Regioselective Hydroalkylation and Arylalkylation of Alkynes by Photoredox/Nickel Dual Catalysis: Application and Mechanism
KAUST DepartmentChemical Science Program
KAUST Catalysis Center (KCC)
Physical Science and Engineering (PSE) Division
Online Publication Date2020-02-03
Print Publication Date2020-03-27
Permanent link to this recordhttp://hdl.handle.net/10754/661463
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AbstractAlkynes are an important class of organic molecules due to their utility as versatile building blocks in synthesis. Although efforts have been devoted to the difunctionalization of alkynes, general and practical strategies for the direct hydroalkylation and alkylarylation of terminal alkynes under mild reaction conditions are less explored. Herein, we report a photoredox/nickel dual-catalyzed anti-Markovnikov-type hydroalkylation of terminal alkynes as well as a one-pot arylalkylation of alkynes with alkyl carboxylic acids and aryl bromides via a three-component cross-coupling. The results indicate that the transformations proceed via a new mechanism involving a single-electron transfer with subsequent energy-transfer activation pathways. Moreover, steady-state and time-resolved fluorescence-spectroscopy measurements, density functional theory (DFT) calculations, and wavefunction analysis have been performed to give an insight into the catalytic cycle.
CitationYue, H., Zhu, C., Kancherla, R., Liu, F., & Rueping, M. (2020). Regioselective Hydroalkylation and Arylalkylation of Alkynes by Photoredox/Nickel Dual Catalysis: Application and Mechanism. Angewandte Chemie. doi:10.1002/ange.201914061
SponsorsC.Z. acknowledges the King Abdullah University of Scienceand Technology (KAUST) for support and the KAUSTSupercomputing Laboratory for providing computationalresources of the supercomputer Shaheen II. The researchleading to these results has received funding from the European Research Council under the European Union sSeventh Framework Programme (FP/2007–2013)/ERC Grant Agreement no. 617044 (SunCatChem).
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