Reactions of α-diazo-β-ketoesters with cyclic ketones, lactones, and carbonates are reported. Thanks to the combined use of salt [CpRu(CH3CN)3][BArF] and 1,10-phenanthroline as catalyst for the diazo decomposition, effective and practical syntheses of spiro bicyclic ketals, orthoesters, and orthocarbonates are afforded.
Download full-text PDF |
Source |
|---|---|
| http://dx.doi.org/10.1021/acs.orglett.5b03380 | DOI Listing |
Publication Analysis
Top Keywords
Similar Publications
Metal Triflate-Promoted Allylic Substitution Reactions of Cinnamyl Alcohol in the Presence of Orthoesters and Acetals.
ACS Omega
October 2019
School of Applied Sciences, University of South Wales, Pontypridd CF37 4AT, UK.
The product distribution of ethers formed from the reaction of cinnamyl alcohol with orthoesters in the presence of indium (III) triflate (InOTf) is dependent on both the reaction temperature and catalyst loading. Carrying out the reaction at room temperature under low loadings of the catalyst leads to a facile reaction generating the unexpected secondary allyl ether as the major product. In contrast, carrying out the reaction under higher catalyst loadings at elevated temperatures provides the expected primary linear ether in high yield and with excellent selectivity.
View Article and Find Full Text PDFPalladium on Carbon-Catalyzed Benzylic Methoxylation for Synthesis of Mixed Acetals and Orthoesters.
Chemistry
August 2017
Laboratory of Organic Chemistry, Gifu Pharmaceutical University, 1-25-4 Daigaku-nishi, Gifu, 501-1196, Japan.
The palladium on carbon (Pd/C)-catalyzed direct methoxylation of the benzylic positions of linear benzyl and cyclic ether substrates proceeded in the presence of i-Pr NEt under an oxygen atmosphere to give the corresponding mixed acetals. Cyclic acetal derivatives could also be converted into orthoesters. The present direct methoxylation via a carbon-hydrogen (C-H) functionalization can be accomplished using the easily-removed Pd/C and molecular oxygen as a green oxidant.
View Article and Find Full Text PDFThe hydrolysis of geminal ethers: a kinetic appraisal of orthoesters and ketals.
Beilstein J Org Chem
August 2016
Faculty of Applied Sciences, University of the West of England, Bristol, BS16 1QY, UK.
A novel approach to protecting jet fuel against the effects of water contamination is predicated upon the coupling of the rapid hydrolysis reactions of lipophilic cyclic geminal ethers, with the concomitant production of a hydrophilic acyclic hydroxyester with de-icing properties (Fuel Dehydrating Icing Inhibitors - FDII). To this end, a kinetic appraisal of the hydrolysis reactions of representative geminal ethers was undertaken using a convenient surrogate for the fuel-water interface (D2O/CD3CN 1:4). We present here a library of acyclic and five/six-membered cyclic geminal ethers arranged according to their hydroxonium catalytic coefficients for hydrolysis, providing for the first time a framework for the development of FDII.
View Article and Find Full Text PDFSynthesis of Spiro Ketals, Orthoesters, and Orthocarbonates by CpRu-Catalyzed Decomposition of α-Diazo-β-ketoesters.
Org Lett
January 2016
Department of Organic Chemistry, University of Geneva, Quai Ernest Ansermet 30, CH-1211 Geneva 4, Switzerland.
Reactions of α-diazo-β-ketoesters with cyclic ketones, lactones, and carbonates are reported. Thanks to the combined use of salt [CpRu(CH3CN)3][BArF] and 1,10-phenanthroline as catalyst for the diazo decomposition, effective and practical syntheses of spiro bicyclic ketals, orthoesters, and orthocarbonates are afforded.
View Article and Find Full Text PDFSynthesis of highly pH-responsive glucose poly(orthoester).
Angew Chem Int Ed Engl
December 2013
Department of Chemistry, Science of Advanced Materials, Central Michigan University, Mount Pleasant, MI 48858 (USA).
pH-Responsive polymers have great potential in biomedical applications, including the selective delivery of preloaded drugs to tissues with low pH values. These polymers usually contain acid-labile linkages such as esters and acetals/ketals. However, these linkages are only mildly pH-responsive with relatively long half-lives (t1/2 ).
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!