Anionic Halocuprate(II) Complexes as Catalysts for the Oxaziridine-Mediated Aminohydroxylation of Olefins

被引:68
作者
Benkovics, Tamas [1 ]
Du, Juana [1 ]
Guzei, Ilia A. [1 ]
Yoon, Tehshik P. [1 ]
机构
[1] Univ Wisconsin, Dept Chem, Madison, WI 53706 USA
关键词
CROSS-COUPLING REACTIONS; CYCLOPROPYLCARBINYL-CYCLOPROPYLCARBINYL; ORGANIC-COMPOUNDS; STEREOCHEMISTRY; REARRANGEMENTS; DERIVATIVES; TRANSITION; HALIDES; OXIDATION; REAGENTS;
D O I
10.1021/jo900902k
中图分类号
O62 [有机化学];
学科分类号
070303 ; 081704 ;
摘要
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.
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页码:5545 / 5552
页数:8
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