This contribution intends to highlight the use of the metal-catalyzed functionalization of unreactive carbon-hydrogen bonds by the carbene insertion methodology, that employs diazo compounds as the carbene source.
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Three-component diels-alder reaction through palladium carbene migratory insertion enabled dearomative C(sp)-H bond activation.
Nat Commun
December 2024
Key Laboratory of Chemical Biology and Traditional Chinese Medicine Research, Ministry of Education of China, Key Laboratory of the Assembly and Application of Organic Functional Molecules of Hunan Province, College of Chemistry and Chemical Engineering, Hunan Normal University, Changsha, Hunan, 410081, China.
Owning to the versatile nature in participation of Diels-Alder (D-A) reactions, the development of efficient approaches to generate active ortho-quinodimethanes (o-QDMs) has gained much attention. However, a catalytic method involving coupling of two readily accessible components to construct o-QDMs is lacking. Herein, we describe a palladium carbene migratory insertion enabled dearomative C(sp)-H activation to form active o-QDM species through the cross-coupling of N-tosylhydrazones with aryl halides.
View Article and Find Full Text PDFAddition and Oxidation Reactivity of a Pentacoordinate Nickelacyclobutane.
Chemistry
December 2024
Universiteit Utrecht, Chemistry, Universiteitsweg 99, 3584CG, Utrecht, NETHERLANDS, KINGDOM OF THE.
Nickelacyclobutanes are reactive intermediates in catalytic cycles involving cyclopropanation and insertion reactions. The stoichiometric study of these intermediates has shown that their reactivity is highly influenced by the coordination environment of the nickel center. A pentacoordinated nickelacyclobutane embedded in a diphosphine pincer ligand has been shown to selectively undergo various reactions with exogenous ligands, including [2+2] cycloreversion and carbene transfer to an isocyanide.
View Article and Find Full Text PDFTropospheric Fate of Methylhydroxycarbene and the Ability of a Single Water Molecule to Efficiently Promote Its Isomerization into Acetaldehyde.
J Am Chem Soc
December 2024
Chemical Sciences Division, Saha Institute of Nuclear Physics, 1/AF Bidhannagar, Kolkata 700064, India.
The ultraviolet (UV) photodissociation of pyruvic acid through the absorption of solar actinic flux generates methylhydroxycarbene (MHC) in the atmosphere. It is recognized that isolated MHC can undergo unimolecular isomerization to form acetaldehyde and vinyl alcohol. However, the rates and mechanism for its possible bimolecular reactions with atmospheric constituents, which can occur in parallel with its unimolecular reaction, is not well understood.
View Article and Find Full Text PDFSingle-Carbon Insertion into Single C-C Bonds with Diazirines.
J Am Chem Soc
December 2024
Institute of Chemical Research of Catalonia (ICIQ-CERCA), The Barcelona Institute of Science and Technology, Països Catalans 16, 43007 Tarragona, Spain.
A novel platform for the skeletal editing of single C-C bonds via a single-carbon insertion has been developed using diazirines. This strategy involves the photogeneration of arylchlorocarbenes as carbynoid species that undergo site-selective carbene insertion into tertiary C-H bonds and a subsequent Wagner-Meerwein rearrangement promoted by a silver salt. Our skeletal editing strategy based on a formal selective carbyne C-C bond insertion has been demonstrated in six core-to-core conversions, including linear and cyclic benzylic substrates, alkanes and late-stage functionalizations.
View Article and Find Full Text PDFTriftosylhydrazone in Single-Atom Skeletal Editing.
Acc Chem Res
January 2025
Department of Chemistry, Northeast Normal University, Changchun 130024, China.
ConspectusIn the past decade, single-atom skeletal editing, which involves the precise insertion, deletion, or exchange of single atoms in the core skeleton of a molecule, has emerged as a promising synthetic strategy for the rapid construction or diversification of complex molecules without laborious synthetic processes. Among them, carbene-initiated skeletal editing is particularly appealing due to the ready availability and diverse reactivities of carbene species. The initial endeavors to modify the core skeleton of heteroarenes through carbon-atom insertion could date back to 1881, when Ciamician and Denstedt described the conversion of pyrroles to pyridines by trapping haloform-derived free carbene.
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