Enantioselective synthesis of axially chiral carbamates and amides with carbon dioxide via copper catalysis

Catalytic asymmetric conversion of carbon dioxide (CO2) into valuable chiral compounds is one of the most challenging research topics in the field of CO2 utilization. Although great progress has recently been made in the transformation of CO2 into centrally chiral compounds, the assembly of axially chiral molecules with CO2 has seldom been explored. Herein, we report a copper-catalyzed asymmetric ring opening reaction of cyclic diaryliodoniums with CO2 and amines, providing direct access to a range of axially chiral carbamates with high yields and enantioselectivities. Moreover, by using the strategy of merging the ring-opening reaction with a remote anionic Fries rearrangement, the synthesis of axially chiral amides was also achieved. The advantages of these methods include mild conditions, broad substrate scope and excellent enantioselectivity. Their synthetic applications were demonstrated by late stage modification of natural products and drug molecules as well as by the diverse transformations of the axially chiral products into various useful chiral biaryls.

Automated summary

This study reports a copper-catalyzed ring opening reaction of carbon dioxide (CO2) with amines, leading to the synthesis of a range of axially chiral carbamates. The method offers mild conditions, broad substrate scope, and excellent enantioselectivity. The synthetic applications of the method were demonstrated through the modification of natural products and drug molecules, as well as the diverse transformations of the axially chiral products.