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Described herein is an efficient copper-catalyzed tandem alkyne indolylcupration-initiated 1,2-indole migration/6π-electrocyclic reaction of allene-ynamides with indoles by the in situ-generated metal carbenes. This method allows the efficient synthesis of valuable indole-fused spirobenzo[]indole-cyclohexanes with high regio- and stereoselectivity. In addition, this reaction affords rapid access to the functionalized spirobenzo[]indole-cyclohexanes in the absence of indoles by a presumable 5-exo-dig cyclization/Friedel-Crafts alkylation via copper-containing all-carbon 1,4-dipoles.
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http://dx.doi.org/10.1021/acs.orglett.4c01483 | DOI Listing |
ACS Electrochem
September 2025
Department of Chemistry, Molecular Sciences Research Hub, Imperial College London, White City Campus, Wood Lane, London W12 0BZ, United Kingdom.
The development of copper-catalyzed C-H functionalization processes is challenging due to the inefficiency of conventional chemical oxidants in regenerating the copper catalyst. This study details the development of a mediated electrosynthetic approach involving triple catalytic cycles in transient C-H functionalization to achieve efficient copper-catalyzed C-(sp)-H sulfonylation of benzylamines with sodium sulfinate salts. The triple catalytic system consists of a copper organometallic cycle for C-H functionalization, an aldehyde transient directing group (TDG) as an organocatalyst for imine formation, and a ferrocenium salt as an electrocatalyst.
View Article and Find Full Text PDFOrg Lett
September 2025
Flavors and Fragrance Engineering and Technology Research Center of Henan Province, College of Tobacco Science, Henan Agricultural University, Zhengzhou 450046, China.
We developed a photocatalytic copper-catalyzed stereodivergent 3,4-hydroalkoxylation of 1,3-dienes. By simply controlling reaction time, this protocol selectively affords either - or -allylic ethers in moderate to excellent yields with high stereoselectivity (up to >20/1). The transformation demonstrates remarkable scalability, maintaining excellent stereocontrol even at gram-scale operations.
View Article and Find Full Text PDFJ Am Chem Soc
September 2025
State Key Laboratory of Bioinspired Interfacial Materials Science, MOE Key Laboratory of Geriatric Diseases and Immunology, Key Laboratory of Organic Synthesis of Jiangsu Province, College of Chemistry, Chemical Engineering and Materials Science, Soochow University, Suzhou 215123, China.
Amide units and relative carbonyl families such as ureas and their derivatives are central important backbones of numerous compounds with activities of relevance to biology or medicinal chemistry. Driven by their prevalence, a general technology that enables sustainable amide-unit synthesis should afford new opportunities for chemical innovation. Generally, stoichiometric quantities of activating reagents, (tri)phosgene and its derivatives, or CO are commonly used in the literature to construct such scaffolds, which represent the drawbacks of these approaches.
View Article and Find Full Text PDFACS Catal
August 2025
Department of Chemistry, Duke University, Durham, North Carolina 27708, United States.
A three-component amino etherification of alkenes presents an ideal and direct strategy to access high-value 1,2-alkylamino ethers yet remains challenging. Herein, we disclosed a catalytic three-component amino etherification of alkenes that enables unprecedented incorporation of versatile aliphatic amines and structurally diverse alkyl or aryl ethers onto alkenes of various substitution patterns. The success of this method relies on a copper-catalyzed electrophilic amination of alkenes using -benzoyl-hydroxylamines and the subsequent C-O bond formation using silyl ethers.
View Article and Find Full Text PDFScience
August 2025
Department of Chemistry, Johns Hopkins University, Baltimore, MD, USA.
Copper-catalyzed radical C(sp)‒N coupling has become a major focus in synthetic catalysis over the past decade. However, achieving this reaction manifold by using enzymes has remained elusive. In this study, we introduce a photobiocatalytic approach for radical benzylic C(sp)‒N coupling using a copper-substituted nonheme enzyme.
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