The Catellani reaction is a powerful strategy that allows the expeditious synthesis of highly substituted arenes, which are not easily accessible through traditional transition-metal-catalyzed cross-coupling reactions. This reaction utilizes the synergistic interplay of palladium and norbornene catalysis to facilitate sequential ortho-C-H functionalization and ipso termination of aryl iodides in a single operation. Since pioneering work by the group of Catellani in 1997, and later by the group of Lautens, this chemistry has attracted considerable attention from the synthetic chemistry community. Dramatic progress has been made by a number of groups in the past two decades. In this Minireview, the alkylating reagents employed in this intriguing reaction and the corresponding applications in organic synthesis are summarized; thus complementing existing reviews to inspire future developments.
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http://dx.doi.org/10.1002/chem.201802818 | DOI Listing |
Nat Chem
January 2025
School of Chemical and Physical Sciences, Victoria University of Wellington, Wellington, New Zealand.
Benzene reduction by molecular complexes remains an important synthetic challenge, requiring harsh reaction conditions involving group I metals. Reductions of benzene, to date, typically result in a loss of aromaticity, although the benzene tetra-anion, a 10π-electron system, has been calculated to be stable and aromatic. Due to the lack of sufficiently potent reductants, four-electron reduction of benzene usually requires the use of group I metals.
View Article and Find Full Text PDFOrg Lett
January 2025
Laboratory of Catalysis and Organic Synthesis, Department of Chemistry, Indian Institute of Technology Roorkee, Roorkee 247667, Uttarakhand, India.
Herein, we have reported the application of bench stable perfluoroalkanoic acids as fluoro-alkylating reagents in combination with DIB and primary amides for sequential one-pot transformation to R-embedded functionalized amides under metal-free conditions. The protocol is tolerant to a range of sensitive functional groups (>33 examples and up to 90% yield), and perfluoro acids. Preliminary mechanistic studies, control experiments, in situ F-NMR analyses, and the synthesis of intermediate species were performed to understand the reaction pathways.
View Article and Find Full Text PDFTheranostics
January 2025
Department of Nuclear Medicine, Tongji Hospital, Tongji Medical College, Huazhong University of Science and Technology, Wuhan, China.
The role of oxidative stress metabolism during hepatocellular carcinoma (HCC) formation potentially allows for positron emission tomography (PET) imaging of oxidative stress activity for early and precise HCC detection. However, there is currently limited data available on oxidative-stress-related PET imaging for longitudinal monitoring of the pathophysiological changes during HCC formation. This work aimed to explore PET-based longitudinal monitoring of oxidative stress metabolism and determine the sensitivity of [18F]-5-fluoroaminosuberic acid ([18F]FASu) for assessing pathophysiological processes in diethylnitrosamine (DEN) induced rat HCC.
View Article and Find Full Text PDFJ Am Chem Soc
January 2025
Advanced Catalysis Research Group, RIKEN Center for Sustainable Resource Science, 2-1 Hirosawa, Wako, Saitama 351-0198, Japan.
Org Lett
January 2025
College of Chemistry, Zhengzhou University, Zhengzhou, Henan 450001, China.
Herein, we report a method for the regioselective alkylation and phosphonation of quinoline C4-H via a BH-mediated nucleophilic addition of Turbo Grignard reagents and phosphine oxide anions to quinolines bearing different substituents, affording the 4-alkyl and 4-phosphoryl quinolines and tetrahydroquinolines after one-pot oxidation or reduction. The results indicate that coordination of the BH group can activate substrates toward a potential 1,4-dearomative addition and subtly control the regioselectivity by preventing the 1,2-dearomative addition.
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