The reaction of strained bicyclic olefins with alkynyl carbenes and terminal olefins involves the creation of five new sigma C-C bonds with the concomitant formation of two new rings, thus creating a complex and densely functionalized structure in a single operation.
Download full-text PDF |
Source |
|---|---|
| http://dx.doi.org/10.1021/ja027176g | DOI Listing |
Publication Analysis
Top Keywords
Similar Publications
Divergent Synthesis of Axially Chiral 2-Pyranones and Fused 2-Pyridones via -Heterocyclic Carbene-Catalyzed Atroposelective [3 + 3] Annulation.
J Org Chem
January 2025
School of Science, China Pharmaceutical University, Nanjing 210009, P. R. China.
An -heterocyclic carbene-catalyzed atroposelective [3 + 3] annulation of alkynyl acylazoliums with benzothiazole derivatives has been developed for the divergent synthesis of axially chiral triaryl 2-pyranones and fused 2-pyridones. The regioselectivity of this protocol depends on the structure of benzothiazoles with three different nucleophilic centers. The obtained axially chiral frameworks represent a new class of arylheterocycle atropisomers, which may be potentially useful in medicinal chemistry.
View Article and Find Full Text PDFScalable deoxygenative alkynylation of alcohols via flow photochemistry.
Commun Chem
November 2024
State Key Laboratory of Chemical Biology and Drug Discovery, Department of Applied Biology and Chemical Technology, The Hong Kong Polytechnic University, Hung Hom, Hong Kong SAR, China.
Internal alkynes are often contained in bioactive pharmaceuticals and crucial intermediates in material sciences, yet their production methods are often limited and challenging, necessitating the development of more efficient and versatile synthetic routes. Here we report a method of deoxygenative alkynylation of alcohols via flow photochemistry. Formation of N-heterocyclic carbene-alcohol adducts undergoes oxidation by a photocatalyst, generating alkyl radicals.
View Article and Find Full Text PDFDFT rationalization of the mechanism and selectivity in a gold-catalyzed oxidative cyclization of diynones with alcohols.
Phys Chem Chem Phys
November 2024
Key Laboratory of Chemical Additives for China National Light Industry, College of Chemistry and Chemical Engineering, Shaanxi University of Science and Technology, Xi'an 710021, P. R. China.
The mechanism, regioselectivity, and chemoselectivity in a gold-catalyzed oxidative cyclization of diynones with alcohols to give furan-3-carboxylate derivatives were explored by density functional theory (DFT). The obtained results revealed that the first step of the global reaction involves a nucleophilic attack of a pyridine--oxide derivative on the catalyst-ligated diynone, forming a vinyl intermediate that can isomerize to an α,α'-dioxo gold carbene upon the cleavage of the N-O bond. In the second step, a nucleophilic addition is also completed pyridine--oxide instead of an alcohol proposed in the experiment.
View Article and Find Full Text PDFCCC-NHC Au(iii) pincer complexes as a reliable platform for isolating elusive species.
Chem Sci
October 2024
Institut de Química Computacional i Catàlisi (IQCC) and Departament de Química, Universitat de Girona, Campus de Montilivi Girona E-17003 Catalonia Spain
The reactivity of unprecedented CCC-NHC Au(iii) pincer complexes has been investigated, employing a novel methodology for their preparation. Notably, this marks the inaugural case of CCC-NHC Au(iii) pincer complexes with a central aryl moiety where the two arms of the pincer ligand consist of N-heterocyclic carbenes (NHC). The stability conferred by the CCC-NHC ligand facilitated the isolation of elusive Au(iii) species, encompassing Au(iii)-formate, Au(iii)-F, Au(iii)-Me, and Au(iii)-alkynyl.
View Article and Find Full Text PDFDirect observation of β-alkynyl eliminations from unstrained propargylic alkoxide Cu(i) complexes by C-C bond cleavage.
Chem Sci
September 2024
Institute for Integrated Catalysis, Pacific Northwest National Laboratory Richland WA 99352 USA
β-Carbon eliminations of aryl, allylic, and propargylic alkoxides of Rh(i), Pd(ii), and Cu(i) are key elementary reactions in the proposed mechanisms of homogeneously catalysed cross-coupling, group transfer, and annulation. Besides the handful of studies with isolable Rh(i)-alkoxides, β-carbon eliminations of Pd(ii)- and Cu(i)-alkoxides are less definitive. Herein, we provide a comprehensive synthetic, structural, and mechanistic study on the β-alkynyl eliminations of isolable secondary and tertiary propargylic alkoxide Cu(i) complexes, LCuOC(H)(Ph)C[triple bond, length as m-dash]CPh and LCuOC(Ar)C[triple bond, length as m-dash]CPh (L = N-heterocyclic carbene (NHC), dppf, -BINAP), to produce monomeric (NHC)CuC[triple bond, length as m-dash]CPh, dimeric [(diphosphine)CuC[triple bond, length as m-dash]CPh], and the corresponding carbonyl.
View Article and Find Full Text PDFWant AI Summaries of new PubMed Abstracts delivered to your In-box?
Enter search terms and have AI summaries delivered each week - change queries or unsubscribe any time!