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使用铜(II)催化剂活化N-磺酰基恶唑烷:苯乙烯和1,3-二烯的氨基羟基化反应

Activation of N-sulfonyl oxaziridines using copper(II) catalysts: aminohydroxylations of styrenes and 1,3-dienes.

作者信息

Michaelis David J, Ischay Michael A, Yoon Tehshik P

机构信息

Department of Chemistry, University of Wisconsin-Madison, 1101 University Avenue, Madison, Wisconsin 53706, USA.

出版信息

J Am Chem Soc. 2008 May 21;130(20):6610-5. doi: 10.1021/ja800495r. Epub 2008 Apr 22.

Abstract

N-Sulfonyl oxaziridines are susceptible to electrophilic activation using copper(II) catalysts and react with styrenes under these conditions to provide 1,3-oxazolidines in a formal aminohydroxylation of the alkene. We propose a two-step mechanism involving a cationic intermediate to account for the rate differences and regioselectivities observed using a variety of styrenes. In accord with our hypothesis, aminohydroxylations of a range of substrates bearing electron-stabilizing groups are successful, and 1,3-dienes are particularly good substrates for copper(II)-catalyzed aminohydroxylation. Reactions of unsymmetrical dienes provide good to excellent olefin selectivity, the sense and magnitude of which can be rationalized upon consideration of the stability of the cationic intermediates suggested by our mechanism. Diastereoselective synthesis of a diverse range of densely functionalized structures can be achieved by polyfunctionalization of dienes using aminohydroxylation as a key complexity-increasing step.

摘要

N-磺酰基恶唑烷可通过铜(II)催化剂进行亲电活化,并在这些条件下与苯乙烯反应,在烯烃的形式氨基羟基化反应中生成1,3-恶唑烷。我们提出了一种涉及阳离子中间体的两步机理,以解释使用各种苯乙烯时观察到的速率差异和区域选择性。根据我们的假设,一系列带有电子稳定基团的底物的氨基羟基化反应是成功的,并且1,3-二烯烃是铜(II)催化氨基羟基化反应的特别好的底物。不对称二烯烃的反应提供了良好到优异的烯烃选择性,考虑到我们机理中提出的阳离子中间体的稳定性,可以合理地解释其方向和大小。通过使用氨基羟基化作为关键的增加复杂性步骤对二烯烃进行多官能化,可以实现各种密集官能化结构的非对映选择性合成。

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