The intermolecular alkylation of pyridine units with simple alkenes has been achieved via a photoredox radical mechanism. This process occurs with complete regiocontrol, where single-electron reduction of halogenated pyridines regiospecifically yields the corresponding radicals in a programmed fashion, and radical addition to alkene substrates occurs with exclusive anti-Markovnikov selectivity. This system is mild, tolerant of many functional groups, and effective for the preparation of a wide range of complex alkylpyridines.
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Transition-Metal-Free Anti-Markovnikov Hydroarylation of Alkenes with Aryl Chlorides through Consecutive Photoinduced Electron Transfer.
Org Lett
February 2024
Division of Molecular Catalysis and Synthesis, Henan Institute of Advanced Technology, Zhengzhou University, Zhengzhou 450001, P. R. China.
The hydroarylation of alkenes has emerged as a powerful strategy for arene functionalization. However, aryl chlorides remain a large challenge in this type of reaction due to the chemical inertness of the C(sp)-Cl bond and high negative reduction potential. Herein, we report an anti-Markovnikov radical hydroarylation of alkenes with aryl chlorides via visible-light photoredox catalysis.
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Org Biomol Chem
January 2024
School of Chemistry and Chemical Engineering, Key Laboratory of Material Chemistry for Energy Conversion and Storage (Ministry of Education), Hubei Key Laboratory of Material Chemistry and Service Failure, Huazhong University of Science and Technology, Wuhan 430074, PR China.
Article Synopsis
- Aniline derivatives are vital nitrogen compounds used in various industries like chemicals and pharmaceuticals.
- Nickel(II) and Lewis acid catalysis enable the efficient hydroamination of olefins with anilines, showing different product outcomes based on the olefin type used.
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Ligand-Regulated Palladium-Catalyzed Regiodivergent Hydroarylation of the Distal Double Bond of Allenamides with Aryl Boronic Acid.
J Org Chem
October 2021
School of Chemistry and Chemical Engineering, Shandong University of Technology, 266 West Xincun Road, Zibo 255049, People's Republic of China.
The ligand-regulated regiodivergent hydroarylation of the distal double bond of allenamides with aryl boronic acid was achieved in the presence of palladium(II) catalysts, delivering a variety of functionalized enamide with excellent E selectivity and Markovnikov/anti-Markovnikov selectivity. Two possible coordination intermediates were proposed to be responsible for the regiodivergent hydroarylation: (1) The coordination , which was proposed to be formed through the coordination of MeCN, distal double bond, phenyl to palladium, led to the aryl group away from the , inducing excellent E selectivity and anti-Markovnikov selectivity. (2) A switch of regioselectivity to 1,2- hydroarylation was obtained using bidentate phosphine ligand (dppf or Xantphos).
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Chem Commun (Camb)
June 2021
Division of Chemistry and Biological Chemistry, School of Physical and Mathematical Sciences, Nanyang Technological University, 637371, Singapore.
A protocol for anti-Markovnikov hydroarylation of alkenes with aryl halides has been developed using polysulfide anions as photocatalysts in the presence of the Hantzsch ester and water under irradiation with visible light.
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Nat Commun
May 2021
School of Chemical and Physical Sciences, Victoria University of Wellington, Wellington, New Zealand.
Although the nucleophilic alkylation of aromatics has recently been achieved with a variety of potent main group reagents, all of this reactivity is limited to a stoichiometric regime. We now report that the ytterbium(II) hydride, [BDIYbH] (BDI = CH[C(CH)NDipp], Dipp = 2,6-diisopropylphenyl), reacts with ethene and propene to provide the ytterbium(II) n-alkyls, [BDIYbR] (R = Et or Pr), both of which alkylate benzene at room temperature. Density functional theory (DFT) calculations indicate that this latter process operates through the nucleophilic (S2) displacement of hydride, while the resultant regeneration of [BDIYbH] facilitates further reaction with ethene or propene and enables the direct catalytic (anti-Markovnikov) hydroarylation of both alkenes with a benzene C-H bond.
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