Sequence-defined l-glutamamide oligomers with pendant supramolecular motifs: Via iterative synthesis and orthogonal post-functionalization

Marcin L. Ślȩczkowski, Ian Segers, Yiliu Liu (Corresponding author), Anja R.A. Palmans (Corresponding author)

Research output: Contribution to journalArticleAcademicpeer-review

Abstract

One of the great challenges in polymer chemistry is to achieve discrete and sequence-defined synthetic polymers that fold in defined conformations and form well-defined three-dimensional structures. Here, we present our progress to arrive at functional, sequence-defined and discrete oligomers by selecting a synthetic approach based on oligo-l-glutamamides. We introduce a solution-based iterative approach and start with an orthogonally protected l-glutamic acid derivative with an alkene or alkyne side chain. Using subsequent deprotection, activation and coupling steps, discrete, sequence-defined octamers were prepared with alkene or alkyne pendants at defined positions. Benzene-1,3,5-Tricarboxamide (BTA) was selected as the supramolecular motif and decyl side chains for enhancing solubility. Full functionalization of the octamer was achieved with subsequent Cu(i)-catalyzed alkyne-Azide and thiol-ene "click"chemistry, affording octamers with two BTA motifs at pre-defined positions. The octamers show a strong propensity to form hydrogen bonds in bulk as evidenced by infrared spectroscopy. In dilute solution, intermolecular aggregation of the amides present in the backbone and/or BTAs is observed. Our work shows that the iterative method serves as an reliable strategy for the synthesis of functionalized sequence-defined, discrete oligomers comprising side chain supramolecular motifs, although further optimizations are required.

Original languageEnglish
Pages (from-to)7393-7401
Number of pages9
JournalPolymer Chemistry
Volume11
Issue number46
DOIs
Publication statusPublished - 14 Dec 2020

Fingerprint Dive into the research topics of 'Sequence-defined l-glutamamide oligomers with pendant supramolecular motifs: Via iterative synthesis and orthogonal post-functionalization'. Together they form a unique fingerprint.

Cite this