Thursday, March 19, 2026 3/19/2026

Catalytically Generated Amidyl Radicals for Site-Selective Intermolecular C-H Functionalization

Award Number: F32GM147975
ORGANIZATION: NATIONAL INSTITUTE OF GENERAL MEDICAL SCIENCES
OPDIV: NIH
AWARD CLASS: DISCRETIONARY
AWARD ACTIVITY TYPE: FELLOWSHIP/SCHOLARSHIP/STUDENT LOANS
PERIOD OF PERFORMANCE START DATE: 05/01/2023
PERIOD OF PERFORMANCE END DATE: 04/30/2025

Group Awards By:

View Award Description

Catalytically Generated Amidyl Radicals for Site-Selective Intermolecular C-H Functionalization - Project Summary The selective activation and functionalization of C–H bonds is one of the most important and challenging chemical transformations. The ability to activate any targeted C–H bond in a given molecule would immensely expand the scope of synthetically accessible chemical transformations and would be a powerful method of late- stage functionalization of complex molecules such pharmaceuticals, natural products, and commodity chemicals. Furthermore, carrying out these reactions using abundant, non-toxic catalysts and renewable energy sources (e.g., solar energy) is critical for the development of sustainable chemical processes. Achieving selectivity in C– H activation is often difficult due to the presence of numerous C–H bonds of similar strength in a given molecule. Even more challenging is discriminately functionalizing strong C–H bonds in proximity to weaker C–H bonds. Selectivity for C–H activation is often dictated by properties of the substrate, and in such cases, reactivity may be limited to the weakest or most acidic C–H bond. However, catalyst-control of selectivity, wherein the structure of the H-atom abstractor dictates selectivity, offers a powerful method of predictably introducing chemical diversity from hydrocarbon feedstocks. Amidyl radicals are potent H-atom abstractors (BDE(N–H) > 100 kcal mol-1) that are capable of cleaving strong C–H bonds, but their applications in intermolecular C–H activation reactions often rely on pre-functionalized amidyl sources, rendering them stoichiometric reagents. The direct activation of amide N–H bonds to generate amidyl radicals would provide catalytic access to these reactive intermediates and would dramatically improve their utility in C–H functionalization reactions. This proposed research strategy aims to develop new electro- and photocatalytic methods for direct N–H bond activation via proton-coupled electron transfer to generate amidyl radicals for selective C–H activation. By exploiting these modes of N–H bond activation in sterically shielded amide catalysts, the steric pressures imposed the amidyl radicals can dictate site-selectivity. A combination of electrochemical kinetics and photophysical studies, including time-resolved transient absorption spectroscopy and photocrystallography, will be employed to delineate the key structural and electronic features that govern selectivity. Overall, these studies will expand our ability to perform catalytic, site-selective C–H functionalization reactivity using sustainable energy sources.


Issue Date FY	Funding FY	Legal Entity Name	Legal Entity Address	Legal Entity City	Legal Entity State	Legal Entity Zip Code	Legal Entity COUNTY	Legal Entity COUNTRY	Assistance Listing	Award Code	Budget Year	Action Date	Action Type	Action Amount

Issue Date FY: 2026 ( Subtotal = -$5 )
2026	2024	PRESIDENT AND FELLOWS OF HARVARD COLLEGE	1033 MASSACHUSETTS AVE STE 3	CAMBRIDGE	MA	02138	MIDDLESEX	USA	Biomedical Research and Research Training	000	2	2/24/2026	NON-COMPETING CONTINUATION	-$5
														Subtotal = -$5

Issue Date FY: 2024 ( Subtotal = $76,756 )
2024	2024	PRESIDENT AND FELLOWS OF HARVARD COLLEGE	1033 MASSACHUSETTS AVE STE 3	CAMBRIDGE	MA	02138	MIDDLESEX	USA	Biomedical Research and Research Training	000	2	3/22/2024	NON-COMPETING CONTINUATION	$71,792
2024	2024	PRESIDENT AND FELLOWS OF HARVARD COLLEGE	1033 MASSACHUSETTS AVE STE 3	CAMBRIDGE	MA	02138	MIDDLESEX	USA	Biomedical Research and Research Training	001	2	5/14/2024	NON-COMPETING CONTINUATION	$4,964
														Subtotal = $76,756

Issue Date FY: 2023 ( Subtotal = $69,500 )
2023	2023	PRESIDENT AND FELLOWS OF HARVARD COLLEGE	1033 MASSACHUSETTS AVE 5TH FL	CAMBRIDGE	MA	02138	MIDDLESEX	USA	Biomedical Research and Research Training	001	1	4/5/2023	NEW	$0
2023	2023	PRESIDENT AND FELLOWS OF HARVARD COLLEGE	1033 MASSACHUSETTS AVE 5TH FL	CAMBRIDGE	MA	02138	MIDDLESEX	USA	Biomedical Research and Research Training	000	1	4/5/2023	NEW	$69,500
														Subtotal = $69,500

Grand Total All Awards = $146,251

Top

All Categories

About

Search

Reports

Data Submission

Award Information

Catalytically Generated Amidyl Radicals for Site-Selective Intermolecular C-H Functionalization

Award Number: F32GM147975

ORGANIZATION: NATIONAL INSTITUTE OF GENERAL MEDICAL SCIENCES

OPDIV: NIH

AWARD CLASS: DISCRETIONARY

AWARD ACTIVITY TYPE: FELLOWSHIP/SCHOLARSHIP/STUDENT LOANS

PERIOD OF PERFORMANCE START DATE: 05/01/2023

PERIOD OF PERFORMANCE END DATE: 04/30/2025

Federal Websites

Department of Health & Human Services

HHS Operating Divisions

HHS Staff Divisions

Download A Document Viewer