Synthesis of Polycyclic Cyclohexadienone through Alkoxy-Oxylactonization and Dearomatization of 3'-Hydroxy-[1,1'-biphenyl]-2-carboxylic Acids Promoted by Hypervalent Iodine.

Alkox-oxylactonization and dearomatization of 3'-hydroxy-[1,1'-biphenyl]-2-carboxylic acid simultaneously promoted by hypervalent iodine have been developed using stoichiometric PhI(OAc)2 or a catalytic amount of chiral aryl-λ3-iodane generated in situ. This reaction provides a concise method to synthesize diverse polycyclic cyclohexadienones as potential inhibitors of DNA polymerase under mild reaction conditions.

Copper-Catalyzed Oxidative Difunctionalization of Terminal Unactivated Alkenes.

The copper(II)-promoted free-radical oxidative difunctionalization of terminal alkenes to access ketoazides by utilizing molecular oxygen has been reported. A series of styrene derivatives have been evaluated and were found to be compatible to give the desired difunctionalized products in moderate to good yields. The role of molecular oxygen both as an oxidant and oxygen atom source in this catalytic transformation has been unquestionably demonstrated by 18O-labeling studies and a radical mechanistic pathway involving the oxidative formation of azidyl radicals is also designed. This environment-friendly catalytic oxidative protocol can transform aldehyde to nitrile.

Iron-catalysed sequential reaction towards α-aminonitriles from secondary amines, primary alcohols and trimethylsilyl cyanide.

We have developed a one-pot iron-catalysed sequential reaction of secondary amines with primary alcohols, trimethylsilyl cyanide and TBHP under mild reaction conditions to give the corresponding α-aminonitriles.