Light-Driven Intermolecular Charge Transfer Induced Reactivity of Ethynylbenziodoxol(on)e and Phenols.

ABSTRACT

Ethynylbenziodoxol(on)es (EBXs) have been widely used in organic synthesis as electrophilic alkyne-transfer reagents involving carbon- and heteroatom-based nucleophiles. However, potential reactions of EBXs with phenols remain uninvestigated. Here, we present the formation of ( Z)-2-iodovinyl phenyl ethers with excellent regio- and stereoselectivity through the reactivity between EBXs and phenols driven by visible light. We propose that this light-activated transformation proceeds through electron donor-acceptor complexes to enable new reactivity beyond existing mechanisms for alkynylation of carbon- and heteroatom-based nucleophiles. This operationally robust process was employed for the synthesis of diverse ( Z)-2-iodovinyl phenyl ethers through irradiating a solution containing a phenyl-EBX, a phenol, and the base Cs2CO3 with a commercially available blue LED at room temperature. The ( Z)-2-iodovinyl phenyl ether products can be further stereospecifically functionalized to form trisubstituted alkenes, demonstrating the potential of these products en route to chemical complexity.