The synthesis of 2,3-disubstituted benzo[]thiophenes with selective placement of a chlorine moiety at the 3 position while maintaining diversity at the 2 position has only been accomplished by a handful of conditions in the past. The development of a greener, less expensive, and simpler method is paramount for the exploration of innovative compounds for application in medicinal and materials chemistry. Herein, the first reported copper-catalyzed electrophilic chlorocyclization method was developed and employed across diverse substrates to generate highly functionalized 2,3-disubstituted benzo[]thiophenes and 2,3,5-trisubstituted thiophenes in very high yields. This method was optimized in both ethanol and acetonitrile in a comparative solvent study. The utility of this method was further expanded beyond chlorocyclization by changing the sodium halide to generate bromo- and iodocyclization products in excellent yields.
Download full-text PDF |
Source |
|---|---|
| http://www.ncbi.nlm.nih.gov/pmc/articles/PMC6648761 | PMC |
| http://dx.doi.org/10.1021/acsomega.9b00300 | DOI Listing |
Publication Analysis
Top Keywords
Similar Publications
Copper-Catalyzed Asymmetric Nucleophilic Substitutions of TsSCF: Synthesis of Chiral SCF-Containing Compounds.
J Org Chem
December 2024
Chengdu Institute of Biology, Chinese Academy of Sciences, Chengdu 610213, China.
By employing electrophilic TsSCF as an efficient SCF source, we reported Cu/ (chiral sulfoxide-phosphine ligand)-catalyzed enantioselective nucleophilic substitutions. Under this protocol, α-pyridyl-α-fluoro esters as latent carbon nucleophiles, compounds containing a C-SCF stereocenter along with azacycles and fluorine atoms, were obtained in good yields and enantioselectivities under mild conditions (up to 68% yield, 92% ee).
View Article and Find Full Text PDFCopper-Catalyzed Regioselective and Enantioselective Hydropyridylation of Dienes for the Synthesis of Chiral Diaryl Compounds via Concerted Nucleophilic Aromatic Substitution.
Angew Chem Int Ed Engl
November 2024
Department of Chemistry, Korea Advanced Institute of Science and Technology (KAIST), Daejeon, 34141, Republic of Korea.
The synthesis of chiral 1,1-diaryl compounds, particularly those containing a pyridine moiety, is of significant interest due to their pharmaceutical applications. Here, we report the development of a copper-catalyzed enantioselective 1,4-hydropyridylation of conjugated dienes. Utilizing 2-fluoropyridine as the electrophile, CuOAc, and the chiral ligand Tol-BINAP, we optimized reaction conditions to achieve the desired chiral 1,1-diaryl products containing both a pyridine and a cis-crotyl group.
View Article and Find Full Text PDFPhotocatalysis Meets Copper Catalysis: A New Opportunity for Asymmetric Multicomponent Radical Cross-Coupling Reactions.
Acc Chem Res
December 2024
Engineering Research Center of Photoenergy Utilization for Pollution Control and Carbon Reduction, Ministry of Education, College of Chemistry, Central China Normal University, 152 Luoyu Road, Wuhan, Hubei 430079, China.
Article Synopsis
- Radical-mediated cross-coupling reactions are a powerful method for creating diverse molecular structures, but they face challenges in controlling reaction pathways and selectivity due to the high reactivity of radicals.
- The use of visible-light photoredox catalysis combined with chiral copper catalysts can enhance control over radical species and improve enantioselective reactions.
- This research focuses on innovative strategies for chiral C-C and C-O bond formation by utilizing dual photoredox/copper catalysis, highlighting the effectiveness of visible light in achieving selectivity in these reactions.
Copper-Catalyzed C(sp)-H α-Acetylation: Generation of Quaternary Centers.
Angew Chem Int Ed Engl
October 2024
Department of Chemistry, Georgetown University, Box 571227, 20057-1227, Washington, DC, USA.
α-substituted ketones are important chemical targets as synthetic intermediates as well as functionalities in natural products and pharmaceuticals. We report the α-acetylation of C(sp)-H substrates R-H with arylmethyl ketones ArC(O)Me to provide α-alkylated ketones ArC(O)CHR at RT with BuOOBu as oxidant via copper(I) -diketiminato catalysts. Proceeding via alkyl radicals R•, this method enables α-substitution with bulky substituents without competing elimination that occurs in more traditional alkylation reactions between enolates and alkyl electrophiles.
View Article and Find Full Text PDFCopper-Catalyzed Carbomagnesiation of 1-Halocyclopropenes.
Org Lett
October 2024
Schulich Faculty of Chemistry and the Resnick Sustainability Center for Catalysis, Technion - Israel Institute of Technology, Technion City, 3200009 Haifa, Israel.
We report a versatile copper-catalyzed carbomagnesiation reaction of poly- and fully substituted 1-halocyclopropenyl esters. By fine-tuning the regioselectivity of the addition, we were able to access configurationally stable fully substituted cyclopropyl carbenoid intermediates. These intermediates were subsequently trapped with electrophiles to furnish stereodefined poly- and fully substituted halocyclopropyl esters.
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!