Ligand-controlled divergent asymmetric C(sp3)−H and C(sp3)−O insertion via vinyl cations

作者：Cui‐Ting Li, Li‐Gao Liu, Jia-Zheng Li, Haoxuan Dong, Роман А. Новиков, Ze‐Shu Wang, Xin Hong, Bo Zhou, Long‐Wu Ye · 发表于：Nature Communications · 年份：2025 · DOI：10.1038/s41467-025-59328-7 · 被引用次数：10 · 研究领域：Cyclopropane Reaction Mechanisms、Catalytic C–H Functionalization Methods、Asymmetric Hydrogenation and Catalysis

The insertion of either C−H bond or C−O bond via bond cleavage has proven to be a very attractive strategy for the construction of C−C and C−O bonds in organic synthesis. However, such divergent catalytic asymmetric reactions for the selective formation of C(sp3)−H insertion and formal C(sp3)−O insertion products from the same precursors are rarely explored. Herein, we report a ligand-controlled divergent asymmetric C(sp3)−H insertion and formal C(sp3)−O insertion reaction via vinyl cations by a non-diazo approach, leading to the practical and atom-economical assembly of a range of chiral spiro and fused polycyclic pyrroles in generally moderate to excellent yields with generally excellent chemo- and enantioselectivities. Importantly, this protocol not only represents a rare example of successful ligand-controlled asymmetric divergent insertion reaction, but also constitutes an enantioselective 1,6-C−H insertion and an asymmetric carbenoid insertion into acetals via a non-diazo approach. Divergent catalytic asymmetric reactions for the selective formation of C(sp3)−H insertion and formal C(sp3)−O insertion products from the same precursors are rarely explored. Here, the authors report a ligand-controlled divergent asymmetric C(sp3)–H insertion and formal C(sp3)–O insertion reaction via vinyl cations, leading to the assembly of a range of chiral spiro and fused polycyclic pyrroles.