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A highly efficient approach to indolo [1,2-a]quinoxaline derivatives through a Pd-catalyzed regioselective C-H olefination/cyclization sequence has been developed. This transformation has a wide range of substrates with various functional groups, and the corresponding heterocyclic products were obtained in good yields.
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http://dx.doi.org/10.1021/ol203275b | DOI Listing |
Org Lett
September 2025
Department of Medicinal Chemistry, National Institute of Pharmaceutical Education and Research (NIPER), Ahmedabad, Gujarat 382355, India.
Herein, we report an easily tunable and regioselective Pd-catalyzed allene-alkyne coupling protocol for the stereodivergent synthesis of - and -1,3-enynes using purine allenamine by a simple switch of ligands P(-tolyl)Ph and Boc-Phe-OH. For the first time, we have explored mono--protected amino acids (MPAAs) as ligands in allene-alkyne coupling to furnish -1,3-enynes selectively. This protocol streamlined the access to chiral 1,3-enynes and addressed the long-standing stereoselectivity challenges associated with 1,3-enynes from allene-alkyne coupling.
View Article and Find Full Text PDFJ Am Chem Soc
August 2025
Leibniz Institute for Catalysis, Albert-Einstein-Straße 29a, 18059 Rostock, Germany.
A unique multimetallic catalyst system that allows for the direct carbonylation of aliphatic and aromatic olefins with carbon dioxide and hydrogen has been developed. The employment of palladium and iridium precursors, in conjunction with 1,2-bis(di--butylphosphinomethyl)benzene (dbpx) or its derivatives as active ligands and Zn(OTf) (OTf: trifluoromethanesulfonate) as an essential acidic additive, has been shown to result in the selective formation of aliphatic esters in CO-based carbonylations, exhibiting unparalleled regioselectivity. Detailed control experiments and mechanistic investigations suggest an initial Ir-catalyzed formation of alkyl formates from carbon dioxide, followed by Pd-catalyzed alkoxycarbonylation at a low CO concentration.
View Article and Find Full Text PDFJ Org Chem
September 2025
Department of Chemistry and Biochemistry, Texas Tech University, Lubbock, Texas 79409, United States.
Carbazole scaffolds exhibit diverse applications in materials and biomedical research. We report here a regioselective acylation reaction of carbazole derivatives via a six-membered palladacycle intermediate, featuring the broad functional group compatibility and unique regioselectivity. Additionally, the tolerance of bromo substituents enables further derivatization of the products.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
August 2025
Frontiers Science Center for Transformative Molecules, Center for Chemical Glycobiology, Shanghai Key Laboratory for Molecular Engineering of Chiral Drugs, State Key Laboratory of Synergistic Chem-Bio Synthesis, School of Chemistry and Chemical Engineering, Zhangjiang Institute for Advanced Study,
The selective modification of carbohydrates to achieve structural complexity has emerged as a crucial strategy in carbohydrate-based drug development. However, the intricate stereochemistry and densely packed functional groups of carbohydrates pose significant challenges for precise stereoselectivity and regioselectivity control. Herein, we report a palladium-catalyzed, stereospecific, and ligand-controlled regiodivergent glycosyl Suzuki-Miyaura coupling of 3-boryl-glycals, establishing a robust platform for glycoside diversification with versatile C1 and C3 modification.
View Article and Find Full Text PDFACS Catal
August 2025
University of Texas at Austin, Austin, Texas 78712, United States.
Alkyl boronic acids and esters are versatile synthetic intermediates that generally require several steps to synthesize. Three-component alkene arylboration reactions allow for the rapid synthesis of alkyl boronic esters. Herein, we report the base-free aerobic Pd-catalyzed three-component alkene arylboration, which allows direct access, in a single step, to alkyl boronic esters from readily available precursors: aryl boronic acids, alkenes, and bis(pinacol)diboron.
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