Ghosh Biki, Harariya Mahesh Singh, Mukherjee Santanu
Department of Organic Chemistry, Indian Institute of Science, Bangalore, 560 012, India.
Angew Chem Int Ed Engl. 2022 Sep 12;61(37):e202204523. doi: 10.1002/anie.202204523. Epub 2022 Aug 1.
Central chirality in arene derivatives arising out of unsymmetrically substituted arene ring is a fascinating yet rarely explored research topic. Here, we report a desymmetrization approach to centrally chiral unfunctionalized arenes, which is enabled by the enantioselective de novo construction of the arene ring. This operationally simple protocol is based on a [4+2]-cycloaddition between polycyclic meso-cyclohexenediones and α,β-unsaturated aldehydes, and doesn't usually require any external oxidant. Catalyzed by a diphenylprolinol silyl ether, this reaction proceeds via dienamine intermediate and greatly simplifies the access to diversely substituted chiral arenes with outstanding enantioselectivities.
由不对称取代的芳烃环产生的芳烃衍生物中的中心手性是一个引人入胜但很少被探索的研究课题。在此，我们报道了一种用于制备中心手性未官能化芳烃的去对称化方法，该方法通过芳烃环的对映选择性从头构建得以实现。这个操作简单的方案基于多环内消旋环己二烯酮与α,β-不饱和醛之间的[4+2]环加成反应，并且通常不需要任何外部氧化剂。在二苯基脯氨醇硅醚的催化下，该反应通过烯胺中间体进行，极大地简化了获得具有出色对映选择性的各种取代手性芳烃的途径。
