# Enabling Triplet-Energy Transfer via NHC Catalysis

> **NIH NIH F32** · UNIVERSITY OF WISCONSIN-MADISON · 2021 · $66,390

## Abstract

PROJECT SUMMARY:
 Stereoselective synthesis is critical for the assessment of drug candidates. Over the last century, the
community understanding of stereocontrol of thermal reactions has matured significantly. By contrast, strategies
for controlling the stereochemistry of photochemical transformations remain underdeveloped, despite the
growing importance of synthetic organic photochemistry. Integral to overcoming this limitation is a deeper
understanding of photoactivation mechanisms and how the photophysical properties of organic molecules and
catalysts can be harnessed to promote enantioselective pathways.
 This proposal outlines a means by which photoexcitation of inexpensive alkenes can be accomplished with
a carbene catalyst, photosensitizer, and visible light. This will allow chemical feedstocks to be directly engaged
in enantioselective photocycloadditions to generate cyclobutanes containing medicinally relevant functional
groups. In the first of two Specific Aims, the concept of this proposal will be developed through an assessment
of the mechanism and of the physical properties of the key reactive intermediate and the features that enable
photoexcitation. These fundamental studies will lay the groundwork to advance asymmetric catalysis of the
cycloaddition reactions. Upon establishment of the viability of the approach, scope and limitations will be defined.
In the second Specific Aim, a first-principles design of new catalysts will be performed to elicit reactivity from
previously inert classes of alkyl-substituted substrates. The fruition of this proposal will directly benefit the drug
discovery process by establishing a powerful new tool to construct biologically active molecules in new areas of
chemical space and a basis to assess the factors that drive selectivity in a new mode of photocatalysis.

## Key facts

- **NIH application ID:** 10223805
- **Project number:** 1F32GM139373-01A1
- **Recipient organization:** UNIVERSITY OF WISCONSIN-MADISON
- **Principal Investigator:** Samuel N Gockel
- **Activity code:** F32 (R01, R21, SBIR, etc.)
- **Funding institute:** NIH
- **Fiscal year:** 2021
- **Award amount:** $66,390
- **Award type:** 1
- **Project period:** 2021-05-15 → 2023-05-14

## Primary source

NIH RePORTER: https://reporter.nih.gov/project-details/10223805

## Citation

> US National Institutes of Health, RePORTER application 10223805, Enabling Triplet-Energy Transfer via NHC Catalysis (1F32GM139373-01A1). Retrieved via AI Analytics 2026-05-24 from https://api.ai-analytics.org/grant/nih/10223805. Licensed CC0.

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