Justin W. Chan

Sequential phosphine-catalyzed, nucleophilic thiol-ene/radical-mediated thiol-yne reactions and the facile orthogonal synthesis of polyfunctional materials.

The first example of highly efficient sequential thiol-ene/thiol-yne reactions conducted in an orthogonal manner is presented and its broad application in the synthesis of polyfunctional materials demonstrated. The anionic chain mechanism of the phosphine-mediated thiol-ene reaction is highlighted, as is the radical-mediated thiol-yne reaction. Kinetic data for a model reaction are presented, followed by a discussion of the synthesis of a range of materials with diverse functionality, including an example of potential biomedical significance.

Convergent synthesis of 3-arm star polymers from RAFT-prepared poly(N,N-diethylacrylamide) via a thiol–ene click reaction

A novel convergent route to 3-arm star polymers is described that takes advantage of RAFT-synthesized homopolymers serving as masked macromolecular terminal thiol-containing materials capable of undergoing thiol-ene click reactions.

Thiol–yne ‘click’ chemistry as a route to functional lipid mimetics

Thiol–alkyne ‘click’ chemistry is a modular, efficient mechanism to synthesize complex A2B 3-arm star polymers. This general motif is similar to a phospholipid where the A blocks correspond to lypophilic chains and the B block represents the polar head group. In this communication we employ thiol–yne chemistry to produce polypeptide-based A2B lipid mimetics. The utility of the thiol–yne reaction is demonstrated by using a divergent and a convergent approach in the synthesis. These polymers self-assemble in aqueous solution into spherical vesicles with a relatively narrow size distribution independent of block composition over the range studied. Using the thiol–yne convergent synthesis, we envision a modular approach to functionalize proteins or oligopeptides with lipophilic chains that can imbed seamlessly into a cell membrane.

Facile polyisobutylene functionalization via thiol–ene click chemistry

Thiol–ene click chemistry was adapted to easily and rapidly modify exo-olefin polyisobutylene with an array of thiol compounds bearing useful functionalities, including primary halogen, primary amine, primary hydroxyl, and carboxylic acid.