Thursday, July 3, 2025 7/3/2025

Transition Metal Catalyzed Reductive Carbene Transfer Reactions

Award Number: R35GM124791
ORGANIZATION: NATIONAL INSTITUTE OF GENERAL MEDICAL SCIENCES
OPDIV: NIH
AWARD CLASS: DISCRETIONARY
AWARD ACTIVITY TYPE: SCIENTIFIC/HEALTH RESEARCH (INCLUDES SURVEYS)
PERIOD OF PERFORMANCE START DATE: 08/08/2017
PERIOD OF PERFORMANCE END DATE: 07/31/2027

Group Awards By:

View Award Description

Transition Metal Catalyzed Reductive Carbene Transfer Reactions - Project Summary/Abstract Carbenes are versatile reactive intermediates capable of engaging in cycloaddition, bond insertion, rearrangement, and coupling reactions. Previous efforts to develop catalytic variants of carbene transfer reactions have largely focused on the use of diazoalkanes. The primary limitation of this approach is that diazoalkanes generally must be stabilized with electron-withdrawing or aryl groups in order to avoid the spontaneous, exothermic elimination of dinitrogen gas. The overarching goal of this program is to study transition metal catalyzed reductive carbene transfer reactions that use readily available gem-dihalo reagents as precursors to non-stabilized carbenes. Catalytic turnover can be achieved using chemical reductants, such as metal powders. Alternatively, the use of photoredox or electrocatalytic reduction makes these reactions compatible with emerging flow synthesis platforms. A broad scope of catalytic cycloaddition reactions will be developed. A particular focus will be on generating odd-membered rings, which are challenging to access by conventional thermal pericyclic processes. For example, transition metal catalysis will allow current limitations of the Simmons–Smith reaction to be addressed, such as the enantioselective synthesis of dimethyl-, spiro-, and methylenecyclopropanes. Asymmetric [4 + 1]-cycloadditions of vinylidenes and 1,3-dienes will generate complex cyclopentene derivatives. Finally, three-component [n + m + 1]-cycloadditions will be developed for the synthesis of five- and seven-membered carbocycles and heterocycles. Some of these reactions will use dinuclear metal catalysts, which provide a unique active site environment to mediate carbene and vinylidene transfer reactions. Transition metal-catalyzed additions of vinylidenes to alkenes can also be diverted to non-cycloaddition pathways by intercepting metalacyclic intermediates prior to ring closure. Reaction design is based on promoting β-X elimination or transmetalation reactions of these metalacycles. Based on this concept, novel carbon–carbon coupling reactions will be developed for the synthesis of chiral alcohol and amine products. The catalysis concepts developed in this project will impact human health by providing access to complex C(sp3)-rich frameworks that can be incorporated into biological probes and therapeutics.


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: 2025 ( Subtotal = $417,603 )
2025	2025	PURDUE UNIVERSITY	2550 NORTHWESTERN AVE # 1100	WEST LAFAYETTE	IN	47906	TIPPECANOE	USA	Biomedical Research and Research Training	002	9	6/24/2025	NON-COMPETING CONTINUATION	$417,603
2025	2024	PURDUE UNIVERSITY	2550 NORTHWESTERN AVE # 1100	WEST LAFAYETTE	IN	47906	TIPPECANOE	USA	Biomedical Research and Research Training	000	8	11/13/2024	NON-COMPETING CONTINUATION	$0
2025	2024	PURDUE UNIVERSITY	2550 NORTHWESTERN AVE # 1100	WEST LAFAYETTE	IN	47906	TIPPECANOE	USA	Biomedical Research and Research Training	001	8	6/11/2025	SUPPLEMENT FOR EXPANSION	$0
														Subtotal = $417,603

Issue Date FY: 2024 ( Subtotal = $526,949 )
2024	2024	PURDUE UNIVERSITY	2550 NORTHWESTERN AVE # 1100	WEST LAFAYETTE	IN	47906	TIPPECANOE	USA	Biomedical Research and Research Training	000	7	1/5/2024	SUPPLEMENT FOR EXPANSION	$40,285
2024	2024	PURDUE UNIVERSITY	2550 NORTHWESTERN AVE # 1100	WEST LAFAYETTE	IN	47906	TIPPECANOE	USA	Biomedical Research and Research Training	001	8	7/17/2024	NON-COMPETING CONTINUATION	$417,603
2024	2024	PURDUE UNIVERSITY	2550 NORTHWESTERN AVE # 1100	WEST LAFAYETTE	IN	47906	TIPPECANOE	USA	Biomedical Research and Research Training	002	8	7/18/2024	SUPPLEMENT FOR EXPANSION	$69,061
														Subtotal = $526,949

Issue Date FY: 2023 ( Subtotal = $417,603 )
2023	2023	PURDUE UNIVERSITY	2550 NORTHWESTERN AVE STE 1900	WEST LAFAYETTE	IN	47906	TIPPECANOE	USA	Biomedical Research and Research Training	001	7	7/10/2023	NON-COMPETING CONTINUATION	$417,603
2023	2021	PURDUE UNIVERSITY	2550 NORTHWESTERN AVE STE 1900	WEST LAFAYETTE	IN	47906	TIPPECANOE	USA	Biomedical Research and Research Training	000	5	6/27/2023	NON-COMPETING CONTINUATION	$0
														Subtotal = $417,603

Issue Date FY: 2022 ( Subtotal = $442,359 )
2022	2022	PURDUE UNIVERSITY	2550 NORTHWESTERN AVE STE 1900	WEST LAFAYETTE	IN	47906	TIPPECANOE	USA	Biomedical Research and Research Training	000	6	8/19/2022	COMPETING CONTINUATION	$442,359
														Subtotal = $442,359

Issue Date FY: 2021 ( Subtotal = $370,571 )
2021	2021	PURDUE UNIVERSITY	155 S GRANT ST	WEST LAFAYETTE	IN	47907	TIPPECANOE	USA	Biomedical Research and Research Training	000	5	7/19/2021	NON-COMPETING CONTINUATION	$370,571
														Subtotal = $370,571

Issue Date FY: 2020 ( Subtotal = $370,571 )
2020	2020	PURDUE UNIVERSITY	155 S GRANT ST	WEST LAFAYETTE	IN	47907	TIPPECANOE	USA	Biomedical Research and Research Training	000	4	7/14/2020	NON-COMPETING CONTINUATION	$370,571
														Subtotal = $370,571

Issue Date FY: 2019 ( Subtotal = $498,140 )
2019	2019	PURDUE UNIVERSITY	155 S GRANT ST	WEST LAFAYETTE	IN	47907	TIPPECANOE	USA	Biomedical Research and Research Training	001	3	8/22/2019	SUPPLEMENT FOR EXPANSION	$127,569
2019	2019	PURDUE UNIVERSITY	401 SOUTH GRANT ST	WEST LAFAYETTE	IN	47907	TIPPECANOE	USA	Biomedical Research and Research Training	000	3	7/16/2019	NON-COMPETING CONTINUATION	$370,571
														Subtotal = $498,140

Issue Date FY: 2018 ( Subtotal = $370,571 )
2018	2018	PURDUE UNIVERSITY	401 SOUTH GRANT ST	WEST LAFAYETTE	IN	47907	TIPPECANOE	USA	Biomedical Research and Research Training	000	2	7/26/2018	NON-COMPETING CONTINUATION	$370,571
														Subtotal = $370,571

Issue Date FY: 2017 ( Subtotal = $354,071 )
2017	2017	PURDUE UNIVERSITY	401 SOUTH GRANT ST	WEST LAFAYETTE	IN	47907	TIPPECANOE	USA	Biomedical Research and Research Training	000	1	8/7/2017	NEW	$354,071
														Subtotal = $354,071

Grand Total All Awards = $3,768,438

Top

All Categories

About

Search

Reports

Data Submission

Award Information

Transition Metal Catalyzed Reductive Carbene Transfer Reactions

Award Number: R35GM124791

ORGANIZATION: NATIONAL INSTITUTE OF GENERAL MEDICAL SCIENCES

OPDIV: NIH

AWARD CLASS: DISCRETIONARY

AWARD ACTIVITY TYPE: SCIENTIFIC/HEALTH RESEARCH (INCLUDES SURVEYS)

PERIOD OF PERFORMANCE START DATE: 08/08/2017

PERIOD OF PERFORMANCE END DATE: 07/31/2027

Federal Websites

Department of Health & Human Services

HHS Operating Divisions

HHS Staff Divisions

Download A Document Viewer