Oxygen-containing organic compounds, such as ethers, carboxylates, and carbamates, have recently received increasing attention because of their newly discovered applications as electrophiles in cross-coupling reactions via transition metal-catalyzed C-O bond activation. However, no cycloaddition reaction involving their C-O bond activation has been demonstrated thus far. The present study developed a Ni(0)-catalyzed unique [3+2] cycloaddition reaction of α,β-unsaturated phenyl esters with alkynes in (i)PrOH to yield cyclopentenone derivatives.
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http://dx.doi.org/10.1021/ja2059999 | DOI Listing |
J Phys Chem A
September 2024
C. Eugene Bennett Department of Chemistry, West Virginia University, Morgantown, West Virginia 26506, United States.
We investigated the reactions of the hydroxyl radical (OH) with cyclopentenone derivatives and cyclopentanone in a quasi-static reaction cell at 4 Torr across a 300-500 K temperature range. The OH radicals were generated using pulsed laser photolysis of hydrogen peroxide vapors, and the ketone reactants were introduced in excess. The relative concentrations of the radicals were monitored as a function of reaction time using laser-induced fluorescence.
View Article and Find Full Text PDFJ Org Chem
October 2024
Dipartimento di Chimica "U. Schiff", Università degli Studi di Firenze, Via della Lastruccia 13, 50019, Sesto Fiorentino (FI), Italy.
A one-pot synthesis of ring-fused, α-hydrazineyl-2-cyclopentenone derivatives is achieved by a gold(I)-catalyzed Rautenstrauch/hetero Diels-Alder/ring opening tandem reaction of suitable propargyl esters. By mixing the latter with a dialkylazodicarboxylate in the presence of a gold(I) catalyst, the 1,2-acyloxy migration/cyclization process (Rautenstrauch reaction) leads to cyclopentadienyl ester intermediates which are trapped by the heterodienophile present in situ. This provides strained intermediates which spontaneously undergo highly regioselective ring opening by a retro aza-Michael reaction promoted by the gold(I) catalyst, eventually yielding the target compounds.
View Article and Find Full Text PDFJ Org Chem
September 2024
School of Pharmacy, China Medical University, Taichung 406040, Taiwan.
Angew Chem Int Ed Engl
September 2024
Laboratorium für Organische Chemie, ETH Zürich, Vladimir Prelog Weg 3, HCI, 8093, Zürich, Switzerland.
Herein we report the development of an oxidative amination process for the streamlined synthesis of pyridones from cyclopentenones. Cyclopentenone building blocks can undergo in situ silyl enol ether formation, followed by the introduction of a nitrogen atom into the carbon skeleton with successive aromatisation to yield pyridones. The reaction sequence is operationally simple, rapid, and carried out in one pot.
View Article and Find Full Text PDFChemistry
August 2024
Department of Chemistry, Faculty of Science, Hokkaido University, Kita 10, Nishi 8, Kita-ku, Sapporo, 060-0810, Japan.
We describe a method for the synthesis of various 2-silyloxy-2-norbornen-7-ones by exploiting the specific reactivity of the 1,4-bis(silyloxy)-1,3-cyclopentadiene framework, which is generated by the silylation of a 2,2-disubstituted-1,3-cyclopentanedione bearing a picolinoyloxy group at the 2' position of its C-2 side chain. The release of the acyloxy group during the reaction generates carbocations that are then attacked by silyloxy-substituted carbons in the 1,4-bis(silyloxy)-1,3-cyclopentadiene moiety skeleton, forming a 4,5-cis-fused ring skeleton. Skeletal rearrangement of the bicyclic core results in the formation of the corresponding 2-silyloxy-2-norbornen-7-one.
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