Catalytic Enantioselective Cation Radical-Mediated Transformations: A New Paradigm in Asymmetric Catalysis The major goal of this research endeavor is to develop new catalyst systems for selective organic transformations that will be broadly applicable to the synthesis of therapeutically relevant small organic molecules. Specifically, our research is focused on developing new practical chemical reagents for the asymmetric catalysis of radical processes in an operationally trivial manner. We will develop moisture and oxygen stable chiral organic single-electron oxidation catalysts that are activated by visible light in order to initiate chemical reactivity. We will demonstrate that our catalysts can be utilized in enantioselective transformations mediated by cation radical species. It is anticipated that reactions such as enantioselective cycloaddition and alkene hydrofunctionalization reactions will be possible and will provide biomedical researchers with additional practical tools for single enantiomer medicinal agent synthesis. The proposed transformations follow the desirable tenants of atom economy, waste reduction and overall redox neutrality. As a consequence, we expect that this catalyst system could provide economic benefits in regards to the production of medicines available to the general public.

Public Health Relevance

Catalytic Enantioselective Cation Radical-Mediated Transformations: A New Paradigm in Asymmetric Catalysis The objective of this research program is to invent new synthetic protocols of relevance to the preparation of medicinal agents. We aim to develop catalysts that absorb visible light to promote reactions that are otherwise outside of the scope of existing chemical transformations.

Agency
National Institute of Health (NIH)
Institute
National Institute of General Medical Sciences (NIGMS)
Type
Research Project (R01)
Project #
5R01GM098340-03
Application #
8540442
Study Section
Synthetic and Biological Chemistry A Study Section (SBCA)
Program Officer
Lees, Robert G
Project Start
2011-09-01
Project End
2016-08-31
Budget Start
2013-09-01
Budget End
2014-08-31
Support Year
3
Fiscal Year
2013
Total Cost
$285,566
Indirect Cost
$84,843
Name
University of North Carolina Chapel Hill
Department
Chemistry
Type
Schools of Arts and Sciences
DUNS #
608195277
City
Chapel Hill
State
NC
Country
United States
Zip Code
27599
Nguyen, Tien M; Manohar, Namita; Nicewicz, David A (2014) anti-Markovnikov hydroamination of alkenes catalyzed by a two-component organic photoredox system: direct access to phenethylamine derivatives. Angew Chem Int Ed Engl 53:6198-201
Riener, Michelle; Nicewicz, David A (2013) Synthesis of cyclobutane lignans via an organic single electron oxidant-electron relay system. Chem Sci 4:
Nguyen, Tien M; Nicewicz, David A (2013) Anti-Markovnikov hydroamination of alkenes catalyzed by an organic photoredox system. J Am Chem Soc 135:9588-91
Perkowski, Andrew J; Nicewicz, David A (2013) Direct catalytic anti-Markovnikov addition of carboxylic acids to alkenes. J Am Chem Soc 135:10334-7