An NHC-catalyzed [2 + 4] cyclization of alkynyl ester with α,β-unsaturated ketone to form a pyran scaffold was developed successfully. The cheap and easily available starting materials, mild reaction conditions, moderate to excellent yields, and high atom economy make this strategy attractive for the syntheses of highly substituted 4-pyran derivatives.
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http://dx.doi.org/10.1021/acs.joc.2c00022 | DOI Listing |
J Org Chem
January 2025
Key Laboratory of Chemistry and Engineering of Forest Products, State Ethnic Affairs Commission, Guangxi Key Laboratory of Chemistry and Engineering of Forest Products, Guangxi Collaborative Innovation Center for Chemistry and Engineering of Forest Products, Laboratory of Optic-electric Chemo/Biosensing and Molecular Recognition, Education Department of Guangxi Zhuang Autonomous Region, Guangxi Minzu University, Nanning 530006, China.
A regioselective [3 + 2] annulation of β,γ-alkynyl-α-ketimino esters with 1,3-dicarbonyls is disclosed. A series of -selective dihydrofurans bearing an exocyclic double bond and a quaternary carbon center are accessed without the usage of base. Control and deuterium-labeling experiments have been investigated to probe into the reaction mechanism.
View Article and Find Full Text PDFAsian J Org Chem
January 2025
Department of Medicinal Chemistry, Ernest Mario School of Pharmacy, Rutgers, The State University of New Jersey, 160 Frelinghuysen Road, Piscataway, New Jersey 08854, USA.
A one-pot process was developed to synthesize in moderate to high yield a series of 2-substituted indoles and 7-azaindoles starting from 2-iodo--mesylarylamines and terminal alkynes in the presence of CuO in DMF at 90-120 °C. Without isolation of any intermediate, our optimized conditions enabled the introduction of ester, phenyl, hydroxymethyl, hydroxyethyl, -Boc-aminomethyl, and methyl at the 2-postion of indoles and 7-azaindoles. The reaction tolerates a variety of substrates containing halogens, or acid- or base-sensitive functional groups without requiring a Pd catalyst, a ligand, or a base.
View Article and Find Full Text PDFJ Org Chem
January 2025
Guangxi Key Laboratory of Petrochemical Resource Processing and Process Intensification Technology, School of Chemistry and Chemical Engineering, Guangxi University, Nanning, Guangxi 530004, China.
Among the known aromatic -heterocycles, pyrroles are significant and versatile privileged components in pharmacologically relevant molecules. Herein, we demonstrate a protocol for the selective construction of alkynylated pyrroles in a diversity-oriented fashion through divergent C2/C5 site-selective alkynylation of pyrrole derivatives by employing a palladium catalyst with two different solvent systems. In the presence of 1,4-dioxane, the C2-alkynylation process via chelation-assisted palladation is favored.
View Article and Find Full Text PDFJ Am Chem Soc
January 2025
State Key Laboratory of Structural Chemistry, Center for Excellence in Molecular Synthesis, Fujian Institute of Research on the Structure of Matter, University of Chinese Academy of Sciences, Fuzhou 350100, China.
Chem Commun (Camb)
December 2024
Advanced Catalysis and Green Manufacturing Collaborative Innovation Center, School of Petrochemical Engineering, Changzhou University, Changzhou 213164, China.
A base-promoted cascade 5- cyclization/carboxylation of -alkynylsulfamides with CO has been accomplished, furnishing a variety of benzosultam-containing acrylates in good yields by using CO as the carboxylic source. Notably, in the case of substrates bearing a TMS-alkyne motif, the -dicarboxylation products were generated unprecedentedly.
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