To advance more efficient dearomatization approaches, we present herein an organocatalyzed asymmetric double dearomatization reaction of tricyclic phenols and alkoxybenzenes by leveraging a novel steric hindrance-regulated dearomatization strategy for nonfunctionalized phenols. This protocol allows the efficient synthesis of structurally complex polycyclic diketones with four tertiary carbon centers under mild conditions while also showcasing the potential of multiple dearomatizations for building intricate molecular frameworks from simple starting materials.
Download full-text PDF |
Source |
|---|---|
| http://dx.doi.org/10.1021/acs.orglett.4c03921 | DOI Listing |
Publication Analysis
Top Keywords
Similar Publications
Organocatalyzed Enantioselective Double Dearomatization of Tricyclic Phenols and Alkoxybenzenes.
Org Lett
December 2024
Key Laboratory of Preclinical Study for New Drugs of Gansu Province, School of Basic Medical Sciences & Research Unit of Peptide Science, Chinese Academy of Medical Sciences, 2019RU066, Lanzhou University, Lanzhou 730000, China.
To advance more efficient dearomatization approaches, we present herein an organocatalyzed asymmetric double dearomatization reaction of tricyclic phenols and alkoxybenzenes by leveraging a novel steric hindrance-regulated dearomatization strategy for nonfunctionalized phenols. This protocol allows the efficient synthesis of structurally complex polycyclic diketones with four tertiary carbon centers under mild conditions while also showcasing the potential of multiple dearomatizations for building intricate molecular frameworks from simple starting materials.
View Article and Find Full Text PDFSynthesis of dispiro-orthoester an acetal oxo-carbenium ion.
Chem Commun (Camb)
November 2024
Department of Chemistry Indian Institution of Technology Kanpur, Kanpur, 208016, Uttar Pradesh, India.
The first dispiro orthoester a spiroacetal oxo-carbenium ion is presented. Oxidative dearomatization of phloretic esters results in a bifunctional electrophilic spiroacetal oxo-carbenium ion, which undergoes a double nucleophilic addition by diol delivering a range of unusual dispiro-orthoesters with an excellent diversity.
View Article and Find Full Text PDFRhodium-Catalyzed Double Dearomatization of 1,2,3-Triazole-Isoxazole Dyads: Synthesis of Nonfused 1-1,3-Diazepines.
Org Lett
September 2024
St. Petersburg State University, Institute of Chemistry, Saint Petersburg 199034, Russia.
A double dearomatization of dyads consisting of 1-sulfonyl-1,2,3-triazoles and 3-aryl-5-methoxyisoxazoles was applied for the efficient synthesis of nonfused 1-1,3-diazepines. The plausible mechanism of the cascade reaction includes transformation of the 1,2,3-triazole to rhodium azavinyl carbene, the -selective hydride shift to form the 1-azabuta-1,3-diene moiety, rhodium-catalyzed ring contraction of the isoxazole to azirine, and pseudopericyclic four-atom ring expansion of the azirine. The synthetic utility and antiproliferative activity of the 1,3-diazepines obtained have been demonstrated.
View Article and Find Full Text PDFCascade Synthesis of Pyrrolo[1,2-]quinolines and Pyrrolo[2,1-]isoquinolines via Formal [3 + 2]-Cycloaddition of Push-Pull Nitro Heterocycles with Carbonyl-Stabilized Quinolinium/Isoquinolinium Ylides.
J Org Chem
July 2024
Samara State Technical University, 244 Molodogvardeyskaya St., Samara 443100, Russian Federation.
Various substituted pyrrolo[1,2-]quinolines and pyrrolo[2,1-]isoquinolines were synthesized in good to high yields by the EtN-mediated reaction of push-pull 3-nitrobenzofurans or 1-Ts-/1-Ms-3-nitroindoles and precursors of carbonyl-stabilized quinolinium and isoquinolinium ylides as 1,3-dipole equivalents. These transformations proceed in a one-pot manner starting with the formal [3 + 2]-cycloaddition stage, which is accompanied by double dearomatization of both quinoline/isoquinoline and benzofuran/indole moieties, followed by ring-opening of cyclic intermediate formed and nitrous acid elimination sequence. [3 + 2]-Cycloadducts were isolated as the final products in cases of impossibility or difficulty of their enolization.
View Article and Find Full Text PDFTungsten-anisole complex provides 3,6-substituted cyclohexenes for highly diversified chemical libraries.
Sci Adv
February 2024
Department of Chemistry, University of Virginia, Charlottesville, VA 22904 USA.
Medicinal chemists use vast combinatorial molecular libraries to develop leads for new pharmaceuticals. The syntheses of these compounds typically rely on coupling molecular fragments through atoms with planar (sp) geometry. These so-called flat molecules often lack the protein binding site specificity needed to be an effective drug.
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!