Single and dual glycoside clustering around calix[4]arene scaffolds via click thiol–ene coupling and azide–alkyne cycloaddition

We present the first synthesis of calix[4]arene-based S-glycoclusters via photoinduced multiple thiol–ene coupling of tetra- and octa-allyl calix[4]arenes with peracetylated glucosyl thiol (67–88% yields). Moreover we describe the dual clustering at the upper and lower rim of a calix[4]arene with two different sugars (galactose and glucose) via sequential copper(I)-catalyzed azide–alkyne cycloaddition and photoinduced thiol–ene coupling