Our work is focused on developing chemical strategies for the synthesis of sequence-ordered copolymers with facilely tailorable properties derived from the repeat unit functionality and sequence. The ability of thiols to react with electron-deficient alkenes under basic conditions (thiol-Michael reaction) and electron-rich alkenes using a radical initiator (thiol-ene reaction) allows for thiols to be reacted selectively with certain enes. By sequentially using the thiol-Michael and thiol-ene reactions, sequence-defined oligomers can be readily synthesized and then polymerized to afford periodic sequence-ordered polymers with monomeric repeats consisting of common organic moieties or biochemical functionalities, e.g., nucleobases. Through the development of these chemical schemes we have furthered the understanding of the thiol-ene reaction, including: establishing that radical thiol-ene is hindered by basic functionalities due to the formation of disulfide radical anions <i>in situ</i>, greatly expanding the library of thiol and ene containing monomers and showing that heterofunctional thiol-ene monomers polymerize through a chain-growth mechanism when the monomer fulfills certain structural criteria, and that aromatic thiols can be triggered to react selectively by direct irradiation with UV-light in the absence of a photoinitiator.<br/>In combination with the thiol-Michael reaction, the aza-Micheal reaction of amines with electron-deficient enes allows for the combinatorial synthesis of multi-(short)block copolymers. Current work is focused on using an automated synthesizer to rapidly produce multi-block polymers with a diverse range of side-group functionalities and polymer architectures.

Development of sequence ordered/functional polymers with thiol-X and aza-Michael reactions

256th National Meeting (2018)

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