Controlled radical polymerization techniques, such as atom transfer radical polymerization (ATRP), nitroxide mediated polymerization (NMP), and reversible addition fragmentation transfer polymerizations (RAFT) are powerful tools for preparing well define polymeric components. ATRP is a particularly attractive approach for making star precursors because of the ability to modify the terminal end group in very high yields.13 The synthesisof polymer �cages� can be achieved by further clicking these end functionalized star polymers with a small molecular caps containing a complementary number of arms with respect to the polymer.�Click� chemistry was selected for the coupling reaction because of its high efficiency and technical simplicity.14  Perhaps the most popular �click� reaction has been the copper catalyzed Huisgen dipolar cycloaddition of a terminal alkyne and an azide to form a 1,4-disubstituted 1,2,3-triazole.15  Its value has been particularly useful in polymer chemistry,16 where less efficient transformations often suffer from incomplete reactions because of the steric inaccessibility of reactive sites within the polymer structure.  Herein we report the first preparation of cage-like multicylic polymers via the �click� coupling of star polymers with the alkyne caps.

Multi-arm globes via "click" coupling

245th National Meeting (2013)

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