Pt(II) complexes containing unsymmetrical (pyridyl)pyrrolide ligands are shown to catalyze the hydroarylation of unactivated alkenes with selectivity for the anti-Markovnikov product. Substitution on the pyrrolide portion of the ligand allows effective tuning of the selectivity to anti-Markovnikov alkylarene products, whereas substitution on the pyridyl portion can promote competitive alkenylarene production.
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http://dx.doi.org/10.1002/chem.201405174 | DOI Listing |
ACS Cent Sci
January 2025
Jiangsu Key Laboratory of New Drug Research and Clinical Pharmacy, School of Pharmacy, Xuzhou Medical University, 209 Tongshan Road, Xuzhou 221004, China.
Herein, we report a visible-light-induced charge-transfer-complex-enabled dicarboxylation and deuterocarboxylation of C=C bonds with oxalate as a masked CO source under catalyst-free conditions. In this reaction, we disclosed the first example that the tetrabutylammonium oxalate could be able to aggregate with aryl substrates via π-cation interactions to form the charge transfer complexes, which subsequently triggers the single electron transfer from the oxalic dianion to the ammonium countercation under irradiation of 450 nm bule LEDs, releasing CO and CO radical anions. Diverse alkenes, dienes, trienes, and indoles, including challenging trisubstituted olefins, underwent dicarboxylation and anti-Markovnikov deuterocarboxylation with high selectivity to access valuable 1,2- and 1,4-dicarboxylic acids as well as indoline-derived diacids and β-deuterocarboxylic acids under mild conditions.
View Article and Find Full Text PDFJ Am Chem Soc
January 2025
Instituto Universitario de Tecnología Química, Universitat Politècnica de València-Consejo Superior de Investigaciones Científicas, Universitat Politècnica de València, Av. De los Naranjos s/n, 46022 Valencia, Spain.
Due to their conductive properties and optoelectronic tunability, MXenes have revolutionized the area of electrocatalysis and active materials in supercapacitors. In comparison, there are only a few reports on MXenes as thermal catalysts for general organic reactions. Herein, the unprecedented catalytic activity of TiC MXene for the hydroamination of alkynes is reported, overcoming the limitations of poor activity, lack of selectivity, and stability, which are generally encountered in the solid catalysts known so far.
View Article and Find Full Text PDFMolecules
December 2024
School of Environmental and Chemical Engineering, Zhaoqing University, Zhaoqing 526061, China.
Herein, we report the first example of molybdenum-catalyzed ()-Selective anti-Markovnikov hydrosilylation of alkynes. The reaction operates effectively with the utilization of minute amounts of the inexpensive, bench-stable pre-catalyst and ligand under mild conditions. Moreover, this molybdenum-catalyzed hydrosilylation process features the advantages of simple operation, excellent selectivity, and broad functional groups tolerance.
View Article and Find Full Text PDFChem Commun (Camb)
January 2025
College of Chemistry and Materials Engineering, Wenzhou University, Wenzhou, 325035, P. R. China.
A selective green-light-induced hydroselenation of alkenes with diselenides using Hantzsch ester as the hydrogen donor has been developed. In the case of electron-neutral diaryl diselenides and diacyl ones, alkenes undergo anti-Markovnikov-selective hydroselenation. When switching to electron-deficient diaryl diselenides and dialkyl ones, Markovnikov-selective hydroselenation occurs.
View Article and Find Full Text PDFChem Sci
December 2024
Advanced Research Institute of Multidisciplinary Science, School of Chemistry and Chemical Engineering, Key Laboratory of Medical Molecule Science and Pharmaceutical Engineering, Ministry of Industry and Information Technology, Beijing Institute of Technology Beijing 100081 P. R. China
We report a light-promoted hydroselenation of alkenes with high -Markovnikov selectivity. Blue light activates an aryl diselenide to generate a seleno radical with subsequent addition into an alkene to form a β-seleno carbon radical. Hydrogen atom transfer (HAT) from the selenol to the carbon radical generates the linear selenide with high selectivity in preference to the branched isomer.
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