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

Authors: Cui-Ting Li, Li-Gao Liu, Jia-Zheng Li, Hao-Xuan Dong, Roman A. Novikov, Ze-Shu Wang*, Xin Hong*, Bo Zhou & Long-Wu Ye*

Abstract: 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.

Full-Link: https://www.nature.com/articles/s41467-025-59328-7