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An unprecedented dearomatized spirocyclopropane intermediate was discovered in a sequential Cp*Rh -catalyzed C-H activation and Wagner-Meerwein-type rearrangement reaction. How the oxidative O-N bond is cleaved and the role of HOAc were uncovered in this study. Furthermore, a Cp*Rh -catalyzed dearomatization reaction of N-(naphthalen-1-yloxy)acetamide with strained olefins was developed, affording a variety of spirocyclopropanes.
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http://dx.doi.org/10.1002/anie.201800803 | DOI Listing |
J Org Chem
August 2025
Área de Química Orgánica, Departamento de Química, Facultad de Ciencias, Universidad de Burgos, Pza. Misael Bañuelos s/n, 09001 Burgos, Spain.
A thermally controlled rare chemodivergent mechanistic trifurcation has been found through experimental and computational efforts. Notably, one of the available paths in this three-way mechanism allows for an unprecedented dearomatization reactivity of non-activated 2-arylphenyl benzyl ethers under very mild thermal conditions after Csp-H bond functionalization through α-lithiation, bringing easy access to regioselectively functionalized dearomatized benzochromene scaffolds via anionic dearomatization enabled by carbolithiation of a non-activated aromatic ring. A [1,2]-Wittig rearrangement and a benzyl migration reaction complete the available product alternatives.
View Article and Find Full Text PDFOrg Lett
July 2025
Department of Chemistry, University of Delhi, Delhi 110007, India.
Oxidative dearomatization of pyrroles is an important organic transformation to deliver pharmaceutically important compounds, especially the synthesis of diaryl maleimides via the dearomatization of pyrroles has always been challenging. Herein, we report an unprecedented protocol for synthesizing functionalized maleimides by NBS-promoted oxidative dearomatization of 2,3,4-trisubstituted pyrroles. The reaction proceeds via three sequential reactions: dearomatization, oxidation, and detosylation.
View Article and Find Full Text PDFJ Am Chem Soc
July 2025
School of Chemical Sciences, University of Chinese Academy of Sciences, Beijing 101408, China.
Cleaving a benzene ring under mild conditions requires disrupting its aromaticity, which is a significant challenge in modern chemistry. Although the generation of cyclic products from cleaving benzene has been reported in a few cases, the formation of acyclic products remains exceedingly rare. Inspired by the transition metal-mediated cleavage of inert bonds through multielectron reduction and functionalization, we have discovered an unprecedented ring-opening protocol for benzene and toluene.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
July 2025
Dalian Institute of Chemical Physics, Chinese Academy of Sciences, 457 Zhongshan Road, Dalian, 116023, China.
Cyclobutane-fused polycyclic scaffolds are structurally interesting cores in natural product synthesis and drug discovery. The construction of these skeletons often requires elaborate synthetic effort and gives low efficiency. We herein demonstrated the divergent construction of various cyclobutane-fused 2D/3D pentacyclic scaffolds by a photocatalytic intermolecular double dearomative cycloaddition of arenes.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
August 2025
Key Laboratory for Advanced Materials and Institute of Fine Chemicals, Key Laboratory for Advanced Materials and Feringa Nobel Prize Scientist, Joint Research Center, School of Chemistry & Molecular Engineering, East China University of Science and Technology, Meilong Road No. 130, Shanghai, 200237,
Cyclization of bicyclo[1.1.0]butanes (BCBs) is an effective way to construct saturated polycyclic 3D structures.
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