Jordan V

An efficient, visible-light-induced diastereoselective [2π+2σ] photocycloaddition between chalcones and 1,3-disubstituted BCBs was achieved through photoactive metal–organic cage (PMOC)confined catalysis. This strategy provides a highly atom economical and diastereoselective route to pharmaceutically relevant BCH bioisosteres, leveraging the unique spatial constraints of the supramolecular cage to control reactivity and selectivity.

Abstract

We disclose a visible-light-induced, diastereoselective [2π+2σ] photocycloaddition between readily available chalcones and 1,3-disubstituted bicyclo[1.1.0]butanes (BCBs) promoted by photoactive metal–organic cage (PMOC). This confined supramolecular catalysis method enables efficient synthesis of pharmaceutically relevant bicyclo[2.1.1]hexane (BCH) bioisosteres with remarkable atom economy and excellent diastereoselectivities, necessitating only 0.1 mol% catalyst loading. The success of this organic transformation arises from the synergistic action of the PMOC as a nanoreactor to combine selective substrate preorganization through host–guest interactions, efficient Ru(II)-mediated triplet energy transfer, and nano-spatial confinement effect that precisely control [2π+2σ] cyclization geometry while preventing competitive homodimerization.