# Supplement: Regio- and Site-Selective Processes Using Main Group and Transition Metal Catalysis

> **NIH NIH R35** · UNIVERSITY OF MICHIGAN AT ANN ARBOR · 2021 · $64,594

## Abstract

Project Summary / Abstract
Rapid and reliable access to synthetically-derived chemical structures plays an essential role in many aspects
of biomedical research. The underlying objective of this proposal is to provide fundamentally new strategies for
highly selective bond formations that will enable more rapid and efficient access to biologically active compounds
of potential therapeutic value. A suite of new reactions will be developed that rely on the boron-catalyzed coupling
of organofluorine and organosilane substrates. Glycosylation reactions that rely on this reactivity paradigm will
be developed in concert with catalyst design, mechanistic study, and computational evaluation. Robust methods
that enable efficient assembly of glycosidic bonds with high degrees of stereocontrol and broad functional group
tolerance will allow access to any desired stereochemical outcome while allowing a platform for iterative
assembly of complex oligosaccharides. New late transition metal-catalyzed processes will be developed utilizing
the framework of connecting organofluorine with organosilane substrates using boron co-catalysis. Methods
where remote complexation of fluorine allows leaving groups to be activated on demand will developed as a
general strategy for applications in carbohydrate chemistry and in carbon-carbon bond-forming methodology.
Following the above focus on the development of new catalytic methods, approaches to the efficient assembly
of glycosylated structures will be pursued to provide new methods for accessing novel chemical probes and
potential therapeutic agents. This component will include developing new strategies for accessing rare
carbohydrates and for the stereoselective glycodiversification of peptides, natural products, and complex
synthetic intermediates. Methods for tailoring complex naturally occurring and synthetic structures will include
derivatization of existing hydroxyl functionality or biocatalytic functionalization of unactivated C-H bonds. These
capabilities will serve as a foundation for a broad array of collaborative studies including the discovery of new
antimicrobial and anticancer therapeutic agents and new chemical probes to provide insight into diverse
biological questions such as mechanisms of transcriptional activation and enzymatic degradation of host and
dietary oligosaccharides. The synthetic approaches developed represent a merger of rarely combined fields of
chemistry and biology: main group element catalysis, transition metal catalysis, carbohydrate chemistry, and
biocatalysis. The unique multidisciplinary perspective allows examination of strategies that cannot be addressed
by conventional approaches. The improved entries to biomedically important structures made possible by this
research will enable their biological function and therapeutic potential to be more efficiently studied. The
improved entries to biomedically important structures made possible by this research will enable their biological
fun...

## Key facts

- **NIH application ID:** 10388498
- **Project number:** 3R35GM118133-06S1
- **Recipient organization:** UNIVERSITY OF MICHIGAN AT ANN ARBOR
- **Principal Investigator:** JOHN MONTGOMERY
- **Activity code:** R35 (R01, R21, SBIR, etc.)
- **Funding institute:** NIH
- **Fiscal year:** 2021
- **Award amount:** $64,594
- **Award type:** 3
- **Project period:** 2016-04-01 → 2026-03-31

## Primary source

NIH RePORTER: https://reporter.nih.gov/project-details/10388498

## Citation

> US National Institutes of Health, RePORTER application 10388498, Supplement: Regio- and Site-Selective Processes Using Main Group and Transition Metal Catalysis (3R35GM118133-06S1). Retrieved via AI Analytics 2026-05-24 from https://api.ai-analytics.org/grant/nih/10388498. Licensed CC0.

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