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Aliphatic Effects in Transition Metal Catalysis

Award Number: R35GM128902
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: 07/15/2018
PERIOD OF PERFORMANCE END DATE: 06/30/2024

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Aliphatic Effects in Transition Metal Catalysis - Project Summary. An incredible diversity of transition metal-catalyzed methods has been developed around a small subset of elementary organometallic reactions. The overarching goal of our research program is to expand this tool box to include new organometallic mechanisms that can in turn be integrated into many new catalytic transformations to generate new organic structures. A central hypothesis of this proposal is that enforcing persistent coordinative-unsaturation in catalyst structures can enable unique organometallic mechanisms, such as in the transmetalation step common to all carbon- carbon and carbon-heteroatom cross-coupling reactions – some of the most practiced reactions at all levels of pharmaceutical research. Our approach is inspired by the potential for substantial attractive van der Waals forces in large aliphatic groups, which we are able to incorporate into metal catalysts structures using large organophosphorus ligands. A primary focus of this work will be to understand the mechanisms of, and to leverage, an unusual series of transmetalation reactions we have observed with mixtures of low-coordinate palladium complexes and protic nucleophiles, such as organoboronic acids. These reactions can occur under very mild conditions even in the absence of strong base, which has been historically necessary in many cross-coupling reactions yet also compromises the compatibility with sensitive compounds. The unique influence of diamondoids, such as in tri(1-adamantyl)phosphine, in promoting this chemistry may reflect the large polarizability and dispersion forces manifested in large aliphatic molecules. In order to generalizing these aliphatic effects, we will concurrently pursue new, modular methods to construct congested C(sp3)−P bonds, which are common motifs in both catalytic structures and also many biologically active compounds. Furthermore, we will expand these aliphatic effects to promote historically challenging transmetalation and oxidative addition reactions in iron and copper catalysis, respectively, which are general problems that have hindered efforts hindered to develop more sustainable cross-coupling methods using abundant base metals Together the catalytic and organophosphorus synthetic efforts of this proposal will generate new biologically active molecular structures through novel carbon-element bond forming reactions.


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 = -$13 )
2025	2022	UNIVERSITY OF HOUSTON SYSTEM	4300 MARTIN LUTHER KING BLVD	HOUSTON	TX	77204	HARRIS	USA	Biomedical Research and Research Training	000	6	3/6/2025	NON-COMPETING CONTINUATION	-$13
														Subtotal = -$13

Issue Date FY: 2022 ( Subtotal = $387,500 )
2022	2022	UNIVERSITY OF HOUSTON SYSTEM	4800 W CALHOUN ST STE 316	HOUSTON	TX	77004	HARRIS	USA	Biomedical Research and Research Training	001	6	9/9/2022	NON-COMPETING CONTINUATION	$387,500
2022	2020	THE TRUSTEES OF PRINCETON UNIVERSITY	1 NASSAU HALL	PRINCETON	NJ	08544	MERCER	USA	Biomedical Research and Research Training	000	3	11/5/2021	NON-COMPETING CONTINUATION	$0
														Subtotal = $387,500

Issue Date FY: 2021 ( Subtotal = $385,947 )
2021	2021	UNIVERSITY OF HOUSTON SYSTEM	4800 W CALHOUN ST STE 316	HOUSTON	TX	77004	HARRIS	USA	Biomedical Research and Research Training	002	5	7/29/2021	NON-COMPETING CONTINUATION	$387,500
2021	2020	TRUSTEES OF PRINCETON UNIVERSITY, THE	1 NASSAU HALL	PRINCETON	NJ	08544	MERCER	USA	Biomedical Research and Research Training	000	3	7/12/2021	NON-COMPETING CONTINUATION	-$382,882
2021	2020	UNIVERSITY OF HOUSTON SYSTEM	4800 W CALHOUN ST STE 316	HOUSTON	TX	77004	HARRIS	USA	Biomedical Research and Research Training	001	4	7/12/2021	CHANGE OF GRANTEE / TRAINING INSTITUTION / AWARDING INSTITUTION	$381,329
														Subtotal = $385,947

Issue Date FY: 2020 ( Subtotal = $389,047 )
2020	2020	TRUSTEES OF PRINCETON UNIVERSITY, THE	1 NASSAU HALL	PRINCETON	NJ	08544	MERCER	USA	Biomedical Research and Research Training	000	3	5/20/2020	NON-COMPETING CONTINUATION	$389,047
														Subtotal = $389,047

Issue Date FY: 2019 ( Subtotal = $389,047 )
2019	2019	TRUSTEES OF PRINCETON UNIVERSITY, THE	1 NASSAU HALL	PRINCETON	NJ	08544	MERCER	USA	Biomedical Research and Research Training	000	2	6/21/2019	NON-COMPETING CONTINUATION	$389,047
														Subtotal = $389,047

Issue Date FY: 2018 ( Subtotal = $376,647 )
2018	2018	TRUSTEES OF PRINCETON UNIVERSITY, THE	1 NASSAU HALL	PRINCETON	NJ	08544	MERCER	USA	Biomedical Research and Research Training	000	1	7/14/2018	NEW	$376,647
														Subtotal = $376,647

Grand Total All Awards = $1,928,175

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Aliphatic Effects in Transition Metal Catalysis

Award Number: R35GM128902

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: 07/15/2018

PERIOD OF PERFORMANCE END DATE: 06/30/2024

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