# An electrocatalytic approach to discovering new synthetic transformations

> **NIH NIH R01** · CORNELL UNIVERSITY · 2021 · $129,365

## Abstract

Project Summary
 Alkenes are prevalent groups in bioactive compounds and are also versatile motifs in
organic synthesis owing to their rich reactivity. While alkenes have traditionally been prepared by
venerable reactions like the Wittig olefination, Grubbs metathesis, and elimination reactions,
much of this chemistry has relied on the use of pre-functionalized starting materials. While
providing enabling tools, these approaches hinder the step economy of fine chemical synthesis
from feedstocks and are often not amenable to late-stage functionalization. As a result, mild
methods for the desaturation of alkanes are highly sought after in organic synthesis. Although
several methods have recently been developed for transforming abundant functional groups like
C–H bonds to alkenes, these approaches typically require the use of precious transition metal
catalysts, suffer from poor turnover numbers, or require stoichiometric oxidants.
 In this proposal, we present a novel and practical method for the synthesis of alkenes from
readily available radical precursors. Specifically, we propose to further develop the proclivity of
sulfur radical cations to trap carbon centered radicals to generate sulfonium ions in situ. These
intermediates will be capable of undergoing an elimination reaction to furnish alkenes. This
approach will leverage two oxidative events at an anode to generate a pair of reactive catalytic
radical intermediates—a transient carbon-centered radical and a persistent sulfur radical cation.
The innate properties of sulfur radical cations such as their relatively long lifetime, reactivity
towards capturing carbon-centered radicals, and electrophilicity of the resultant alkyl sulfonium
ions will enable productive transformations. This radical-polar crossover reaction will provide an
electrochemical alkane desaturation method that avoids the use of stoichiometric activating
groups and harsh oxidants typically used by other methods. This project has three specific aims:
1) establish proof-of-concept reactivity of sulfur radical cations in the context of decarboxylative
desaturation of carboxylic acids, and 2) expansion of this reactivity to simple alkanes through
hydrogen atom abstraction. To achieve the second aim, we will investigate a number of known
and new electrochemical mediators as H-atom acceptors for C–H activation. Lastly, 3) this
method will be used for nucleophilic substitution to rapidly access a host of functionalities using
readily available nucleophiles.

## Key facts

- **NIH application ID:** 10406065
- **Project number:** 3R01GM130928-04S1
- **Recipient organization:** CORNELL UNIVERSITY
- **Principal Investigator:** Song Lin
- **Activity code:** R01 (R01, R21, SBIR, etc.)
- **Funding institute:** NIH
- **Fiscal year:** 2021
- **Award amount:** $129,365
- **Award type:** 3
- **Project period:** 2018-09-20 → 2023-08-31

## Primary source

NIH RePORTER: https://reporter.nih.gov/project-details/10406065

## Citation

> US National Institutes of Health, RePORTER application 10406065, An electrocatalytic approach to discovering new synthetic transformations (3R01GM130928-04S1). Retrieved via AI Analytics 2026-05-26 from https://api.ai-analytics.org/grant/nih/10406065. Licensed CC0.

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