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The dearomatization of 2-naphthols represents a simple method for the construction of complex 3D structures from simple planar starting materials. We describe a cyclopropanation of 2-naphthols that proceeds via cyclopropene ring-opening using rhodium and acid catalysis under mild conditions. The vinyl cyclopropane molecules were formed with high chemoselectivity and scalability, which could be further functionalized at different sites. Both computational and experimental evidence were used to elucidate the reaction mechanism.
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http://dx.doi.org/10.1002/anie.202116171 | DOI Listing |
Nat Commun
April 2025
Faculty of Chemistry and Life Sciences, Changchun University of Technology, 2055 Yan'An Street, Changchun, Jilin, 130012, P. R. China.
Since its advent 120 years ago, the [2+n] coupling cyclization of ketene has been prevalently used for the synthesis of N- and O-heterocycles. In contrast, its vinylogous version, i.e.
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April 2025
State Key Laboratory of Elemento-Organic Chemistry, Frontiers Science Center for New Organic Matter, College of Chemistry, Nankai University, Tianjin, 300071, China.
The ring opening of cyclopropenes provides a compelling platform for the rapid synthesis of various polysubstituted acyclic alkenes. However, radical-mediated reactions of this type remain underexplored, and none of the existing methods have successfully produced tetrasubstituted olefins with high stereoselectivity. We present here an aminative ring-opening of cyclopropenes with iron-aminyl radical to afford tetrasubstituted alkenyl nitriles in a highly stereoselective manner.
View Article and Find Full Text PDFChem Rev
March 2025
Institut de Chimie Organique et Analytique, ICOA, CNRS UMR 7311, University of Orléans, 45100 Orléans, France.
Cyclopropylamines are an important subclass of substituted cyclopropanes that combine the unique electronic and steric properties of cyclopropanes with the presence of a donor nitrogen atom. In addition to their presence in a diverse array of biologically active compounds, cyclopropylamines are utilized as important synthetic intermediates, particularly in ring-opening or cycloaddition reactions. Consequently, the synthesis of these compounds has constituted a significant research topic, as evidenced by the abundant published synthetic methods.
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March 2025
Institute of Green Chemistry and Molecular Engineering, School of Chemistry, Sun Yat-sen University Guangzhou 510275 China
In this paper, we describe a new type of cross-coupling between simple diazo and vinyldiazo compounds that gives access to unusual allyldiazo products. Blue light discriminates two diazo compounds towards free carbene formation, triggering sequential cyclopropenation, (3+2) cycloaddition and ring opening rearrangement processes. This strategy involves an overall reshuffle of diazo functionality and olefinic carbons of vinyldiazo compounds with an extrusion of nitrogen.
View Article and Find Full Text PDFOrg Lett
January 2025
Shenzhen Institute of Advanced Technology, Chinese Academy of Sciences, Shenzhen 518055, P. R. China.
Sulfone motifs play important roles in bioactive compounds and functional materials. The development of efficient methodologies for constructing sulfonyl-containing compounds has thus attracted considerable attention. Here, we introduce a protocol for the preparation of alkyl aryl sulfones under mild conditions.
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