An α-vinylation of enolizable ketones has been developed by using β-bromostyrenes and a KO tBu/NMP system. β,γ-Unsaturated ketones of E configuration were obtained in excellent yield and selectivity. Further synthetic possibilities are highlighted by one-pot functionalization via trapping of intermediate dienolates with alkyl, allyl, benzyl, and propargyl halides to generate quaternary centers. The reported transformation is believed to involve phenylacetylene and propargylic alcohol derivatives.
Download full-text PDF |
Source |
|---|---|
| http://dx.doi.org/10.1021/acs.orglett.8b04004 | DOI Listing |
Publication Analysis
Top Keywords
Similar Publications
Polarity-Reversed Functionalization of Aliphatic Aldehydes via Divergent Nickel Hydride Catalysis.
Angew Chem Int Ed Engl
December 2024
State Key Laboratory of Coordination Chemistry, Engineering Research Center of Photoresist Materials, Ministry of Education, Chemistry and Biomedicine Innovation Center (ChemBIC), School of Chemistry and Chemical Engineering, Nanjing University, 210093, Nanjing, China.
Divergent catalysis represents an exciting frontier for unlocking molecular structural diversity and exploring new activation modes. Here, we report the unexpected discovery of polarity-reversed divergent activation and functionalization of aliphatic aldehydes, where enolizable aliphatic aldehydes are selectively activated by nickel hydride to form two distinct alkylnickel intermediates divergently. This mild and operationally simple process enables the transformation of a wide variety of readily available aliphatic aldehydes, along with alkyl or aryl electrophiles, into the corresponding secondary alcohols or more challenging deoxygenated alkanes with excellent chemoselectivity.
View Article and Find Full Text PDFTargeted isolation of antiviral cinnamoylphloroglucinol-terpene adducts from by building blocks-based molecular networking approach.
Acta Pharm Sin B
October 2024
State Key Laboratory of Bioactive Molecules and Druggability Assessment, Jinan University, Guangzhou 510632, China.
The building blocks-based molecular network (BBMN) strategy was applied to the phytochemical investigation of , leading to the targeted isolation of eighteen novel cinnamoylphloroglucinol-terpene adducts (CPTAs) with diverse skeleton types (cleistoperones A-R, -). Their structures including absolute configurations were determined by extensive spectroscopic methods, quantum chemical calculations, and single-crystal X-ray crystallographic experiments. Cleistoperone A (), consisting of a cinnamoylphloroglucinol motif and two linear monoterpene moieties, represents an unprecedented macrocyclic CPTA, whose densely functionalized tricyclo[15.
View Article and Find Full Text PDFCatalytic Asymmetric Synthesis of Bicyclic Isothioureas from a Common Enolizable Template.
J Org Chem
November 2024
Department of Organic Chemistry I, Faculty of Chemistry, University of the Basque Country UPV/EHU, Manuel Lardizabal Pasealekua 3, Donostia-San Sebastian 20018, Spain.
While bicyclic isothiourea (ITU) moieties are found in biologically active molecules and organocatalysts, a catalytic asymmetric synthesis of ITUs is pending. Here, we report the catalytic, enantioselective functionalization of enolizable template with a variety of electrophiles, including unsaturated ketones, esters, sulfones, nitro compounds, and thiolating reagents, as an entry to enantioenriched bicyclic ITUs . Scope and limitations are shown, as well as examples of product derivatization.
View Article and Find Full Text PDFStereoselective mechanochemical synthesis of thiomalonate Michael adducts via iminium catalysis by chiral primary amines.
Beilstein J Org Chem
September 2024
Faculty of Bioorganic Chemistry, Wrocław University of Science and Technology, wyb. Wyspiańskiego 27, 50-370 Wrocław, Poland.
The study presents a novel approach utilizing iminium salt activation and mild enolization of thioesters, offering an efficient and rapid synthesis of Michael adducts with promising stereoselectivity and marking a significant advancement in mechanocatalysis. The stereoselective addition of bisthiomalonates - to cyclic enones and 4-chlorobenzylideneacetone proceeds stereoselectively under iminium activation conditions secured by chiral primary amines, in contrast to oxo-esters as observed in dibenzyl malonate addition. Mild enolization of thioesters allows for the generation of Michael adducts with good yields and stereoselectivities.
View Article and Find Full Text PDFMining for antifungal agents to inhibit biofilm formation of Candida albicans: A study on green synthesis, antibiofilm, cytotoxicity, and in silico ADME analysis of 2-amino-4H-pyran-3-carbonitrile derivatives.
Microb Pathog
November 2024
Department of Chemistry, PDEA's Prof. Ramkrishna More College, Pune, 411044, India; Interdisciplinary School of Science (IDSS), Savitribai Phule Pune University, Pune 411007, India. Electronic address:
Candida albicans (C. albicans) biofilm infections are quite difficult to manage due to their resistance against conventional antifungal drugs. To address this issue, there is a desperate need for new therapeutic drugs.
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!