Atroposelective synthesis of biaxial bridged eight-membered terphenyls via a Co/SPDO-catalyzed aerobic oxidative coupling/desymmetrization of phenols

作者：Shuanghu Wang, Shiqiang Wei, Ye Zhang, Xiao‐Ming Zhang, Shu‐Yu Zhang, Kun‐Long Dai, Yong‐Qiang Tu, Ka Lu, Tong‐Mei Ding · 发表于：Nature Communications · 年份：2024 · DOI：10.1038/s41467-024-48858-1 · 被引用次数：22 · 研究领域：Axial and Atropisomeric Chirality Synthesis、Molecular spectroscopy and chirality、Plant and Fungal Species Descriptions

Abstract Bridged chiral biaryls are axially chiral compounds with a medium-sized ring connecting the two arenes. Compared with plentiful methods for the enantioselective synthesis of biaryl compounds, synthetic approaches for this subclass of bridged atropisomers are limited. Here we show an atroposelective synthesis of 1,3-diaxial bridged eight-membered terphenyl atropisomers through an Co/SPDO (spirocyclic pyrrolidine oxazoline)-catalyzed aerobic oxidative coupling/desymmetrization reaction of prochiral phenols. This catalytic desymmetric process is enabled by combination of an earth-abundant Co(OAc) 2 and a unique SPDO ligand in the presence of DABCO (1,4-diaza[2.2.2]bicyclooctane). An array of diaxial bridged terphenyls embedded in an azocane can be accessed in high yields (up to 99%) with excellent enantio- (>99% ee) and diastereoselectivities (>20:1 dr).