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

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.