B(CF) and the corresponding anion [B(CF)] are ubiquitous in main group and transition metal chemistry. Known derivatives are generally limited to the incorporation of electron donating substituents. Herein we describe electrophilic fluorination and dearomatization of such species using XeF in the presence of BF or Lewis acidic cations. In this fashion the anions [HB(CF)], [B(CF)] and [(CF)BC≡NB(CF)], are converted to [FB(CF)], [B(CF)], and [(CF)BC≡NB(CF)], respectively. Similarly, the borane adducts (L)B(CF) (L=MeCN, OPEt) are produced. These rare examples of electrophilic attack of electron deficient rings proceed as [XeF][BF] acts as a frustrated Lewis pair effecting fluorination and dearomatization of CF rings.
Download full-text PDF |
Source |
|---|---|
| http://dx.doi.org/10.1002/chem.202401776 | DOI Listing |
Publication Analysis
Top Keywords
Similar Publications
Halogen Radical-Enabled Dearomatization of -Arylpropiolamides via Photoinduced Sequential Halogenation/Spirocyclization/Oxidation Process.
J Org Chem
December 2024
Hunan Provincial Key Laboratory of Cytochemistry, School of Chemistry and Chemical Engineering, Changsha University of Science and Technology, Changsha 410114, China.
Here we report a strategy that eliminates the need for photocatalysts and external additives, which provides an operable and mild method for halogen radical-enabled dearomatization of -arylpropiolamides under an oxygen atmosphere at room temperature. The method is applicable to a wide range of substrates, extending beyond the limited scope of -methoxyl -phenylpropynamides. Furthermore, several functional synthetic intermediates and anticancer bioactive molecules were successfully derived from 3-halogenated azaspiro[4.
View Article and Find Full Text PDFFormal -C-H-Fluorination of Pyridines and Isoquinolines through Dearomatized Oxazinopyridine Intermediates.
J Am Chem Soc
November 2024
Organisch-Chemisches Institut, Universität Münster, 48149 Münster, Germany.
Organofluorine compounds, including fluorinated pyridines and isoquinolines, play a crucial role in pharmaceuticals, agrochemicals, and materials science. However, step-economic selective C-H-functionalization to access these fluorinated azaarenes is still underexplored, with selective -C-H-fluorination proving to be especially elusive. Here we present a practical method for formal -C-H-fluorination of pyridines and isoquinolines.
View Article and Find Full Text PDFFluorination/Dearomatization of CF Groups: An FLP Route to an Electrophilic Borane and Non-Coordinating Anions.
Chemistry
August 2024
Department of Chemistry, University of Toronto, 80 St. George Street, Toronto, Ontario, M5S 3H6, Canada.
B(CF) and the corresponding anion [B(CF)] are ubiquitous in main group and transition metal chemistry. Known derivatives are generally limited to the incorporation of electron donating substituents. Herein we describe electrophilic fluorination and dearomatization of such species using XeF in the presence of BF or Lewis acidic cations.
View Article and Find Full Text PDFCarbene-Assisted Arene Ring-Opening.
J Am Chem Soc
June 2024
State Key Laboratory of Natural and Biomimetic Drugs, School of Pharmaceutical Sciences, Peking University, 100191 Beijing, China.
Despite the significant achievements in dearomatization and C-H functionalization of arenes, the arene ring-opening remains a largely unmet challenge and is underdeveloped due to the high bond dissociation energy and strong resonance stabilization energy inherent in aromatic compounds. Herein, we demonstrate a novel carbene assisted strategy for arene ring-opening. The understanding of the mechanism by our DFT calculations will stimulate wide application of bulk arene chemicals for the synthesis of value-added polyconjugated chain molecules.
View Article and Find Full Text PDFSynthesis of Fluorine-Containing Multisubstituted Oxa-Spiro[4,5]cyclohexadienones via a Fluorinated Alcohol-Catalyzed One-Pot Sequential Cascade Strategy.
J Org Chem
March 2024
Advanced Research Institute and School of Pharmaceutical Science, Taizhou University, Jiaojiang, Zhejiang 318000, P.R. China.
In recent years, the application of fluorinated alcohols as solvents, cosolvents, or additives has become important in modern organic synthesis. However, their potential as efficient catalysts in organic synthesis has not been well-explored. In this article, we report on the development of a one-pot sequential cascade reaction of -quinone methides with difluoroenoxysilanes using hexafluoroisopropanol as catalyst.
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!