We report herein the phosphine-catalyzed 1,2-diacylation of alkynes using acyl fluorides and acylsilanes as acyl sources. The key to the success of the reaction is a formal oxidative addition-ligand metathesis-reductive elimination cycle based on phosphine redox catalysis, which allows for the installation of two different acyl groups into an alkyne in a regioselective manner.
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http://dx.doi.org/10.1021/acs.orglett.2c03910 | DOI Listing |
Chemistry
January 2025
Université de Rennes 1, Chemistry, Equipe CORINT, Institut des Sciences Chimiques de Rennes, Université de Rennes 1 - UMR 6226 CNRS, Bâtiment 10A, Bureau 158, Avenue du Général Leclerc, 35042, Rennes, FRANCE.
Capozzi's groundbreaking work in 1982 introduced a fascinating reaction involving highly reactive tertiary aliphatic cations and silylated alkynes. This reaction provided an innovative solution to the challenge of coupling a fully substituted tertiary aliphatic fragment with an alkyne moiety. Building upon Capozzi's pioneering efforts, we started an extensive exploration of reaction conditions to expand the initial scope of this reaction.
View Article and Find Full Text PDFBiosensors (Basel)
January 2025
Department of Chemical Engineering, University of California Davis, Davis, CA 95616, USA.
Polydiacetylenes (PDAs) are conjugated polymers that are well known for their colorimetric transition from blue to red with the application of energetic stimulus. Sensing platforms based on polymerized diacetylene surfactant vesicles and other structures have been widely demonstrated for various colorimetric biosensing applications. Although less studied and utilized, the transition also results in a change from a non-fluorescent to a highly fluorescent state, making polydiacetylenes useful for both colorimetric and fluorogenic sensing applications.
View Article and Find Full Text PDFNat Chem
January 2025
TUM School of Natural Sciences, Department of Chemistry, Chair of Inorganic and Metal-Organic Chemistry and Catalysis Research Center, Technical University of Munich, Garching, Germany.
The exploration of ligated metal clusters' chemical space is challenging, partly owing to an insufficiently targeted access to reactive clusters. Now, dynamic mixtures of clusters, defined as living libraries, are obtained through organometallic precursor chemistry. The libraries are populated with interrelated clusters, including transient and highly reactive ones, as well as more accessible but less reactive species.
View Article and Find Full Text PDFSci Rep
January 2025
Plant Biotechnology Lab, Department of Botany, Faculty of Science, Dayalbagh Educational Institute (Deemed to be University), Dayalbagh, Agra, 282005, India.
Piper longum, commonly known as long pepper, is highly valued for its bioactive alkaloid piperine, which has diverse pharmaceutical and culinary applications. In this study, we used high-throughput sequencing and de novo transcriptome assembly to analyze the transcriptomes of P. longum leaves, roots, and spikes.
View Article and Find Full Text PDFJ Org Chem
January 2025
Antibiotics Research and Re-evaluation Key Laboratory of Sichuan Province, Sichuan Industrial Institute of Antibiotics, School of Pharmacy, Chengdu University, 2025 Chengluo Avenue, Chengdu 610016, P. R. China.
We report a highly regioselective 1,2-addition of P(O)-H compounds to the in situ generated β,γ-alkynyl-α-ketimine derived from 3-alkynyl-3-hydroxyisoindolinones, which provided a general protocol for the preparation of 3,3-disubstituted isoindolinones featuring both phosphoryl and alkynyl groups at a quaternary carbon center. The use of only 2-5 mol % of an inexpensive catalyst (In(ClO)·8HO or Bi(OTf)) allowed the smooth output of the desired products under mild conditions (25 °C, 0.5-24 h) with a broad substrate scope (35 examples) in up to >99% yield.
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