Iterative exponential growth of stereo- and sequence-controlled polymers

• Published in: Nature chemistry Vol. 7; no. 10; pp. 810 - 815
• Main Authors: Barnes, Jonathan C, Ehrlich, Deborah J C, Gao, Angela X, Leibfarth, Frank A, Jiang, Yivan, Zhou, Erica, Jamison, Timothy F, Johnson, Jeremiah A
• Format: Journal Article
• Language: English
• Published: England Nature Publishing Group 01.10.2015
• Subjects: Biopolymers; Polymers; Polymers - chemistry; Proton Magnetic Resonance Spectroscopy; Spectrometry, Mass, Matrix-Assisted Laser Desorption-Ionization
• ISSN: 1755-4330; 1755-4349
• DOI: 10.1038/nchem.2346

Chemists have long sought sequence-controlled synthetic polymers that mimic nature's biopolymers, but a practical synthetic route that enables absolute control over polymer sequence and structure remains a key challenge. Here, we report an iterative exponential growth plus side-chain functionalization (IEG+) strategy that begins with enantiopure epoxides and facilitates the efficient synthesis of a family of uniform >3 kDa macromolecules of varying sequence and stereoconfiguration that are coupled to produce unimolecular polymers (>6 kDa) with sequences and structures that cannot be obtained using traditional polymerization techniques. Selective side-chain deprotection of three hexadecamers is also demonstrated, which imbues each compound with the ability to dissolve in water. We anticipate that these new macromolecules and the general IEG+ strategy will find broad application as a versatile platform for the scalable synthesis of sequence-controlled polymers.