We here describe an alkynylative [5+1] benzannulation of 3-acetoxy-1,4-enynes with terminal alkynes, which enables both the construction of a benzene ring skeleton and intermolecular incorporation of an alkynyl group in a single reaction using Pd and Cu cooperative catalysts. The method represents efficient access to internal aryl alkynes through divergent functionalization of two terminal alkyne components: one alkyne serves as the one-carbon unit to realize the [5+1] benzannulation and the other alkyne as a nucleophile terminates the reaction.
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http://dx.doi.org/10.1039/d0cc06793h | DOI Listing |
Chemistry
December 2024
Institut für Anorganische und Analytische Chemie, Goethe-Universität Frankfurt am Main, Max-von-Laue-Straße 7, 60438, Frankfurt am Main, Germany.
Organo(chloro)silanes are essential chemicals, but the synthesis of compounds of the formula RSiCl with defined values of n is usually laborious. Herein, we first disclose that a [4+2]-cycloaddition between readily available ClSiC≡CSiCl and selected dienes provides facile access to vicinal bis(trichlorosilylated) benzenes and bicyclo[2.2.
View Article and Find Full Text PDFCarbazole alkaloids carbazoquinocin A-F possessing a 1-alkyl-2-methyl-3,4--carabazoquinone framework were isolated from the microorganism in 1995. Furthermore, they were found to exhibit strong inhibitory activity against lipid peroxidation. Herein, we report the integrated synthesis of -Me-analogues of 5 members of the carbazoquinocin family of natural products, namely, -Me-carbazoquinocin A, B and D-F.
View Article and Find Full Text PDFOrg Lett
July 2024
Université de Bordeaux, ISM (CNRS-UMR 5255), 351 cours de la Libération, 33405 Talence Cedex, France.
An enantioselective synthesis of the bacterial metabolite (+)-strepantibin A, a novel inhibitor of the hexokinase II (HK2) in cancer cells, is described. Its monomethylated resorcinolic -terphenyl core was conveniently prepared through a Danheiser benzannulation. The elaboration of its -quinolic chiral center was accomplished by relying on an iodyl-promoted regio- and enantioselective hydroxylative dearomatization.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
September 2024
EaStCHEM, School of Chemistry, University of St Andrews, St Andrews, Fife, KY16 9ST, UK.
The development of methods to allow the selective acylative dynamic kinetic resolution (DKR) of tetra-substituted lactols is a recognised synthetic challenge. In this manuscript, a highly enantioselective isothiourea-catalysed acylative DKR of tetra-substituted morpholinone and benzoxazinone-derived lactols is reported. The scope and limitations of this methodology have been developed, with high enantioselectivity and good to excellent yields (up to 89 %, 99 : 1 er) observed across a broad range of substrate derivatives incorporating substitution at N(4) and C(2), di- and spirocyclic substitution at C(5) and C(6), as well as benzannulation (>35 examples in total).
View Article and Find Full Text PDFChem Commun (Camb)
April 2024
Département de Chimie and Centre de Recherche sur les Matériaux Avancés (CERMA), Université Laval, 1045 Ave de la Médecine, Québec, Canada G1V 0A6.
The solution-phase synthesis of a non-benzenoid nanoribbon from an azulene-containing polymer alkyne benzannulation is reported. The nanoribbon is soluble in common organic solvents and exhibits conductivity values up to 1.5 × 10 S cm once doped by protonation in the thin film state.
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