Remote Nickel-Catalyzed Cross-Coupling Arylation via Proton-Coupled Electron Transfer-Enabled C–C Bond Cleavage
KAUST DepartmentChemical Science Program
KAUST Catalysis Center (KCC)
Physical Science and Engineering (PSE) Division
Online Publication Date2020-02-04
Print Publication Date2020-02-19
Embargo End Date2021-02-04
Permanent link to this recordhttp://hdl.handle.net/10754/661459
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AbstractCross-coupling reactions for carbon–carbon and carbon–heteroatom bond formation are of great importance in modern chemical synthesis. In addition to classical cross-couplings involving preformed or preactivated coupling partners, more recently breakthroughs have been made in the selective, direct coupling of abundant aliphatic carbon–hydrogen bonds using hydrogen atom transfer reactions in which the bond-dissociation energy is the thermodynamic driving force. The more challenging carbon–carbon bond activation is still rather underdeveloped due to the bond inertness. Herein, we report a mild and general strategy for the activation of a diverse set of readily available cyclic alcohols for the remote and site-specific arylation of ketones via the combination of photoredox-mediated multisite concerted proton–electron transfer (MS-PCET) and nickel catalysis. The current cross-coupling proceeds with the generation of an alkoxy radical utilizing bond-dissociation free energy (BDFE) as the thermodynamic driving force. Subsequently, the resulting remote carbon-centered radicals formed by C–C cleavage merge with the nickel catalytic cycle to create the challenging C(sp3)–C(sp2) bonds.
CitationHuang, L., Ji, T., & Rueping, M. (2020). Remote Nickel-Catalyzed Cross-Coupling Arylation via Proton-Coupled Electron Transfer-Enabled C–C Bond Cleavage. Journal of the American Chemical Society. doi:10.1021/jacs.9b12490
SponsorsThe authors acknowledge King Abdullah University of Science and Technology (KAUST) for support. The research leading to these results has also received funding from the European Research Council under the European Union’s Seventh Framework Programme (FP/2007-2013)/ERC Grant Agreement no. 617044 (SunCatChem).
PublisherAmerican Chemical Society (ACS)