not require the presence of directing groups in the substrate.

1 - 37 . (canceled) 
     
     
         38 . A catalyst, comprising:
 a complex of a metal, a tetradentate ligand, at least one ancillary ligand, and a counterion;   where when 0.005 mmol of the complex is combined with 19.8 mg cis-4-methylcyclohexyl pivalate and 3.0 mg acetic acid in 0.15 mL acetonitrile, and then treated dropwise at 25° C. over 45 seconds with 0.12 mmol H 2 O 2  in 0.9 mL acetonitrile, the yield of trans-4-hydroxy-4-methylcyclohexyl pivalate after 15 minutes at 25° C. as determined by gas chromatography is at least 30%.   
     
     
         39 . The catalyst of  claim 38 , where the tetradentate ligand comprises a N-heterocyclic-N,N′-bis(pyridyl)-ethane-1,2-diamine group. 
     
     
         40 . The catalyst of  claim 38 , where the tetradentate ligand comprises a N,N′-bis(heterocyclic)-N,N′-bis(pyridyl)-ethane-1,2-diamine group. 
     
     
         41 . The catalyst of  claim 38 , where the yield of trans-4-hydroxy-4-methylcyclohexyl pivalate after 15 minutes at 25° C. as determined by gas chromatography is at least 35%. 
     
     
         42 . The catalyst of  claim 38 , where the yield of trans-4-hydroxy-4-methylcyclohexyl pivalate after 15 minutes at 25° C. as determined by gas chromatography is at least 38%.