# Stereoselective Polymerization Methods for the Synthesis of Degradable Biomaterials

> **NIH NIH R35** · UNIV OF NORTH CAROLINA CHAPEL HILL · 2024 · $345,332

## Abstract

Project Summary / Abstract
The goal of research in the Leibfarth group is to develop platform synthetic methods that enhance the
thermomechanical, adhesion, and degradation properties of polymers while also uncovering mechanistic insights
that broadly inform synthetic method development. This goal informs our two complementary research areas
that seek to 1) leverage chemo- and regioselective C–H functionalization to enhance the properties of commodity
polymers and 2) develop stereoselective polymerization methods that uncover emergent polymer properties from
simple chemical building blocks. We have identified a compelling opportunity to make progress on a grand
challenge in biomedicine – the discovery of degradable biomaterials with concomitant control of
thermomechanical properties, degradation profile, and metabolic fate – by leveraging our expertise at the
interface of asymmetric catalysis, C–H functionalization, and polymer chemistry. In the five-year period of this
MIRA grant, we propose to develop new catalytic approaches to control the stereochemistry of degradable
polymers and establish a domain-selective approach to tune the material properties of polymers post-production.
These methods will provide access to heretofore unknown semicrystalline biomaterials where critical parameters
such as the chemical composition, polymer molar mass, and percent crystallinity can be systematically varied.
The novel polymer structures accessed as a result of this work and the comprehensive evaluation of their
degradation mechanism will enable the identification of design rules for the development of new classes surface
eroding biomaterials. More specifically, we aim to develop new catalytic methods for the stereoselective
polymerization of cyclic monomers through complementary kinetic resolution and enantioconvergent synthetic
approaches. We envision that the discovery of previously unprecedented stereodefined polymers can be
accomplished by developing a comprehensive understanding of structure–reactivity relationships that determine
stereoselective addition of monomers to a reactive polymer chain-end. Further elaboration of this stereoselective
polymerization philosophy will enable the pursuit of methods for stereoselective radical polymerization in a
controlled manner through chiral Lewis acid catalysis, thus providing a strategy to create highly functional and
stereodefined polymers from widely-available vinyl monomers. Complementary to the pursuit of stereoselective
polymerization, we have identified late-stage functionalization as an underutilized approach to diversify the
properties of existing polymers relevant to biomedicine without resorting to de novo synthesis. This philosophy
can be used on current materials in medical devices as well as further expand the utility of the new, stereodefined
polymers we discover in the course of our research program. By developing methods to conduct domain-
selective C–H functionalization reactions, we propose ...

## Key facts

- **NIH application ID:** 10834200
- **Project number:** 5R35GM142666-04
- **Recipient organization:** UNIV OF NORTH CAROLINA CHAPEL HILL
- **Principal Investigator:** Frank Albert Leibfarth
- **Activity code:** R35 (R01, R21, SBIR, etc.)
- **Funding institute:** NIH
- **Fiscal year:** 2024
- **Award amount:** $345,332
- **Award type:** 5
- **Project period:** 2021-07-01 → 2026-04-30

## Primary source

NIH RePORTER: https://reporter.nih.gov/project-details/10834200

## Citation

> US National Institutes of Health, RePORTER application 10834200, Stereoselective Polymerization Methods for the Synthesis of Degradable Biomaterials (5R35GM142666-04). Retrieved via AI Analytics 2026-05-24 from https://api.ai-analytics.org/grant/nih/10834200. Licensed CC0.

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