Herein, we report an improved protocol for the concise synthesis of functionalized 1,4- and 1,6-dicarbonyl-derived monosilyl enol ethers via ionization of α'-hydroxy silyl enol ethers to generate unsymmetrical silyloxyallyl cations that were subsequently captured by TBS silyl enolates. These transformations were efficiently performed in acetonitrile at room temperature by employing pyridinium triflate as a catalyst. Our new reaction conditions are operationally more practical and broaden the accessibility of various 1,4- and 1,6-dicarbonyl groups, which include diketone, ketoester, and ketothioester functionalities.
Download full-text PDF |
Source |
|---|---|
| http://dx.doi.org/10.1021/acs.joc.7b01687 | DOI Listing |
Publication Analysis
Top Keywords
Similar Publications
A Hexavalent Tellurium-Based Chalcogen Bonding Catalysis Platform: High Catalytic Activity and Controlling of Selectivity.
J Am Chem Soc
January 2025
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.
Herein, we describe a hexavalent tellurium-based chalcogen bonding catalysis platform capable of addressing reactivity and selectivity issues. This research demonstrates that hexavalent tellurium salts can serve as a class of highly active chalcogen bonding catalysts for the first time. The tellurium centers in these hexavalent catalysts have only one exposed interaction site, thus providing a favorable condition for the controlling of reaction selectivity.
View Article and Find Full Text PDFPhotocatalyzed Azidofunctionalization of Alkenes via Radical-Polar Crossover.
Angew Chem Int Ed Engl
January 2025
Laboratory of Catalysis and Organic Synthesis, Institute of Chemical Sciences and Engineering, École Polytechnique Fédérale de Lausanne, CH-1015, Lausanne, Switzerland.
The azidofunctionalization of alkenes under mild conditions using commercially available starting materials and easily accessible reagents is reported based on a radical-polar crossover strategy. A broad range of alkenes, including vinyl arenes, enamides, enol ethers, vinyl sulfides, and dehydroamino esters, were regioselectively functionalized with an azide and nucleophiles such as azoles, carboxylic acids, alcohols, phosphoric acids, oximes, and phenols. The method led to a more efficient synthesis of 1,2-azidofunctionalized pharmaceutical intermediates when compared to previous approaches, resulting in both reduction of step count and increase in overall yield.
View Article and Find Full Text PDFBlock Electrochemiluminescence of Luminol through O-Etherification and Its Application in Sensing of β-Glucosidase.
Anal Chem
January 2025
School of Chemistry and Chemical Engineering, South China University of Technology, Guangzhou 510632, China.
Luminol is a well-known electrochemiluminescence (ECL) fluorophore that is applied in various sensing fields as an ECL reporter. Regulating the signal off/on transition of an ECL fluorophore offers great opportunities for sensors' design; however, such attempts on luminol are extremely scarce as it was regarded to lack promising modification sites. In this study, we developed four luminol derivatives with modification at the amine site and the enol site and systematically explored possible caging strategies to regulate ECL emission.
View Article and Find Full Text PDFChemoenzymatic Formation of Oxa-Terpenoids by Sesqui- and Diterpene Synthase-Mediated Biotransformations with 9-Oxy-FPP Ether Derivatives.
Biochemistry
January 2025
Institute of Organic Chemistry, Leibniz University Hannover, Schneiderberg 1B, Hannover 30167, Germany.
Farnesyl pyrophosphate derivatives bearing an additional oxygen atom at position 5 proved to be very suitable for expanding the substrate promiscuity of sesquiterpene synthases (STSs) and the formation of new oxygenated terpenoids. Insertion of an oxygen atom in position 9, however, caused larger restraints that led to restricted acceptance by STSs. In order to reduce some of the proposed restrictions, two FPP-ether derivatives with altered substitution pattern around the terminal olefinic double bond were designed.
View Article and Find Full Text PDFDegradable Radical Polymer Cathode for Lithium Battery with Long-Term Cycling Capability.
Angew Chem Int Ed Engl
January 2025
Department of Chemistry and Shanghai Key Laboratory of Molecular Catalysis and Innovative Materials, Institute of New Energy, iChEM (Collaborative Innovation Center of Chemistry for Energy Materials), Fudan University, Shanghai, 200433, China.
Polymer-based organic electrodes for rechargeable batteries are attractive due to their design flexibility, sustainability, and environmental compatibility. Unfortunately, waste management of conventional polymer materials typically involves incineration, which emits greenhouse gases. Consequently, degradable polymers should be ideal candidates for future green batteries.
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!