A simple and straightforward approach to the synthesis of trifluoromethyl and difluoromethyl ketones from widely available carboxylic acids is disclosed. The transformation utilizes an acyloxyphosphonium ion as the active electrophile, conveniently generated in situ from the carboxylic acid substrate by using commodity chemicals. The utility of the reaction system is exemplified by its chemoselectivity, with tolerance to a variety of important functional groups. The late-stage functionalization of carboxylic acid active pharmaceutical ingredients and pharmaceutically relevant compounds is also discussed.
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http://dx.doi.org/10.1002/chem.202102854 | DOI Listing |
Angew Chem Int Ed Engl
January 2025
Nanjing University, Chemistry, Xianlin 163Hao, Nanjing 210023, 210023, Nanjing, CHINA.
The simple and efficient conversion of carboxylic acids into structurally diverse organic molecules is highly desirable in chemical synthesis. This review covers recent developments in photocatalytic methodology for late-stage transformations of complex carboxylic acids and their derivatives enabled by radical decarboxylation and deoxygenation, highlighting some representative and significant contributions in this field. These advancements are categorized based on the reactivity patterns exhibited by the carboxylic acids.
View Article and Find Full Text PDFFood Chem X
January 2025
Center of Food and Fermentation Technologies (TFTAK), Mäealuse 2/4B, 12618 Tallinn, Estonia.
Cassava is a starchy staple typically consumed in tropical countries; however, its high moisture content renders it susceptible to post-harvest deterioration. Fermentation has been used to improve shelf-life, functional properties, nutrient bioavailability, minimize toxic compounds, and alter aroma. In this study, the effect of added salt (5-25 %) on the pH, titratable acidity (TTA), and volatile compounds (VOCs) in cassava fermented was investigated.
View Article and Find Full Text PDFThis study aim is to elucidate the relationship between the microbial community dynamics and the production of volatile flavor compounds during the fermentation process of bacterial-type i. Using high-throughput sequencing (HTS) and headspace solid-phase microextraction, gas chromatography-mass spectrometry (HS-SPME-GC-MS) was used to investigate microbial diversity and volatile compound profiles at different fermentation stages. Spearman correlation analysis was employed to identify potential associations between microbial genera and flavor compounds.
View Article and Find Full Text PDFNature
January 2025
Department of Chemistry, The Scripps Research Institute, La Jolla, CA, USA.
C-H activation is the most direct way of functionalizing organic molecules. Many advances in this field still require specific directing groups to achieve the necessary activity and selectivity. Developing C-H activation reactions directed by native functional groups is essential for their broad application in synthesis.
View Article and Find Full Text PDFJ Am Chem Soc
January 2025
Department of Chemistry and Biochemistry, University of California-Los Angeles, Los Angeles, California 90095-1569, United States.
The homolytic cleavage of C-C bonds adjacent to specific functional groups has lately emerged as a versatile approach for molecular diversification. Despite the ubiquity and synthetic utility of ketones, radical fragmentation of their α-C-C bonds has proven to be a formidable challenge. Here, we present a broadly applicable deacylative strategy designed to homolytically cleave aliphatic ketones of various complexities, including transformations of cycloalkanones into carboxylic acids tethered to C-centered free radicals that can be engaged in diverse radical-based processes.
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