AI Article Synopsis
Article Abstract
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.
Download full-text PDF |
Source |
|---|---|
| http://dx.doi.org/10.1002/anie.202116171 | DOI Listing |
Publication Analysis
Top Keywords
Similar Publications
β-Thioamide Sulfone Enabled Copper-Catalyzed Ring-Opening/Sulfonylation of Cyclopropenes: Access to Alkyl Aryl Sulfones.
Org 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.
View Article and Find Full Text PDFChalcogen Bonding Catalysis Enables Ring-Opening of Cyclopropene and Ring Expansion of Aryl Ketones.
Angew Chem Int Ed Engl
December 2024
School of Chemistry and Chemical Engineering, Key Laboratory of Colloid and Interface Chemistry of the Ministry of Education, Shandong University, Jinan, 250100, P. R. China.
Catalytic transformation of carbene species constitutes a fundamental part in organic synthesis, and the research in this direction has been dominated by transition metals while organic catalysts are difficult to mimic such transition-metal-like reactivity. It would significantly advance carbene chemistry if organic catalysts enable achieving classical metal-carbene approaches otherwise unrealizable reactions. Herein, we report that chalcogen bonding catalysis can solve reactivity problem to achieve an elusive Buchner ring expansion of aryl ketones appending a cyclopropene moiety as carbene precursor.
View Article and Find Full Text PDFSynthesis of Multisubstituted Cyclopentadiene Derivatives from 3,3-Disubstituted Cyclopropenes and Internal Alkynes Catalyzed by Low-Valent Niobium Complexes.
J Am Chem Soc
December 2024
Department of Applied Chemistry, Graduate School of Engineering, Osaka University, Suita, Osaka 565-0871, Japan.
A low-valent niobium species generated from NbCl and 1-methyl-3,6-bis(trimethylsilyl)-1,4-cyclohexadiene (-Me-CHD) in combination with PPh catalyzed a [2+2+1]-cycloaddition reaction of 3,3-disubstituted cyclopropenes and 2 equiv of diaryl/dialkylalkynes, leading to isomeric mixtures of multisubstituted cyclopentadienes -. The initial catalyst activation process was a one-electron reduction of NbCl with -Me-CHD to provide [NbCl(μ-Cl) (L)] (L = PMePh (), L = PPh ()) in the presence of phosphine ligands. An NMR spectroscopic time course experiment using complex as the catalyst revealed an induction period for the product formation, corresponding to an additional one-electron reduction of by the substrates to give catalytically active η-alkyne complexes of NbCl.
View Article and Find Full Text PDFStereoselective Hydroxyallylation of Cyclopropenes with Cyclopropanols via NHC Catalysis of Transient Organozinc Species.
Angew Chem Int Ed Engl
November 2024
Graduate School of Pharmaceutical Sciences, Tohoku University, 6-3 Aoba, Aramaki, 980-8578, Sendai, Japan.
A stereoselective hydroxyallylation reaction of cyclopropenes with cyclopropanols is achieved under zinc-mediated conditions, affording densely functionalized cyclopropanes with excellent diastereocontrol over three contiguous stereocenters within and outside the cyclopropane ring. A racemic variant of the reaction is synergistically promoted by catalytic N-heterocyclic carbene (NHC) and organic base, whereas chiral amino alcohol-derived bifunctional NHC enables a catalytic enantioselective variant. The reaction likely involves the generation of enolized zinc homoenolate via ring-opening of zinc cyclopropoxide and enolization of the resulting homoenolate, followed by its addition to the cyclopropene as a prochiral allylzinc nucleophile.
View Article and Find Full Text PDFSynthesis of (1-silyl)allylboronates by KOBu-catalyzed ring-opening -silylborylation of cyclopropenes.
Chem Commun (Camb)
July 2024
Division of Chemistry, Department of Materials Engineering Science, Graduate School of Engineering Science, Osaka University, Toyonaka, Osaka 560-8531, Japan.
A KOBu-catalyzed ring-opening -silylborylation of cyclopropenes with silylboronates has been developed for the synthesis of (1-silyl)allylboronates, a useful class of compounds in organic synthesis. The reaction proceeds with high selectivity under mild conditions, and the reaction mechanism has been theoretically investigated using DFT calculations.
View Article and Find Full Text PDFWant AI Summaries of new PubMed Abstracts delivered to your In-box?
Enter search terms and have AI summaries delivered each week - change queries or unsubscribe any time!