Herein, we report the first environmentally friendly systematic fluoroalkoxylation reactions in bicyclic systems. New oxyfluorination products were obtained with excellent yields (up to 98%) via Wagner-Meerwein rearrangement using benzonorbornadiene and the chiral natural compound (+)-camphene as bicyclic alkenes, selectfluor as an electrophilic fluorine source, and water and various alcohols as nucleophile sources. The structure of bicyclic oxy- and alkoxyfluorine compounds was determined by NMR and QTOF-MS analyses.
Download full-text PDF |
Source |
|---|---|
| http://www.ncbi.nlm.nih.gov/pmc/articles/PMC11228819 | PMC |
| http://dx.doi.org/10.3762/bjoc.20.129 | DOI Listing |
Publication Analysis
Top Keywords
Similar Publications
Single-Carbon Insertion into Single C-C Bonds with Diazirines.
J Am Chem Soc
December 2024
Institute of Chemical Research of Catalonia (ICIQ-CERCA), The Barcelona Institute of Science and Technology, Països Catalans 16, 43007 Tarragona, Spain.
A novel platform for the skeletal editing of single C-C bonds via a single-carbon insertion has been developed using diazirines. This strategy involves the photogeneration of arylchlorocarbenes as carbynoid species that undergo site-selective carbene insertion into tertiary C-H bonds and a subsequent Wagner-Meerwein rearrangement promoted by a silver salt. Our skeletal editing strategy based on a formal selective carbyne C-C bond insertion has been demonstrated in six core-to-core conversions, including linear and cyclic benzylic substrates, alkanes and late-stage functionalizations.
View Article and Find Full Text PDFBioinspired Synthesis of Cucurbalsaminones B and C.
Angew Chem Int Ed Engl
November 2024
Frontiers Science Center for Transformative Molecules, Shanghai Key Laboratory for Molecular Engineering of Chiral Drugs, School of Chemistry and Chemical Engineering, Zhangjiang Institute for Advanced Study, Shanghai Jiao Tong University, No. 800, Dongchuan Road, Shanghai, 200240, China.
Cucurbalsaminones B (1) and C (2) are two abeo-cucurbitane triterpenoids with a unique 5/6/3/6/5-fused ring system and exhibit potent multidrug resistance (MDR)-reversing activity. Herein, we report the first synthesis of these two natural products, both of them were accomplished in 14 steps from commercially available inexpensive resource compound lanosterol. Key features of this synthesis include a biomimetic tandem Wagner-Meerwein type lanostane-to-cucurbitane rearrangement followed by a bioinspired photochemical oxa-di-π-methane (ODPM) rearrangement to complete the skeleton construction and an Eosin Y photoinduced Barton-McCombie deoxygenation to realize the challenging oxidation state adjustment of the sterically hindered C11 position.
View Article and Find Full Text PDF[4+1] Heteroannulation to Form 1-Pyrrolines through Alder-Ene Reaction of in situ Generated Ynimines: Development and Application in Total Synthesis of Borrecapine.
Angew Chem Int Ed Engl
August 2024
Laboratory of Synthesis and Natural Products I, nstitute of Chemical Sciences and Engineering, Ecole Polytechnique Fédérale de Lausanne, EPFL-SB-ISIC-LSPN, BCH 5304, 1015, Lausanne, Switzerland.
We report in this paper a novel Cu-catalyzed synthesis of polysubstituted 1-pyrrolines. The reaction of β,γ-unsaturated oxime esters 4 with terminal alkynes 5 in the presence of a catalytic amount of Cu(OAc) and 2,2'-biquinoline affords the corresponding 1,6-enynimines, which undergo a highly stereoselective Alder-ene reaction to afford 1-pyrrolines with concomitant generation of a quaternary carbon and a 2-azadiene motif. It represents an unusual [4+1] heteroannulation reaction wherein terminal alkynes act as a one carbon donor and are 1,1-difunctionalized.
View Article and Find Full Text PDFSelectfluor and alcohol-mediated synthesis of bicyclic oxyfluorination compounds by Wagner-Meerwein rearrangement.
Beilstein J Org Chem
July 2024
Department of Chemistry, Faculty of Science, Ataturk University, Erzurum, Turkey.
Herein, we report the first environmentally friendly systematic fluoroalkoxylation reactions in bicyclic systems. New oxyfluorination products were obtained with excellent yields (up to 98%) via Wagner-Meerwein rearrangement using benzonorbornadiene and the chiral natural compound (+)-camphene as bicyclic alkenes, selectfluor as an electrophilic fluorine source, and water and various alcohols as nucleophile sources. The structure of bicyclic oxy- and alkoxyfluorine compounds was determined by NMR and QTOF-MS analyses.
View Article and Find Full Text PDFSesquiterpene Cyclase BcBOT2 Promotes the Unprecedented Wagner-Meerwein Rearrangement of the Methoxy Group.
J Am Chem Soc
July 2024
Institute of Organic Chemistry, Leibniz Universität Hannover, Schneiderberg 1B, 30167 Hannover, Germany.
Presilphiperfolan-8β-ol synthase (BcBOT2), a substrate-promiscuous sesquiterpene cyclase (STC) of fungal origin, is capable of converting two new farnesyl pyrophosphate (FPP) derivatives modified at C7 of farnesyl pyrophosphate (FPP) bearing either a hydroxymethyl group or a methoxymethyl group. These substrates were chosen based on a computationally generated model. Biotransformations yielded five new oxygenated terpenoids.
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!