Anionic Halocuprate(II) Complexes as Catalysts for the Oxaziridine-Mediated Aminohydroxylation of Olefins
Tamas Benkovics
Juana Du
Ilia A. Guzei
Tehshik P. Yoon
10.1021/jo900902k.s003
https://acs.figshare.com/articles/dataset/Anionic_Halocuprate_II_Complexes_as_Catalysts_for_the_Oxaziridine_Mediated_Aminohydroxylation_of_Olefins/2837332
We have discovered that the oxaziridine-mediated copper-catalyzed aminohydroxylation reaction recently discovered in our laboratories is dramatically accelerated in the presence of halide additives. The use of this more active catalyst system enables the efficient aminohydroxylation of electronically and sterically deactivated styrenes and also enables the use of nonstereogenic 3,3-dialkyl oxaziridines as terminal oxidants in the aminohydroxylation reaction. We present evidence that anionic halocuprate(II) complexes are the catalytically active species responsible for the increased reactivity under these conditions. This unexpected observation has led us to re-evaluate our mechanistic understanding of this reaction. On the basis of the results of a variety of radical trapping experiments, we propose a modified mechanism that involves a homolytic reaction of the olefin with a copper(II)-activated oxaziridine. Together, the observation that anionic additives significantly increase the oxidizing ability of oxaziridines and the recognition of the radical nature of reactions of oxaziridines under these conditions suggest that a variety of new oxidative transformations catalyzed by halocuprate(II) complexes should be possible.
2009-08-07 00:00:00
oxaziridine
halide additives
variety
complex
oxidative transformations
aminohydroxylation reaction
homolytic reaction
terminal oxidants
oxidizing ability
halocuprate
catalyst system