An efficient method for the generation of an oxidopyrylium ylide from 6-acetoxy-6-acetoxymethyl-2H-pyran-3(6H)-one using a Pd catalyst and [5+2] cycloadditions of the resulting ylide are described. Among substituted styrene derivatives as dipolarophiles, electron-rich styrenes showed higher yield (up to 80%). The [5+2] cycloaddition reactions can also be applied to exo-methylene cyclic compounds, and an improved method for the synthesis of polygalolide intermediate has been demonstrated.
Download full-text PDF |
Source |
|---|---|
| http://dx.doi.org/10.1039/c7cc09552j | DOI Listing |
Publication Analysis
Top Keywords
Similar Publications
The case for an oxidopyrylium intermediate in the mechanism of quercetin dioxygenases.
J Inorg Biochem
October 2023
Department of Chemistry and Biochemistry, Baylor University, Waco, TX 76798, United States of America. Electronic address:
The quercetin dioxygenases (QDOs) are unusual metalloenzymes in that they display ring-opening dioxygenase activity with several different first-row transition metal ions which do not undergo redox changes during turnover. The QDOs are also unique in that the substrate binds as an η-flavonolate rather than the ηbidentate mode seen in all reported model complexes. The flavonol substrates were early examples of excited state intramolecular proton transfer (ESIPT) phenomena, in which photoexcitation causes an H-atom exchange between the adjacent hydroxyl and ketone, generating an oxidopyrylium emissive state.
View Article and Find Full Text PDFSilver-Catalyzed Tandem Cycloisomerization/[5 + 2] Cycloaddition of 3-Cyclopropylideneprop-2-en-1-ones with Oxidopyrylium Ylides to Form Bibridged Benzocycloheptanones.
J Org Chem
July 2023
State Key Laboratory, College of Chemistry, Institute of Elemento-Organic Chemistry, Nankai University, Weijin Road 94, Tianjin 300071, China.
Herein, we report a mild, one-pot method for silver-catalyzed tandem cycloisomerization/[5 + 2] cycloaddition reactions between readily accessible cyclopropyl-tethered allenyl ketones and benzopyranone-derived oxidopyrylium ylides. The reactions proceed a cyclobutene-fused furan intermediate generated by a cycloisomerization/1,2-carbene transfer/ring-expansion cascade. This method, which features an unprecedented formal [5 + 2] cycloaddition, delivers good to excellent yields of structurally complex bibridged benzocycloheptanones bearing a strained cyclobutane ring and an -bridged ring.
View Article and Find Full Text PDFEnantioselective 1,3-Dipolar (5+3) Cycloadditions of Oxidopyrylium Ylides and Vinylcyclopropanes toward 9-Oxabicyclononanes.
Org Lett
April 2022
State Key Laboratory and Institute of Elemento-Organic Chemistry, College of Chemistry, Nankai University, Weijin Road 94, Tianjin 300071, China.
We have developed an efficient and mild enantioselective palladium-catalyzed (5+3) cycloaddition of vinylcyclopropanes and oxidopyrylium ylides generated in situ from benzopyranones, in the presence of a chiral PHOX ligand. These reactions afford various highly functionalized bridged oxa-[3.3.
View Article and Find Full Text PDFSynthesis of Polyoxygenated Tropolones and their Antiviral Activity against Hepatitis B Virus and Herpes Simplex Virus-1.
Chemistry
February 2022
Department of Chemistry, Brooklyn College of the City University of New York, Brooklyn, NY 11210, USA.
Polyoxygenated tropolones possess a broad range of biological activity, and as a result are promising lead structures or fragments for drug development. However, structure-function studies and subsequent optimization have been challenging, in part due to the limited number of readily available tropolones and the obstacles to their synthesis. Oxidopyrylium [5+2] cycloaddition can effectively generate a diverse array of seven-membered ring carbocycles, and as a result can provide a highly general strategy for tropolone synthesis.
View Article and Find Full Text PDFTotal Synthesis of Natural Products with Bridged Bicyclo[m.n.1] Ring Systems via Type II [5 + 2] Cycloaddition.
Acc Chem Res
March 2020
Shenzhen Grubbs Institute and Department of Chemistry, Southern University of Science and Technology (SUSTech), Shenzhen 518055, China.
Natural products containing bridged ring systems are widely identified and show significant biological activity. The development of efficient synthesis reactions and strategies to construct bridged ring systems is a long-standing but very significant challenge in organic chemistry. In 2014, our group developed a unique type II [5 + 2] cycloaddition reaction that provides a facile and direct methodology for constructing highly functionalized bridged bicyclo[4.
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!