Regioselective C-H alkenylation of -dialkylanilines with ynamides was developed using AgNTf as a catalyst. This approach represents a facile hydroarylation of ynamides, allowing for the introduction of an alkenyl group exclusively at the position of aniline derivatives. As a result, a series of 4-alkenyl -dialkylanilines were synthesized with excellent regioselectivities.
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http://dx.doi.org/10.1021/acs.joc.1c02263 | DOI Listing |
Chemistry
December 2024
Université de Liège: Universite de Liege, Laboratory of Organometallic Chemistry and Homogeneous Catalysis, Institut de chimie B6a, Sart-Tilman, 4000, Liege, BELGIUM.
Thirteen imidazolium iodides bearing benzyl, mesityl, or 2,6-diiso-propyl-phenyl substituents on their nitrogen atoms, and C1 to C4 alkyl chains on their C2 carbon atom were readily deuterated with D2O as a cheap and non-toxic deuterium source in the presence of Cs2CO3, a weak, innocuous, inorganic base. The isotopic exchange proceeded quickly and efficiently under mild, aerobic conditions to afford a range of aNHC and NHO precursors regioselectively labeled on their C2α exocyclic position and/or C4=C5 heterocyclic backbone. A "carbene-free" mechanism was postulated, in which the carbonate anion acts as a catalyst to activate an exocyclic, acidic C-H bond and ease a deuterium transfer from D2O to the imidazolium salt in a concerted fashion.
View Article and Find Full Text PDFJACS Au
December 2024
State Key Laboratory of Fine Chemicals, School of Chemistry, Dalian University of Technology, Dalian 116024, China.
Nitroaromatics, as an important member and source of nitrogen-containing aromatics, is bringing enormous economic benefits in fields of pharmaceuticals, dyes, pesticides, functional materials, fertilizers, and explosives. Nonetheless, the notoriously polluting nitration industry, which suffers from excessive discharge of fumes and waste acids, poor functional group tolerance, and tremendous purification difficulty, renders mild, efficient, and environmentally friendly nitration a formidable challenge. Herein, we develop a visible-light-driven biocompatible arene C-H nitration strategy with good efficiency and regioselectivity, marvelous substrate applicability and functional group tolerance, and wide application in scale-up synthesis, total synthesis, and late-stage functionalization.
View Article and Find Full Text PDFChem Commun (Camb)
December 2024
College of Biological, Chemical Sciences and Engineering, Jiaxing University, Jiaxing 314001, Zhejiang, China.
This paper describes a ferric nitrene/photoredox dual-catalyzed anti-Markovnikov ring-opening of epoxides under neutral conditions for providing α-substituted acetophenones. A DFT-based calculation supported the reaction regioselectivity. The catalytic system could also be applied to the formation of C-O and C-N bonds nucleophilic functionalization of benzylic C-H bonds.
View Article and Find Full Text PDFChem Sci
December 2024
Department of Chemistry, University of Bayreuth Universitätsstraße 30 95447 Bayreuth Germany
The direct functionalization of C-H bonds has revolutionized the field of synthetic organic chemistry by enabling efficient and atom-economical modification of arenes by avoiding prefunctionalization. However, the inherent challenges of inertness and regioselectivity in different C-H bonds, particularly for distal positions, necessitate innovative approaches. In this aspect, photoredox catalysis by utilizing both transition metal and organic photocatalysts has emerged as a powerful tool for addressing these challenges under mild reaction conditions.
View Article and Find Full Text PDFMolecules
December 2024
Department of Chemistry, Faculty of Science, Umm Al-Qura University, Makkah 21955, Saudi Arabia.
The development of efficient synthetic procedures to access fused N, O-heterocyclic skeletons has been a pivotal research topic in organic synthesis for several years. Owing to the applications of N, O-fused heterocycles in organic synthesis, material sciences, and medicinal chemistry, significant efforts have been dedicated to design novel methods for their construction. To this end, 1,3-benzoxazin-4-ones are privileged candidates for N, O-heterocyclic molecules often found in natural products, agrochemicals, and materials science applications.
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