Asymmetric [3+2] photocycloadditions of cyclopropylamines with electron-rich and electron-neutral olefins

Radical addition to olefins is a common and useful chemical transformation. In the context of offering enantioenriched three-dimensional molecules via such a highly reactive process, chiral hydrogen-bonding (H-bonding) catalysis has been widely used to provide enantiocontrol. The current strategies for operating H-bonding induction are confined to following that are prevalent in ionic-type manifolds. Here, we report a novel protocol towards electron-rich olefins based on converting these species from acting as H-bonding donors to acceptors. It facilitates the first development of asymmetric [3 + 2] photocycloadditions with cyclopropylamines. The method is also effective for electron-neutral olefins, in which the successful construction of all-carbon quaternary stereocentres from 1,1-diaryl ethylenes that feature two structurally similar aryl substituents demonstrates the versatility of this new chiral H-bonding catalytic strategy. Furthermore, the importance of the obtained six kinds of products in pharmaceuticals and asymmetric catalysis underscores the practicability of this work.

Automated summary

This article presents a novel protocol based on chiral hydrogen-bonding catalytic strategy for converting electron-rich olefins to acceptors, and successfully carries out asymmetric photocycloadditions. The method is effective for electron-neutral olefins and allows the construction of all-carbon quaternary stereocentres with structurally similar aryl substituents.