We report chemo- and regioselective direct reductive deoxygenation of 1-en-4-yn-3-ols into 1,4-enynes through FeF3 and TfOH cooperative catalysis under NBSH-mediated conditions. Further, we show the efficient synthesis of a pharmaceutically significant 1,4-enyne. The present methodology can also be used for chemo- and regioselective direct deoxygenation of other alcohols.
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http://dx.doi.org/10.1039/c5cc10518h | DOI Listing |
Carbohydr Res
January 2025
Glycochemistry Laboratory, School of Physical Sciences, Jawaharlal Nehru University, New Delhi, 110067, India. Electronic address:
Glycohybrids are biologically significant molecules with variety of biological functions and are found as structural motifs in numerous natural products. Here, we report the synthesis of various new coumarin-based O-glycoconjugates as glycohybrids that are chirally enriched and bridged by 1,2,3-triazoles ring system. The1,2,3-triazoles bridging was done via CuAAC click-chemistry.
View Article and Find Full Text PDFOrg Biomol Chem
January 2025
Catalysis Laboratory, School of Chemistry, University of Hyderabad, Hyderabad-500 046, India.
Benzothiazole and benzoxazole heterocyclic ring-containing 1,4,5-trisubstituted-1,2,3-triazoles are well known for their wide range of applications in pharmaceutical and medicinal chemistry, but their high-yielding metal-free selective synthesis has always remained challenging as no comprehensive simple protocol has been outlined to date. Owing to their structural and medicinal importance, herein, we synthesized various benzothiazole and benzoxazole heterocyclic ring-containing 1,4,5-trisubstituted-1,2,3-triazoles in high to excellent yields with chemo-/regioselectivity from the library of benzothiazole/benzoxazole-ketones and aryl/alkyl-azides through an enolate-mediated organocatalytic azide-ketone [3 + 2]-cycloaddition under ambient conditions in a few hours. The commercial availability or quick synthesis of the starting materials and catalysts, a diverse substrate scope, chemo-/regioselectivity, quick synthesis of pharmaceutically active known compounds and their analogues, and numerous medicinal applications of functionalized benzothiazole/benzoxazole-triazoles are the key attractions of this metal-free organo-click reaction.
View Article and Find Full Text PDFOrg Lett
January 2025
Guangzhou Municipal and Guangdong Provincial Key Laboratory of Molecular Target & Clinical Pharmacology, School of Pharmaceutical Sciences, Guangzhou Medical University, Guangzhou, Guangdong 511436, China.
Presented herein is a nickel-catalyzed chemo- and regioselective three-component tandem carboamination and cyclization of terminal alkynes with organoboronic acids and anthranils for facile and modular access to 2,3-substituted quinolines. In this process, anthranil has dual roles: serving as an electrophilic aminating reagent and a redox buffer to suppress the generation of an off-cycle Ni(0) complex. Moreover, the anionic acetylacetonate (acac) ligand was found to be vital to ensure a productive Ni(I)-Ni(III)-Ni(I) catalytic cycle.
View Article and Find Full Text PDFAcc Chem Res
January 2025
Department of Chemistry, University of Wisconsin, 1101 University Avenue, Madison, Wisconsin 53706, United States.
ConspectusThe manipulation of strained rings is a powerful strategy for accessing the valuable chemical frameworks present in natural products and active pharmaceutical ingredients. Aziridines, the smallest N-containing heterocycles, have long served as building blocks for constructing more complex amine-containing scaffolds. Traditionally, the reactivity of typical aziridines has been focused on ring-opening by nucleophiles or the formation of 1,3-dipoles.
View Article and Find Full Text PDFChem Sci
December 2024
Key Laboratory of Drug-Targeting and Drug Delivery System of the Education Ministry and Sichuan Province, Sichuan Research Center for Drug Precision Industrial Technology, West China School of Pharmacy, Sichuan University Chengdu 610041 China +86 28 85502609.
As a class of readily available and multifunctional building blocks, the chemistry of 4-alken-2-ynyl carbonates remains to be explored. Presented herein is a palladium-catalysed cascade transformative reaction between 4-alken-2-ynyl carbonates and -functionalised activated alkenes. Achiral 1,1-bisalkyl-4-alken-2-ynyl carbonates undergo highly regioselective propargylic substitution with -hydroxyphenyl-tethered activated alkenes, and an auto-tandem vinylogous addition, unusual central-carbon Tsuji-Trost alkylation, protonation and β-H elimination process is followed to furnish fused and spirocyclic frameworks with high structural complexity.
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