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Hydroarylation of internal alkynes by cost-effective Co-catalysis, directed by N-tert-butyl amides, is achieved to avail mono- or dihydroarylated amide products selectively in an atom and step economic way. Several important functional groups were tolerated under the reaction conditions, and syn-hydroarylation products were exclusively isolated. Notably, a 4-fold C-H hydroarylation provided a highly conjugated organic framework in one step. Kinetic study with extensive deuterium labeling experiments were performed to support the proposed mechanism.
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http://dx.doi.org/10.1021/acs.joc.6b02516 | DOI Listing |
Chem Commun (Camb)
August 2025
Department of Chemistry, Graduate School of Science, Osaka Metropolitan University, Sumiyoshi, Osaka 558-8585, Japan.
Transition-metal-catalysed direct C-H functionalisation has emerged as one of the most efficient molecular transformations, offering excellent atom and step economy. This methodology eliminates the need for pre-functionalisation of substrates, enabling the direct use of readily available starting materials, such as alkenes, to access valuable compounds. In particular, enantioselective variants of these reactions have attracted considerable attention in recent years due to their utility in constructing complex molecules.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
July 2025
Centro Singular de Investigación en Química Biolóxica e Materiais Moleculares (CiQUS) and Departamento de Química Orgánica, Universidade de Santiago de Compostela, Santiago de Compostela, 15782, Spain.
We report a versatile, highly enantioselective intramolecular hydroarylation of allenyl-tethered pyrroles and indoles. The reaction, promoted by an iridium(I)/bisphosphine chiral catalyst, provides a direct access heteropolycyclic systems bearing either tertiary or quaternary carbon stereocenters and a synthetically appealing alkenyl pendant. The method allows a highly efficient assembly of five-, six- and even seven-membered fused indole and pyrrole products, providing enantiomeric excesses of up to 99%.
View Article and Find Full Text PDFAcc Chem Res
January 2025
Department of Chemistry and Chemistry Institution for Functional Materials, Pusan National University, Busan 46241, Republic of Korea.
ConspectusControlling selectivity through manipulation of reaction intermediates remains one of the most enduring challenges in organic chemistry, providing novel solutions for selective C-C π-bond functionalization. This approach, guided by activation principles, provides an effective method for selective functional group installation, enabling direct synthesis of organic molecules that are inaccessible through conventional pathways. In particular, the selective functionalization of N-conjugated allenes and alkynes has emerged as a promising research focus, driven by advances in controlling reactive intermediates and activation strategies.
View Article and Find Full Text PDFChem 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.
View Article and Find Full Text PDFJ Am Chem Soc
July 2024
Department of Chemistry and Biochemistry, The Ohio State University, Columbus, Ohio 43210, United States.
Herein, we report room temperature, atom-economic protocols for high regio- and enantioselective tandem cycloisomerization-hydroarylation and cycloisomerization-hydroalkenylation of 1,6-enynes leading to vicinal -functionalized pyrrolidines, tetrahydrofurans, and cyclopentanes. The latter steps in these processes involve carbonyl-coordination-assisted C-H activation of aromatic aldehydes and esters, and, a similar, yet rarely seen, β-C-H activation in the case of the acrylates. Synthetically useful enantioselective versions of such reactions are rare and are limited to the C-H activation of indoles and pyrroles.
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