A novel Pd-catalyzed chemo- and regiocontrolled tandem cyclization/cross-coupling reaction of 3-alkynyl chromone with aryl iodide was developed for the synthesis of 4-furo[3,2-]chromenes and xanthones. The difunctionalization of alkynes through O-attack/5-- and C-attack/6-- cyclization was reported by this rare approach, which was selectively controlled by the addition of KF or a bidentate phosphine ligand. A one-pot tandem process was demonstrated directly from γ-alkynyl-1,3-diketone for this method.
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http://dx.doi.org/10.1021/acs.orglett.2c02476 | DOI Listing |
J Org Chem
September 2024
Department of Chemistry and Chemical Sciences, Central University of Jammu, Rahya-Suchani (Bagla), District-Samba, Jammu, Jammu and Kashmir 181143, India.
Palladium-catalyzed regiocontrolled intramolecular oxypalladation-initiated cascades of multifunctional internal alkyne bearing an -tosyl tether deliver functionalized benzazepine as an exclusive product via 6- pathway in 1,4-dioxane solvent and tetrahydroquinoline scaffold as a major product via the 5- pathway in the DMSO solvent. The role of the solvent in controlling the regioselectivity is still unknown which can be a major hurdle for further reaction development. Moreover, the reaction in DMSO suffered from having a mixture of products, and no exclusive formation of tetrahydroquinoline was achieved.
View Article and Find Full Text PDFInt J Mol Sci
September 2023
Postovsky Institute of Organic Synthesis, Ural Branch of the Russian Academy of Sciences, 620108 Yekaterinburg, Russia.
A convenient approach to substituted pyrazoles and pyridazinones based on 1,2,4-triketones is presented. Chemo- and regiocontrol in condensations of -Bu, Ph-, 2-thienyl-, and COEt-substituted 1,2,4-triketone analogs with hydrazines are described. The direction of preferential nucleophilic attack was shown to be switched depending on the substituent nature in triketone as well as the reaction conditions.
View Article and Find Full Text PDFOrg Lett
September 2022
Tianjin Key Laboratory of Structure and Performance for Functional Molecules, College of Chemistry, Tianjin Normal University, Tianjin 300387, People's Republic of China.
Org Lett
September 2022
National Research Institute of Chinese Medicine, Ministry of Health and Welfare, Taipei 11221, Taiwan, ROC.
A novel Pd-catalyzed chemo- and regiocontrolled tandem cyclization/cross-coupling reaction of 3-alkynyl chromone with aryl iodide was developed for the synthesis of 4-furo[3,2-]chromenes and xanthones. The difunctionalization of alkynes through O-attack/5-- and C-attack/6-- cyclization was reported by this rare approach, which was selectively controlled by the addition of KF or a bidentate phosphine ligand. A one-pot tandem process was demonstrated directly from γ-alkynyl-1,3-diketone for this method.
View Article and Find Full Text PDFNat Commun
December 2019
Shenzhen Grubbs Institute and Department of Chemistry, Southern University of Science and Technology, Shenzhen, 518055, China.
Transition metal-catalyzed enantioselective Sonogashira-type oxidative C(sp)-C(sp) coupling of unactivated C(sp)-H bonds with terminal alkynes has remained a prominent challenge. The difficulties mainly stem from the regiocontrol in unactivated C(sp)-H bond functionalization and the inhibition of readily occurring Glaser homocoupling of terminal alkynes. Here, we report a copper/chiral cinchona alkaloid-based N,N,P-ligand catalyst for asymmetric oxidative cross-coupling of unactivated C(sp)-H bonds with terminal alkynes in a highly regio-, chemo-, and enantioselective manner.
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