One-Step Construction of Atropisomers Bearing 1,5-Central and Axial Chirality via Catalytic Diastereo- and Atroposelective Remote Desymmetrizing Alkynylation

作者：Shan Wang, Long Li, Ming Jiang, Kaixin Zhao, Daming He, Xiaoguang Li, Zheng Wang, Yingcheng Wang, Fangzhi Peng, Zhihui Shao · 发表于：ACS Catalysis · 年份：2024 · DOI：10.1021/acscatal.4c06332 · 被引用次数：7 · 研究领域：Axial and Atropisomeric Chirality Synthesis、Synthesis of Indole Derivatives、Molecular spectroscopy and chirality

Catalytic asymmetric construction of atropisomers with multiple stereogenic elements has recently become an emerging area. However, general methods that produced atropisomers bearing remote 1,5-axial and central chirality efficiently and stereoselectively are scarce yet highly challenging. We herein report a catalytic diastereo- and atroposelective remote desymmetrizing alkynylation of axially prochiral dialkynes with ortho -quinone methides ( o -QMs), furnishing atropisomers bearing 1,5-remote centrally and axially stereogenic elements. The remote control of prochiral axis far from the reaction site could be simultaneously achieved during the stereoselective C(sp 3 )–C(sp) bond-forming process to generate a stereogenic center. In addition, a kinetic resolution of axially racemic alkynes via diastereo- and atroposelective remote alkynylation with o -QMs has been developed, further enriching structural diversity of atropisomers bearing 1,5-central and axial chirality. The present method expands the chemical space of atropisomeric molecules bearing multiple chiral elements by facile downstream diversification of C–C triple bonds. Finally, the alkynylation of o -QMs can also be applied for the construction of chiral motifs bearing 1,9- and 1,10-stereogenic centers.