Ye Zidan, Liu Wei, Gu Huanchao, Yang Xiaoyu
School of Physical Science and Technology, ShanghaiTech University, Shanghai 201210, China.
Org Lett. 2023 Aug 11;25(31):5838-5843. doi: 10.1021/acs.orglett.3c02100. Epub 2023 Jul 31.
Highly efficient and stereoselective dearomatization of substituted phenols was achieved via chiral phosphoric acid-catalyzed electrophilic -amination with commercially available azodicarboxylates. This protocol readily afforded a series of chiral 2,5-cyclohexadienones bearing 4-aza-quaternary stereocenters with excellent yields and enantioselectivities (≤99% yield and >99% ee). Easy scale-up of this reaction to a gram scale and diverse derivatizations of the chiral products into α-tertiary amines and α-tertiary heterocycles derivatives well demonstrated the potential of this method.
通过手性磷酸催化的亲电胺化反应，利用市售的偶氮二羧酸酯实现了取代酚的高效立体选择性去芳构化。该方法能够方便地得到一系列带有4-氮杂季碳中心的手性2,5-环己二烯酮，产率和对映选择性优异（产率≤99%，对映体过量值>99%）。该反应易于放大到克级规模，且手性产物能方便地衍生化为α-叔胺和α-叔杂环衍生物，充分展示了该方法的潜力。
