Enantioselective transition metal-catalyzed allylic

tions have been developed as fundamentally important crosscoupling reactions. In general, the heteroatom nucleophiles in these reactions have been largely limited to alkylamines, anilines, carboxylates and phenols. Our laboratory is interested in searching the synthetically useful heteroatom nucleophiles for the synthesis of functionalized allylic compounds (Fig. 1). As our successful examples, we have recently reported the utility of oximes 1 and guanidines 5 and 6 as nucleophiles in the transition metal-catalyzed allylic substitution. Hydroxylamines are also attractive synthetic reagents for allylic substitution, since they have nitrogen and oxygen atoms as nucleophiles. However, the allylic substitution with hydroxylamines has not been studied well and is limited to a simple palladium-catalyzed amination; thus, there are no reports on asymmetric reactions. We have recently reported that hydroxylamines 2 and 3 having an N-electron-withdrawing substituent, also known as hydroxamic acids, act as reactive oxygen nucleophiles in the enantioselective allylic substitution (Fig. 1). As a part of our program directed toward searching the synthetically useful heteroatom nucleophiles, we describe in detail the study of hydroxylamines 4 as nitrogen nucleophiles in the regioand enantioselective iridium-catalyzed allylic substitutions. In this study, we also expected that comparison with alkylamines, p-anisidine, and 4-methoxyphenol would lead to informative suggestions regarding the asymmetric reaction using the iridium complex of pybox (bis(oxazolinyl)pyridine) ligand.