抄録
Our laboratory is interested in developing the effective oxygen nucleophiles directly connected with heteroatoms. Recently, we have been found that the oxygen atoms of oximes and hydroxylamines having an N-electron-withdrawing substituent act as reactive nucleophiles. The selective formation of the branched products was observed in the iridium-catalyzed allylic substitution. Based on these results, we investigated the enantioselective iridium-catalyzed O-allylic substitution with oxime. The iridium complex of pybox having phenyl group catalyzed the reaction with high activity to form the branched oxime ethers with good enantioselectivities. The stability of conjugate base of oximes was important for the nucleophilic property of an oxygen atom of oximes. Thus, the reaction of aldoxime containing an electron-withdrawing substituent proceeded smoothly.
