CHAPTER 6: Thiol‐ene/yne Chemistry for the Synthesis of Branched and Star‐shaped Macromolecules

The advances and discoveries that have been made in the synthesis of dendrimers and other hyper‐branched materials by employing the anionic thiol‐ene or thiol‐Michael reaction, as well as the free‐radical thiol‐ene and thiol‐yne reactions, are discussed. The characterization methods and potential applications of the resulting materials are also mentioned. The initial examples presented involve using the thiol‐Michael reaction for the convergent synthesis of star polymers, divergent synthesis of dendritic molecules, and dendronizing linear polymers. The free‐radical thiol‐ene and free‐ radical thiol‐yne reactions are discussed next, specifically using these “click” reactions for the divergent synthesis of dendritic molecules and for the syntheses of hyperbranched polymers. Finally, examples of using the thiol‐Michael reaction and the free‐radical thiol‐yne reactions in sequence for the preparation of hyper‐branched materials are conveyed.