An efficient and practical protocol for completely regioselective and highly stereoselective synthesis of vinyldiazaphosphonates from N-heterocyclic phosphine (NHP) and allenes via phospha-Michael/intramolecular nucleophilic substitution reaction has been developed. This transformation enabled the synthesis of valuable densely functionalized vinyldiazaphosphonates with a β-, γ-unsaturated ester moiety under mild reaction conditions. Synthetic utility of vinyldiazaphosphonates was demonstrated by a series of synthetic manipulations.
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http://dx.doi.org/10.1021/acs.joc.5b02184 | DOI Listing |
Angew Chem Int Ed Engl
January 2025
CNRS/UCSD, Chemistry, University of California, San Diego, 5213 Pacific Hall,, Department of Chemistry, 92093-0343, La jolla, UNITED STATES.
N-Heterocyclic carbene (NHC) ligands possess the ability to stabilize metal-based nanomaterials for a broad range of applications. With respect to metal-hydride nanomaterials, however, carbenes are rare, which is surprising if one considers the importance of metal-hydride bonds across the chemical sciences. In this study, we introduce a bottom-up approach leveraging preexisting metal-metal m-center-n-electron (mc-ne) bonds to access a highly stable cyclic(alkyl)amino carbene (CAAC) copper-hydride nanocluster, [(CAAC)6Cu14H12][OTf]2 with superior stability compared to Stryker's reagent, a popular commercial phosphine-based copper hydride catalyst.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
November 2024
Institute of Catalysis for Energy and Environment, College of Chemistry and Chemical Engineering, Shenyang Normal University, Shenyang, 110034, China.
Metal nanoclusters stabilized by N-heterocyclic carbene (NHC) ligands have attracted increasing interest for their special structures and diverse applications. However, developing synthetic strategies and extending the database of NHC-protected nanoclusters are still challenging tasks. In this work, a novel and rapid synthetic method is developed to prepare AuAg alloy nanocluster ligated by carbene based on the reactivity of nanoclusters.
View Article and Find Full Text PDFDalton Trans
December 2024
Department of Inorganic Chemistry, Faculty of Chemistry and Advanced Materials Center, Gdańsk University of Technology, Narutowicza 11/12, 80-233 Gdańsk, Poland.
The reactivity of the phosphinoborenium cation supported by a 1,3,4,5-tetramethylimidazolin-2-ylidene ligand toward small molecules was explored. The phosphinoborenium cation exhibited dual Lewis acid-base properties due to the presence of the Lewis acidic boron center and the Lewis basic phosphido ligand connected by a covalent bond. The reaction of the title cation with CO led to the insertion of a CO molecule into the P-B bond.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
January 2025
Institute of Chemistry, Academia Sinica Taipei, Taiwan, ROC.
Chemistry
December 2024
Department of Pure and Applied Chemistry, University of Strathclyde, Glasgow, G1, Scotland, 1XL, U.K.
Hydrogen isotope exchange (HIE) via C-H activation constitutes an efficient method for the synthesis of isotopically-enriched compounds, which are crucial components of the drug discovery process and are extensively employed in mechanistic studies. A series of iridium(I) complexes, bearing a chelating phosphine-N-heterocyclic carbene ligand, was designed and synthesized for application in the catalytic HIE of challenging N- and O-aryl carbamates. A broad range of substrates were labeled efficiently, and applicability to biologically-relevant systems was demonstrated by labeling an ʟ-tyrosine-derived carbamate with excellent levels of deuterium incorporation.
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