Nature Communications ( IF 14.7 ) Pub Date : 2024-05-30 , DOI: 10.1038/s41467-024-48858-1 Shuang-Hu Wang 1 , Shi-Qiang Wei 1 , Ye Zhang 1 , Xiao-Ming Zhang 2 , Shu-Yu Zhang 1 , Kun-Long Dai 1 , Yong-Qiang Tu 1, 2 , Ka Lu 2 , Tong-Mei Ding 1
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).
中文翻译:
通过Co/SPDO催化的酚类有氧氧化偶联/去对称化选择性合成双轴桥八元三联苯
桥联手性联芳基是轴向手性化合物,具有连接两个芳烃的中等大小的环。与对映选择性合成联芳基化合物的丰富方法相比,此类桥联阻转异构体的合成方法是有限的。在这里,我们展示了通过Co/SPDO(螺环吡咯烷恶唑啉)催化的前手性酚的有氧氧化偶联/去对称反应,1,3-二轴桥联的八元三联苯阻转异构体的阻转选择性合成。这种催化不对称过程是通过在 DABCO(1,4-二氮杂[2.2.2]双环辛烷)存在下将地球上丰富的 Co(OAc) 2和独特的 SPDO 配体结合实现的。可以高产率(高达 99%)获得嵌入偶氮烷中的一系列双轴桥联三联苯,并具有优异的对映选择性(>99% ee)和非对映选择性(>20:1 dr)。