The intramolecular C(sp3)-H/C(sp2)-H cross-coupling of 1,3-dicarbonyl compounds has been achieved through Cp2Fe-catalyzed electrochemical oxidation. The key to the success of these dehydrogenative cyclization reactions is the selective activation of the acidic α-C-H bond of the 1,3-dicarbonyl moiety to generate a carbon-centered radical.
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http://dx.doi.org/10.1039/c8cc02472c | DOI Listing |
J Org Chem
January 2025
Department of Pharmacy, College of Pharmacy, Kyung Hee University, 26 Kyungheedae-ro, Dongdaemun-gu, Seoul 02447, Republic of Korea.
In this study, we developed palladium-catalyzed dehydrogenative cyclization to transform 1-(2-aminoaryl)-3-arylpropan-1-ones into 2-arylquinolin-4(1)-ones, also known as aza-flavones which are the bioisosteres of flavones, in an atom-economic manner. This method exhibited excellent chemical compatibility with a broad substrate scope, accommodating up to 25 derivatives. Additionally, kinetic studies were performed to elucidate the reaction mechanism.
View Article and Find Full Text PDFSci Bull (Beijing)
December 2024
State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, University of Chinese Academy of Sciences, Chinese Academy of Sciences, Shanghai 200032, China. Electronic address:
Divergent synthesis of valuable molecules through common starting materials and metal catalysis represents a longstanding challenge and a significant research goal. We here describe chemodivergent, highly enantio- and regioselective nickel-catalyzed reductive and dehydrogenative coupling reactions of alkynes, aldehydes, and silanes. A single chiral Ni-based catalyst is leveraged to directly prepare three distinct enantioenriched products (silyl-protected trisubstituted chiral allylic alcohols, oxasilacyclopentenes, and silicon-stereogenic oxasilacyclopentenes) in a single chemical operation.
View Article and Find Full Text PDFOrg Lett
January 2025
Institute of Next Generation Matter Transformation, College of Material Sciences Engineering at Huaqiao University, 668 Jimei Boulevard, Xiamen, Fujian 361021, China.
Domino cascade reactions, which can construct multiple bonds in one pot, are efficient methods to synthesize N-heterocycles and other useful skeletons. Herein, we report an expedient synthesis of polysubstituted benzo[][1,5]naphthyridine via Mn(III)-mediated C-C bond cleavage of cyclopropanols. These reactions were initiated by addition of β-carbonyl radicals, generated from cyclopropyl alcohols in the presence of Mn(III), to 2-(2-isocyanophenyl)acetonitriles to give quinolin-3-amines, which went through intramolecular cyclizations and dehydrogenation to give the final products.
View Article and Find Full Text PDFLangmuir
December 2024
Key Laboratory for Green Chemical Process of Ministry of Education, Hubei Novel Reactor & Green Chemical Technology Key Laboratory, School of Chemical Engineering and Pharmacy, Wuhan Institute of Technology, Wuhan, Hubei 430205, China.
The synergetic effect of different zinc active sites with a Brønsted acid site (BAS) in Zn-MCM-22 for -octane dehydrogenation cracking and ethane dehydroaromatization was investigated. Zn-MCM-22 catalysts containing ZnO were prepared via incipient wetness impregnation (IM) using liquid ion grafting, whereas those containing [ZnO] were prepared via atom-planting (AP) using the gas dechlorination reaction. The synergetic effects of BAS with micropore incorporated [ZnO] and external surface ZnO species on the dehydrogenation of different molecule size reactants -octane and ethane were compared.
View Article and Find Full Text PDFOrg Lett
January 2025
Max-Planck-Institute for Chemical Energy Conversion, Stiftstraße 34-36, 45470 Mülheim an der Ruhr, Germany.
A novel polycyclic naphthalenone motif was obtained by electrochemical synthesis starting from naphthols. The process is solvent controlled, and the highly diastereoselective cyclization is due to a solvent cage. The direct, anodic dehydrogenative sp-coupling was carried out by flow electrolysis.
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