Photoinduced hydroarylation of alkenes is an appealing synthetic strategy for arene functionalization. Herein, we demonstrated that aryl radicals generated from electron-deficient aryl chlorides/bromides could be trapped by an array of terminal/internal aryl alkenes in the presence of [Pt(O^N^C^N)] under visible-light (410 nm) irradiation, affording anti-Markovnikov hydroarylated compounds in up to 95 % yield. Besides, a protocol for [Pt(O^N^C^N)]-catalyzed intramolecular photocyclization of acrylanilides to give structurally diverse 3,4-dihydroquinolinones has been developed.
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http://dx.doi.org/10.1002/anie.202011841 | DOI Listing |
Chem Sci
October 2024
Wöhler Research Institute for Sustainable Chemistry (WISCh), Georg-August-Universität Tammannstraße 2 37077 Göttingen Germany
Hydroarylation reactions have emerged as a valuable tool for the direct functionalization of C-H bonds with ideal atom economy. However, common catalytic variants for these transformations largely require harsh reaction conditions, which often translate into reduced selectivites. In contrast, we herein report on a photo-induced hydroarylation of unactivated olefins at room temperature employing a readily available ruthenium(ii) catalyst.
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August 2024
School of Chemistry and Chemical Engineering, Anhui University of Technology Ma'anshan Anhui 243002 P. R. China
Transition-metal-catalyzed hydroarylation of unactivated alkenes metal hydride hydrogen atom transfer (MHAT) is an attractive approach for the construction of C(sp)-C(sp) bonds. However, this kind of reaction focuses mainly on using reductive hydrosilane as a hydrogen donor. Here, a novel photoinduced Co/Ni-cocatalyzed Markovnikov hydroarylation of unactivated alkenes with aryl bromides using protons as a hydrogen source has been developed.
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September 2024
Chemical Sciences and Technology Division, CSIR-National Institute for Interdisciplinary Science and Technology (CSIR-NIIST), Thiruvananthapuram 695019, Kerala, India.
The visible light-promoted -alkenylation of phenols and naphthols with terminal alkynes is achieved using 2,4,6-tris(4-fluorophenyl)pyrylium tetrafluoroborate (T(-F)PPT) as a photocatalyst at room temperature without the need of any external ligand or additive. Apart from its excellent functional group tolerance, the protocol described herein represents an appealing alternative strategy to classical transition-metal catalysed hydroarylation reactions. Mechanistic investigations revealed that the reaction involves a radical pathway.
View Article and Find Full Text PDFOrg Lett
July 2024
Flow Chemistry Group, van't Hoff Institute for Molecular Sciences (HIMS), University of Amsterdam, 1098 XH Amsterdam, The Netherlands.
Light-mediated Halogen-Atom Transfer (XAT) has become a significant methodology in contemporary synthesis. Unlike α-aminoalkyl and silyl radicals, ligated boryl radicals (LBRs) have not been extensively explored as halogen atom abstractors. In this study, we introduce NHC-ligated boranes as optimal radical chain carriers for the intermolecular reductive radical hydroalkylation and hydroarylation of electron-deficient olefins by using direct UV-A light irradiation.
View Article and Find Full Text PDFOrg 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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