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

• Published in: Nature communications Vol. 16; no. 1; pp. 4107 - 12
• Main Authors: Li, Cui-Ting, Liu, Li-Gao, Li, Jia-Zheng, Dong, Hao-Xuan, Novikov, Roman A., Wang, Ze-Shu, Hong, Xin, Zhou, Bo, Ye, Long-Wu
• Format: Journal Article
• Language: English
• Published: London Nature Publishing Group UK 02.05.2025; Nature Publishing Group; Nature Portfolio
• Subjects: 140/131; 140/58; 639/638/403/933; 639/638/403/934; Acetals; Asymmetry; Cations; Chemical synthesis; Divergence; Enantiomers; Humanities and Social Sciences; Hydrogen bonds; Insertion; Ligands; multidisciplinary; Precursors; Pyrroles; Science; Science (multidisciplinary)
• ISSN: 2041-1723; 2041-1723
• DOI: 10.1038/s41467-025-59328-7

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(sp 3 )−H insertion and formal C(sp 3 )−O insertion products from the same precursors are rarely explored. Herein, we report a ligand-controlled divergent asymmetric C(sp 3 )−H insertion and formal C(sp 3 )−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.