New methods for C(sp3)–H functionalization: from C–C bond formation to fluorination
In recent years, the development of light-driven reactions has contributed numerous advances in synthetic organic chemistry.
This seminar will describe Abigail Doyle’s group’s efforts to develop new methods for C(sp3)–H functionalization via Ni-photoredox and photoredox catalysis. Using the combination of Ni-photoredox catalysis, they have developed a suite of cross-coupling reactions between chloride-containing electrophiles and abundant C(sp3)–H partners. In these reactions, photoinduced activation of the nickel catalyst contributes to the generation of chlorine radical as a potent hydrogen atom transfer agent.
The group has also recently developed a suite of reactions for C(sp3)–H oxidation to aliphatic fluorides, chlorides, alcohols, ethers, and thioethers via photoredox catalysis. In these reactions, sequential hydrogen atom transfer and oxidative radical-polar crossover enable access to a carbocation from a C(sp3)–H partner that can be trapped by a variety of nucleophiles, including halides, water, alcohols, and thiols under exceptionally mild conditions.
The development, scope, and mechanistic analysis of these methods will be presented.
Abigail Doyle is the A. Barton Hepburn Professor of Chemistry in the Chemistry Department at Princeton University. She obtained her Ph.D. in catalysis and physical organic chemistry at Harvard University in 2008 under the direction of Prof. Eric Jacobsen after receiving her A.B. and A.M. in chemistry and chemical biology from Harvard in 2002. She joined the faculty at Princeton University in 2008 and is currently a co-PI for the NSF CCI Center for Computer Assisted Synthesis (C-CAS) and the DOE EFRC Bioinspired Light-Escalated Chemistry (BioLEC). The Doyle laboratory is interested in developing new approaches to chemical synthesis and catalysis, with a focus on Ni-catalyzed cross-coupling and nucleophilic fluorination methodology.
• Tim Gorman – YCP/Evotec
• Daniel Hamza – FCG/Sygnature
• Fred Hancock – FCG
• Joe Howard – YCP/BioTechne
• Caroline Low – FCG/Caroline Low Consultancy
• Antonio Misale – FCG/Johnson and Johnson
• Oliver Ring – YCP/AstraZeneca
• Jason Tierney – FCG/Anima Biotech
Tel: +44 (0)20 7598 1561