The precise and efficient construction of axially chiral scaffolds, particularly toward the aryl-alkene atropoisomers with impeccably full enantiocontrol and highly structural diversity, remains greatly challenging. Herein, we disclose an organocatalytic asymmetric nucleophilic aromatic substitution (S_NAr) reaction of aldehyde-substituted styrenes involving a dynamic kinetic resolution process via a hemiacetal intermediate, offering a novel and facile way to significant axial styrene scaffolds. Upon treatment of the aldehyde-containing styrenes bearing (o-hydroxyl)aryl unit with commonly available fluoroarenes in the presence of chiral peptide-phosphonium salts, the S_NAr reaction via an exquisite bridged biaryl lactol intermediate undergoes smoothly to furnish a series of axially chiral aldehyde-containing styrenes decorated with various functionalities and bioactive fragments in high stereoselectivities (up to >99% ee) and complete E/Z selectivities. These resulting structural motifs are important building blocks for the preparation of diverse functionalized axial styrenes, which have great potential as efficient and privileged chiral ligands/catalysts in asymmetric synthesis.

精确有效地构建轴向手性支架，特别是对于具有无可挑剔的完全对映体控制和高度结构多样性的芳基烯烃阻转异构体，仍然具有很大的挑战性。在此，我们公开了醛取代苯乙烯的有机催化不对称亲核芳香取代（SN _Ar）反应，涉及通过半缩醛中间体的动态动力学拆分过程，为重要的轴向苯乙烯支架提供了一种新颖且简便的方法。在手性肽-鏻盐存在下，用常用的氟代芳烃处理带有（邻羟基）芳基单元的含醛苯乙烯后，通过精致的桥联联芳基乳醇中间体发生 S _N Ar 反应，顺利进行，提供一系列轴向手性含醛苯乙烯，装饰有各种功能和生物活性片段，具有高立体选择性（高达 >99% ee）和完整的E / Z选择性。这些所得的结构基序是制备多种官能化轴向苯乙烯的重要组成部分，它们在不对称合成中作为高效且独特的手性配体/催化剂具有巨大的潜力。