# An Electrochemical Approach to Amine Synthesis from Nitrogen

> **NIH NIH F32** · CALIFORNIA INSTITUTE OF TECHNOLOGY · 2024 · $73,828

## Abstract

Project Summary/Abstract
Nitrogen-containing functionalities constitute one of the largest classes within health-relevant small molecules.
Therefore, the development of new methods to construct carbon–nitrogen bonds remains paramount among
opportunities for innovation in chemical synthesis. The Haber–Bosch process is arguably the most important
synthetic catalytic process, wherein atmospheric nitrogen (N2) is reduced to ammonia (NH3) by an iron catalyst
under high temperature and pressure. In contrast, nature’s N2 fixation catalysts, nitrogenases, operate at ambient
conditions using a bimetallic active site. As such, many well-defined coordination complexes have been
developed to study key bond-forming steps in N2 reduction, with the goal of designing more efficient catalysts for
the synthesis of ammonia and other value-added compounds. While there has been some success in catalytic
N2 silylation to give tris(trialkylsilyl)amines, there are no examples of the analogous catalytic process for amine
synthesis through carbon–nitrogen bond-formation from N2. Current strategies for the direct conversion of N2
amines require multistep synthetic sequences of metal–N2 complexes with organic electrophiles and subsequent
product release under harsh conditions. To circumvent these limitations, the proposed research employs
metallocene-based catalysts to promote proton-coupled electron-transfer pathways for radical functionalization
of metal–N2 catalysts. Enabled by a renaissance in organic radical generation, easy access to a suite of abundant
olefins, and by exploiting complementary reactivity modes of metal–N2 catalysts, a diverse range of primary,
secondary, and aryl amine products can be synthesized. The research plan outlines specific approaches that
will deliver fundamental insights into reactions of metal–N2 complexes with organic radicals and metal nitrides,
commonly proposed intermediates in N2 reduction, with alkenes. These studies will provide the foundation for
the realization of a catalytic synthesis of medicinally relevant functional groups from the most abundant source
of nitrogen—N2.

## Key facts

- **NIH application ID:** 10914036
- **Project number:** 5F32GM151784-02
- **Recipient organization:** CALIFORNIA INSTITUTE OF TECHNOLOGY
- **Principal Investigator:** John Michael Ovian
- **Activity code:** F32 (R01, R21, SBIR, etc.)
- **Funding institute:** NIH
- **Fiscal year:** 2024
- **Award amount:** $73,828
- **Award type:** 5
- **Project period:** 2023-08-09 → 2026-08-08

## Primary source

NIH RePORTER: https://reporter.nih.gov/project-details/10914036

## Citation

> US National Institutes of Health, RePORTER application 10914036, An Electrochemical Approach to Amine Synthesis from Nitrogen (5F32GM151784-02). Retrieved via AI Analytics 2026-05-23 from https://api.ai-analytics.org/grant/nih/10914036. Licensed CC0.

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