# Metal-Free Electrocatalysis for Fine-Chemical Synthesis

> **NIH NIH R35** · TEXAS A&M UNIVERSITY · 2020 · $349,658

## Abstract

Project Summary
 Oxidative substrate functionalization provides the opportunity to introduce new chemical functionality and
structural complexity. Synthetic electrocatalysis provides a conceptual platform for sustainable oxidation
technologies by obviating the need for stoichiometric chemical oxidants, and the attendant waste implied by
these reagents. In practice, slow interfacial electron transfer chemistry of many organic molecules prevents
widespread application of electrochemical methods to fine-chemical synthesis. Further, single electron-transfer
processes, which are the currency of electrochemical strategies, are not common elementary steps in
synthetically important transformations. The central hypothesis of this proposal is that development of
hypervalent iodine electrocatalysis will provide a platform to achieve a broad array of oxidative substrate
functionalization electrochemically. This hypothesis is predicated on the rich chemistry of hypervalent iodine
reagents, which are well-known to participate in selective two-electron oxygenation, amination, halogenation,
and hydrocarbyl transfer reactions. Successful development of hypervalent iodine electrocatalysis would
substantially impact the synthesis of fine chemicals, such as molecular therapeutics.
 This proposal aims to first develop electrocatalysis via electrochemically generated hypervalent iodine
species. Specifically, the proposed strategy leverages a previously unappreciated strategy for the synthesis of
hypervalent iodine species – that one-electron pathways provide efficient access to selective two-electron
chemical oxidants based on hypervalent iodine compounds – to develop synthetic hypervalent iodine
electrocatalysis. Preliminary data indicate that electrochemically generated carboxy radicals enable facile
electrosynthesis of hypervalent iodine species and that electrochemically generated hypervalent iodine species
are competent mediators of oxidative C–H / N–H coupling. We propose to extend these preliminary results to
develop new synthetically useful transformations, such as oxidative C–H functionalization. Further, the
fundamental understanding of the elementary steps involved in the oxidation of aryl iodides provides the
chemical insight necessary to develop novel methods of hypervalent iodine synthesis that will substantially
expand the synthetic scope of hypervalent iodine catalyzed substrate oxidation. A long-term goal of these
efforts is to identify new catalyst scaffolds to enable catalyst-controlled site- and stereoselective C–H
functionalization which would provide direct access to complex molecular architectures functionalized at
positions of metabolic consequence, which would impact the evaluation of drug metabolites and impact the
discovery of new therapeutics. Together, the proposed research efforts will provide both new sustainable
synthetic methods and expand the synthetic toolbox of transformations that are available for the synthesis of
functional mole...

## Key facts

- **NIH application ID:** 10029022
- **Project number:** 1R35GM138114-01
- **Recipient organization:** TEXAS A&M UNIVERSITY
- **Principal Investigator:** David C Powers
- **Activity code:** R35 (R01, R21, SBIR, etc.)
- **Funding institute:** NIH
- **Fiscal year:** 2020
- **Award amount:** $349,658
- **Award type:** 1
- **Project period:** 2020-08-01 → 2025-07-31

## Primary source

NIH RePORTER: https://reporter.nih.gov/project-details/10029022

## Citation

> US National Institutes of Health, RePORTER application 10029022, Metal-Free Electrocatalysis for Fine-Chemical Synthesis (1R35GM138114-01). Retrieved via AI Analytics 2026-05-23 from https://api.ai-analytics.org/grant/nih/10029022. Licensed CC0.

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