Hydroacylation of alkynes is undoubtedly the simplest and most atom-efficient approach for the synthesis of enones with diverse synthetic applications. Despite significant progress in hydroacylations, no hydroacylations exist that make use of aldehydes without a chelating group, especially when combined with terminal alkynes. Here we report a synergistic nickel-photocatalytic system that allows for the highly regio- and stereoselective hydroacylation of unactivated aldehydes and alkynes in milder conditions without the use of chelating groups.
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http://dx.doi.org/10.1021/acs.orglett.2c03481 | DOI Listing |
J Org Chem
January 2025
Department of Medical Chemistry, Faculty of Chemistry, Adam Mickiewicz University, Uniwersytetu Poznańskiego 8, 61-614 Poznań, Poland.
There has been a long search for a simple preparation of new cyclic analogues of ionophore antibiotics. We report a simple and general synthesis of three new cyclic derivatives of polyether ionophore, monensin A (MON). The application of the Huisgen 1,3-dipolar cycloaddition of azides and terminal alkynes to macrocyclization results in a concise, synthetic route to monensin lacton or lactam in only 4 steps.
View Article and Find Full Text PDFOrg Lett
January 2025
School of Pharmacy, Guizhou University of Traditional Chinese Medicine, Guiyang 550025, China.
In this work, coixalkyne A (), a natural polynuclear calcium complex with a novel cross-shaped molecular architecture, was isolated from L. along with the undescribed analogue coixalkyne B (). Their structures were identified by means of NMR spectroscopy, ECD calculations, and single-crystal X-ray diffraction.
View Article and Find Full Text PDFDalton Trans
January 2025
Department of Chemistry, Indian Institute of Technology Kharagpur, Kharagpur, 721302 India.
The reaction between 1,3-bis(3,5-dimethylpyrazolylmethyl)hexahydropyrimidine L and Mo(CO) in CHCN at 130 °C afforded a binuclear Mo(0) complex 1 containing a new macrocycle formed upon C-N bond cleavage in L in good yield. Conversely, a clean reaction takes place between L and [Mo(CO)(COD)] in THF at 60 °C to give a new metalloligand complex [Mo(CO)(κ-,-L)] 2 containing a spectator pyrazole arm in 83% yield. Their structures were determined by X-ray diffraction methods, and a plausible mechanism is proposed for the C-N bond cleavage leading to complex 1.
View Article and Find Full Text PDFChem Sci
December 2024
Department of Chemistry and Biochemistry, University of California, San Diego La Jolla California 92093 USA
Metal-organic frameworks (MOFs) can be prepared from oligomeric organic ligands to prepare materials referred to as oligoMOFs. Studies of oligoMOFs are relatively limited, with most existing reports focused on fundamental structure-property relationships. In this report, functional groups, such as terminal alkynes and pyridine groups, are installed on the tether between 1,4-benzene dicarboxylic acid (Hbdc) groups of the dimer ligands.
View Article and Find Full Text PDFNat Commun
December 2024
Department of Food Science, College of Agricultural and Life Sciences, Cornell University, Stocking Hall, Ithaca, NY, USA.
The rising demand for gold requires innovative methods for its recovery from e-waste. Here we present the synthesis of two tetrazine-based vinyl-linked covalent organic frameworks: TTF-COF and TPE-COF that adsorb gold ions and nanoparticles and catalyze the carboxylation of terminal alkynes. These covalent organic frameworks have low band gaps and high photocurrent responses.
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