Productive Exchange of Thiols and Thioesters to Form Dynamic Polythioester-Based Polymers.

Polymers that possess dynamic covalent bonds activated at ambient conditions are ideal platforms for smart, responsive materials. Herein, a class of dynamic covalent polymerizations is developed based on the thiol-thioester exchange, that is, transthioesterification, reaction. Shifts in the equilibrium extent of the exchange reactions are deliberately utilized to drive the formation of oligomers and polymers.

Dynamic and Responsive DNA-like Polymers.

The synthesis of thiolactone monomers that mimic natural nucleosides and engage in robust ring opening polymerizations (ROP) is herein described. As each repeat unit contains a thioester functional group, dynamic rearrangement of the polymer is feasible via thiol-thioester exchange, demonstrated here by depolymerization of the polymers and coalescing of two polymers of different molecular weight or chemical composition. This approach constitutes the first step toward a platform that enables for the routine synthesis of sequence controlled polymers via dynamic template directed synthesis.