Institute of Microbial Chemistry (BIKAKEN), 3-14-23 Kamiosaki, Shinagawa-ku, Tokyo 141-0021, Japan.
Org Lett. 2021 Nov 5;23(21):8617-8621. doi: 10.1021/acs.orglett.1c03328. Epub 2021 Oct 23.
Catalytic asymmetric nitrene transfer has emerged as a reliable method for the synthesis of nitrogen-containing chiral compounds. Herein, we report the copper-catalyzed intramolecular asymmetric electrophilic amination of aromatic rings. The reactive intermediate is a copper-alkyl nitrene generated from isoxazolidin-5-ones. Copper catalysis promotes three classes of asymmetric transformations, namely, asymmetric desymmetrization, parallel kinetic resolution, and kinetic resolution, expanding the repertoire of alkyl nitrene transfer and providing various cyclic and linear β-amino acids in their enantioenriched forms.
手性氮宾转移催化已成为合成含氮手性化合物的可靠方法。在此，我们报告了铜催化的芳香环分子内不对称亲电胺化反应。反应中间体是由异噁唑烷-5-酮生成的铜-烷基氮宾。铜催化促进了三类不对称转化，即不对称去对称化、平行动力学拆分和动力学拆分，扩展了烷基氮宾转移的范围，以手性富集的形式提供了各种环状和线性β-氨基酸。
