# Photocatalyzed and Enantioselective Umpolung C-C Bond Forming Reactions of Carbonyls

> **NIH NIH R15** · OCCIDENTAL COLLEGE · 2020 · $280,280

## Abstract

Project Summary
 New methods for the formation of carbon-carbon bonds are always at the forefront of organic reaction
development. Of particular interest are those that require benign reagents, are atom-economical, and have low
energy input. The projects detailed herein aim to develop new umpolung carbon-carbon bond forming reactions
with visible-light mediated photocatalysis. Specifically, the projects seek to generate radical species by electron
transfer to ketone-containing functional groups. This reactivity will be enabled by photocatalytic electron transfer
either to or from an activated carbonyl species. Two specific goals will be approached: 1) Initial work will extend
preliminary experimental results that have shown that ketyl radicals can be generated by the combined activity
of photocatalysts and Lewis acids to enantioselective 1,4-additions with the use of chiral Lewis acids. 2) Electron
transfer from 1,3-dicarbonyls is proposed to generate electrophilic radicals for carbon-carbon bond formation
with nucleophiles. A variety of carbon-carbon bond forming reactions that involve 1,3-dicarbonyl radicals are
proposed, including hydro-, amido-, and dialkylation of alkenes. In total, these new catalytic processes will
provide highly efficient methods for the use of visible light to construct carbon-carbon bonds in complex and
biologically relevant molecular settings. The achievement of the designed umpolung reactivity of carbonyl-
containing compounds by single electron reduction or oxidation would broaden the scope of reactivity for these
widely available reagents. As a result, this proposal will contribute to the general toolbox of carbon-carbon bond
forming reactions with new methods that are able to simultaneously build molecular complexity and adjust
oxidation state. The projects are specifically tailored to be carried out by a research team composed entirely of
undergraduates and is therefore broken up into discrete individual projects. This proposal would enhance the
research training and outcomes of a diverse group of undergraduates pursuing careers in the biomedical
sciences.

## Key facts

- **NIH application ID:** 9964343
- **Project number:** 1R15GM137238-01
- **Recipient organization:** OCCIDENTAL COLLEGE
- **Principal Investigator:** Jeffrey Cannon
- **Activity code:** R15 (R01, R21, SBIR, etc.)
- **Funding institute:** NIH
- **Fiscal year:** 2020
- **Award amount:** $280,280
- **Award type:** 1
- **Project period:** 2020-09-05 → 2024-08-31

## Primary source

NIH RePORTER: https://reporter.nih.gov/project-details/9964343

## Citation

> US National Institutes of Health, RePORTER application 9964343, Photocatalyzed and Enantioselective Umpolung C-C Bond Forming Reactions of Carbonyls (1R15GM137238-01). Retrieved via AI Analytics 2026-05-24 from https://api.ai-analytics.org/grant/nih/9964343. Licensed CC0.

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