Time for SOme MOre: For the first time SOMO (singly occupied molecular orbital) activation has been exploited to allow a new approach to the alpha-chlorination of aldehydes. This transformation can be readily implemented as part of a linchpin catalysis approach to the enantioselective production of terminal epoxides.
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http://dx.doi.org/10.1002/anie.200901855 | DOI Listing |
J Am Chem Soc
December 2024
Graduate School of Pharmaceutical Sciences, Kyoto University, Sakyo, Kyoto 606-8501, Japan.
β-Amino acids serve as crucial building blocks for a broad range of biologically active molecules and peptides with potential as peptidomimetics. While numerous methods have been developed for the synthesis of β-amino acids, most of them require multistep preparation of specific reagents and substrates, which limits their synthetic practicality. In this regard, a homologative transformation of abundant and readily available α-amino acids would be an attractive approach for β-amino acid synthesis.
View Article and Find Full Text PDFJ Am Chem Soc
December 2024
Laboratory of Asymmetric Catalysis and Synthesis, Institute of Chemical Sciences and Engineering, Ecole Polytechnique Fédérale de Lausanne (EPFL), 1015 Lausanne, Switzerland.
Asymmetric -heterocyclic carbene (NHC) organocatalysis is a cornerstone of synthetic organic chemistry. The emerging concept of single-electron NHC catalysis broadened the scope of C-C bond-forming reactions, facilitating the synthesis of a variety of attractive racemic compounds. However, the development of effective and selective chiral NHC catalysts for asymmetric radical-mediated reactions has been challenging.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
November 2024
Centre for Catalysis Research and Innovation, Department of Chemistry and Biomolecular Sciences, University of Ottawa, 10 Marie-Curie Pvt, Ottawa, ON, K1N 6N5, Canada.
Linchpin reagents are building blocks that can be chemoselectively functionalized to afford products with a common, useful functional group. In this work, we describe the development and validation of the first amide linchpin reagent and demonstrate its use as a doubly electrophilic building block for the synthesis of a variety of amides, including challenging classes. The linchpin reagent was first functionalized via rhodium-catalyzed electrophilic amination.
View Article and Find Full Text PDFNat Commun
September 2024
Key Laboratory of Precision and Intelligent Chemistry, and Department of Chemistry, University of Science and Technology of China, Hefei, 230026, P. R. China.
The incorporation of difluoromethylene (CF) group into chemical molecules often imparts desirable properties such as lipophilicity, binding affinity, and thermal stability. Consequently, the increasing demand for gem-difluoroalkylated compounds in drug discovery and materials science has continued to drive the development of practical methods for their synthesis. However, traditional synthetic methods such as deoxofluorination often confront challenges including complicated substrate synthesis sequences and poor functional group compatibility.
View Article and Find Full Text PDFNat Plants
September 2024
Key Laboratory of Plant Development and Environmental Adaptation Biology, Ministry of Education, School of Life Science, Shandong University, Qingdao, China.
A transformation in plant cell wall evolution marked the emergence of grasses, grains and related species that now cover much of the globe. Their tough, less digestible cell walls arose from a new pattern of cross-linking between arabinoxylan polymers with distinctive ferulic acid residues. Despite extensive study, the biochemical mechanism of ferulic acid incorporation into cell walls remains unknown.
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