# Photoredox Catalysis Applications in Organometallics and Chemical Biology

> **NIH NIH R35** · PRINCETON UNIVERSITY · 2021 · $918,859

## Abstract

Abstract. A central goal of our research program is to develop new platforms for the late-stage
functionalization of small molecules and biomolecules such as proteins. In recent years, these efforts have
focused on the application of photoredox catalysis as a uniquely enabling paradigm in synthetic chemistry.
The distinct features of photocatalysts, in particular their ability to readily effect single-electron transfers
and thereby generate reactive open-shell radical species, have created new opportunities for reaction
development, providing highly enabling, novel bond disconnections in synthetic sequences. An area in
which the application of photoredox catalysis has been notably successful is metallaphotoredox catalysis,
the combination of photocatalysis with transition-metal catalysis. Metallaphotoredox platforms facilitate
entry into reaction platforms that enable non-traditional partners to participate in cross-coupling chemistry.
Accordingly, efforts by our group and others have addressed many long-standing synthetic challenges. This
research proposal outlines new fields in which photoredox protocols have the potential to achieve
significant impact. The objective of Research Program I is to develop new photoredox-mediated
methodologies that will enable the selective bioconjugation of tyrosine and methionine residues in native
proteins for application in drug delivery and bioimaging. In Research Program II, we propose to harness
the ability of photoredox catalysis to reversibly cleave and form C–H bonds. This strategy will facilitate
hydrogen isotope exchange and will enable dynamic control of C–H stereochemistry for application in
uphill isomerizations and dynamic kinetic resolutions. Finally, Research Program III aims to explore
novel directions in metallaphotoredox catalysis, such as harnessing photoredox activation modes to
circumvent challenging elementary steps in copper and cobalt catalysis, as well as to expand the utility and
scope of nickel/photoredox dual catalysis.

## Key facts

- **NIH application ID:** 10077569
- **Project number:** 5R35GM134897-02
- **Recipient organization:** PRINCETON UNIVERSITY
- **Principal Investigator:** David W MacMillan
- **Activity code:** R35 (R01, R21, SBIR, etc.)
- **Funding institute:** NIH
- **Fiscal year:** 2021
- **Award amount:** $918,859
- **Award type:** 5
- **Project period:** 2020-01-01 → 2024-12-31

## Primary source

NIH RePORTER: https://reporter.nih.gov/project-details/10077569

## Citation

> US National Institutes of Health, RePORTER application 10077569, Photoredox Catalysis Applications in Organometallics and Chemical Biology (5R35GM134897-02). Retrieved via AI Analytics 2026-05-24 from https://api.ai-analytics.org/grant/nih/10077569. Licensed CC0.

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