Description:
Princeton Docket # 15-3146-1
Researchers in the Department of Chemistry at Princeton University have developed a new C-H fluorination method that uses uranium as a visible light photocatalyst.
The fluorination of unactivated Csp3–H bonds remains a desirable, challenging transformation for pharmaceutical, agricultural, and materials scientists. Current methods for the C–H fluorination of unactivated substrates (e.g. alkanes) rely on either highly reactive oxidant species and/or the use of high energy ultraviolet light.
This invention uses a modular visible light photocatalyst, uranyl nitrate hexahydrate, as a convenient, hydrogen atom abstraction catalyst, in conjunction with a commercial, bench stable fluorine source to achieve a mild fluorination of unactivated C–H bonds. Effective catalysts and precatalysts for this transformation are commercially available and the reaction can be carried out at room temperature using visible light irradiation. This earth-abundant photocatalyst exhibits remarkable selectivity in unactivated alkanes over short-chain ketones, compared to the previously reported, UV-active species.
Applications
• Fluorination of unactivated C-H bond
• Fluorine incorporation in drug candidates and biomolecules
• Drug diversification
Advantages
• Uses commercially available catalysts
• Mild reaction conditions using room temperature and visible light irradiation
• Higher selectivity than UV-active species
• Quantitative removal of catalyst when reaction is complete
Key Words
Catalysis, uranium, uranyl nitrate hexahydrate, near-UV irradiation, fluorination
Related Publications
Julian G. West, T. Aaron Bedell, and Erik J. Sorensen The Uranyl Cation as a Visible-Light Photocatalyst for C(sp3)-H Fluorination, Angew.Chem.Int.Ed. 2016, 55, 1-6
Inventors
Erik J. Sorensen, Ph.D. and Julian G. West
The Inventors
Erik J. Sorensen, Arthur Allan Patchett Professor in Organic Chemistry
The Sorensen laboratory is interested in the field of complex chemical synthesis, questions about the structural origins of architecturally unique natural products, and evaluating hypotheses about the chemical basis of the biological activities of natural products and non-natural molecules. His research aims to increase the capabilities of organic synthesis through the development of powerful reactions and strategies.
Professor Sorensen was born and raised in upstate New York and received his B. A. degree in Chemistry from Syracuse University, where he performed undergraduate research with Professor Roger Hahn. In 1989, he began his graduate studies in chemical synthesis at the University of California, San Diego. Under the direction of Professor K. C. Nicolaou, he synthesized a novel family of DNA cleaving, 10-membered ring enediynes, contributed to a laboratory synthesis of the cancer drug taxol and co-authored a book titled Classics in Total Synthesis, and obtained his Ph. D. degree in 1995. From 1995-1997, he was a National Science Foundation postdoctoral fellow in the laboratory of Professor Samuel Danishefsky at The Memorial Sloan-Kettering Cancer Center in New York, where he contributed to total syntheses of the epothilone class of antitumor agents. In 1997, he started his independent career at The Scripps Research Institute and became an Associate Professor with tenure in 2001. In 2003, he moved his research group to Princeton University, where he is the Arthur Allan Patchett Professor in Organic Chemistry.
For his achievements in chemical research and education, Professor Sorensen has received a Beckman Young Investigator Award, a Camille Dreyfus Teacher-Scholar Award, the AstraZeneca Award for Excellence in Chemistry, the Lilly Grantee Award, the Pfizer Global Research Award for Excellence in Organic Chemistry, and the Bristol-Myers Squibb Unrestricted Grant in Synthetic Organic Chemistry. In 2001, Professor Sorensen was a Woodward Scholar at Harvard University. In 2007, he was the Givaudan/Karrer Distinguished Visiting Professor at the University of Zürich. In 2009, he received the Arthur C. Cope Scholar Award from the American Chemical Society.
Julian G. West is a graduate student member of the NSF-CCHF who is interested in the design of new, practical, and sustainable chemical reactions using underutilitzed catalysts. He obtained his B.Sc. (Hons.) from the University of British Columbia, Vancouver in 2013 where he studied iridium photocatalysis under the guidance of professor Glenn M. Sammis. He then joined the group of professor Erik J. Sorensen at Princeton University where he is currently exploring the application of tungsten, cobalt, and uranium catalysts to selective C–H functionalization reactions. For his achievements in chemical research, Julian has been awarded a NSF Graduate Research Fellowship, a NSERC Postgraduate Scholarship (Doctoral, 3 Years), a Walker-McKinney ’50 Life Sciences Fellowship, and a 2016 Alfred R. Bader Award in Student Innovation.
Intellectual Property Status
Patent applications are pending. Princeton is seeking industrial collaborators for further development and commercialization of this technology.
Contact
Laurie Tzodikov
Princeton University Office of Technology Licensing
• (609) 258-7256• tzodikov@princeton.edu
Xin (Shane) Peng
Princeton University Office of Technology Licensing
• (609) 258-5579• xinp@princeton.edu