# Administrative Supplement for Equipment

> **NIH NIH R35** · MASSACHUSETTS INSTITUTE OF TECHNOLOGY · 2024 · $173,149

## Abstract

NOT-GM-24-021
Parent Grant: R35-GM122483. Metal Catalyzed Methods for Organic Synthesis
Research Plan:
 Our group's research focuses on developing methods for forming carbon-heteroatom and carbon-
carbon bonds. Creating highly functionalized molecules in a reliable manner is crucial for organic
synthesis, underpinning drug discovery, development, and scale-up. Our techniques are widely adopted
in academia and industry for synthesizing complex molecules, serving as important processes for
synthetic chemists. By inventing new methods, we not only gain access to important compounds but also
the ability to modify them efficiently and selectively, altering their properties and minimizing side effects.
 Our ongoing projects encompass various areas, including palladium-catalyzed cross coupling
methods for generating heterocyclic carbon-nitrogen bonds; copper-catalyzed methods for the
construction of carbon-oxygen or carbon-nitrogen bonds; copper-catalyzed methods for the highly regio-
diastereo-, and enantioselective synthesis of aliphatic amines; and copper-catalyzed methods for the
asymmetric formation of carbon-carbon bonds. Mechanistic studies have helped us to investigate the
fundamental aspects of these transformations, guiding us to enhance their efficiency and applicability.
The substrates we target are integral structural components found in pharmaceuticals, natural products,
agrochemicals and sensors.
 In our continued efforts in Pd-catalyzed cross coupling reactions we have developed easily
accessible precursors for Pd oxidative addition complexes.1 We have also designed new ligands and mild
reaction conditions for the C–N cross coupling of five-membered heteroaryl halides with secondary,
primary aliphatic amines and anilines.2
Ullmann-type C–N coupling reactions represent an important alternative to well-established
palladium-catalyzed approaches due to the differing reactivity, lower cost, and diminished toxicity of
copper. Using a combination of experimental and theoretical methods we have established a new class
of anionic ligands for Cu-catalyzed C–N coupling of aryl bromides and alkyl amines at room temperature.3
Using our newly developed N1,N2-diarylbenzene-1,2-diamine ligand class, we have also developed a Cu-
catalyzed method for the coupling of alcohols and (hetero)aryl bromides.4
 We have introduced new copper-hydride methods for the enantioselective olefin
hydromethylation,5 alkyne hydroalkylation,6 and the asymmetric formal hydroformylation of vinyl arenes.7
 Since the submission of our last renewal in 2022, we have reported 14 publications that were
funded by the parent grant R35-122483. We dedicate significant efforts to make our methods user-
friendly, practical, and applicable across a broad spectrum of compounds. We systematically optimize
the limitations and range of conditions and substrates they can accommodate. Several analytical
instruments play important roles in our studies including, nuclear magnetic spectroscopy (NMR)
sp...

## Key facts

- **NIH application ID:** 11100057
- **Project number:** 3R35GM122483-08S1
- **Recipient organization:** MASSACHUSETTS INSTITUTE OF TECHNOLOGY
- **Principal Investigator:** STEPHEN L BUCHWALD
- **Activity code:** R35 (R01, R21, SBIR, etc.)
- **Funding institute:** NIH
- **Fiscal year:** 2024
- **Award amount:** $173,149
- **Award type:** 3
- **Project period:** 2017-06-01 → 2027-05-31

## Primary source

NIH RePORTER: https://reporter.nih.gov/project-details/11100057

## Citation

> US National Institutes of Health, RePORTER application 11100057, Administrative Supplement for Equipment (3R35GM122483-08S1). Retrieved via AI Analytics 2026-05-26 from https://api.ai-analytics.org/grant/nih/11100057. Licensed CC0.

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