Supramolecular catalysis with ethers enabled by dual chalcogen bonding activation

The activation of ethers by weak interactions is a long-standing objective in supramolecular catalysis, but yet it remains an underdeveloped topic. The obstacles towards solving this problem are prominent since it is difficult for a weak interaction to cleave a relatively strong C-O sigma-bond and moreover, the ionic intermediate composing of an alkoxide ion and an electrophilic carbocation would deactivate weak interaction donors. Herein, we describe a distinctive activation mode, dual Se center dot center dot center dot pi and Se center dot center dot center dot O bonding, that could activate benzylic as well as allylic ether C-O sigma-bonds to achieve cyclization, coupling and elimination reactions. This dual Se center dot center dot center dot pi and Se center dot center dot center dot O bonding catalysis approach could tolerate various alkoxide leaving groups, while the other representative weak interaction donors showed no catalytic activity. The activation of ethers by weak interactions in supramolecular catalysis remains challenging. Here, the authors describe an activation mode based on dual Se center dot center dot center dot pi and Se center dot center dot center dot O bonding, that can activate benzylic as well as allylic ether C-O sigma-bonds to achieve cyclization, coupling and elimination reactions.

Automated summary

The activation of ethers by weak interactions in supramolecular catalysis remains challenging. In this study, the authors describe an activation mode based on dual Se···π and Se···O bonding, that can activate benzylic as well as allylic ether C-O σ-bonds to achieve cyclization, coupling and elimination reactions.