The first enantioselective carbometalation reaction of azabicycloalkenes has been achieved by iron catalysis to in situ form optically active organozinc intermediates, which are amenable to further synthetic elaborations. The observed chiral induction, along with the DFT and XAS analyses, reveals the direct coordination of the chiral phosphine ligand to the iron centre during the carbon-carbon and carbon-metal bond forming step. This new class of iron-catalysed asymmetric reaction will contribute to the synthesis and production of bioactive molecules.
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http://dx.doi.org/10.1039/d1cc02387j | DOI Listing |
J Am Chem Soc
July 2023
Chemistry Research Laboratory, Department of Chemistry, University of Oxford, Oxford OX1 3TA, United Kingdom.
Piperidines are frequently found in natural products and are of importance to the pharmaceutical industry. A generally useful asymmetric route to enantiomerically enriched 3-substituted piperidines remains elusive. Here we report a cross-coupling approach to enantioenriched 3-piperidines from pyridine- and sp-hybridized boronic acids.
View Article and Find Full Text PDFJ Am Chem Soc
February 2023
State Key Laboratory of Organometallic Chemistry, Center for Excellence in Molecular Synthesis, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, 345 Lingling Road, Shanghai, China, 200032.
Catalytic enantioselective functionalization of cyclobutenes constitutes a general and modular strategy for construction of enantioenriched complex cyclobutanes bearing multiple stereogenic centers, as chiral four-membered rings are common motifs in biologically active molecules and versatile intermediates in organic synthesis. However, enantioselective synthesis of cyclobutanes through such a strategy remained significantly limited. Herein, we report a series of unprecedented cobalt-catalyzed carbon-carbon bond forming reactions of cyclobutenes that are initiated through enantioselective carbometalation.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
March 2023
Department of Chemistry, Chemistry Research Laboratory, Department of Chemistry, University of Oxford, 12 Mansfield Road, Oxford, OX1 3TA, UK.
Complex cyclobutanes are important motifs in both bioactive molecules and natural products, yet their enantioselective preparation has not been widely explored. In this work, we describe rhodium-catalyzed enantioselective additions of aryl and vinyl boronic acids to cyclobutenone ketals. This transformation involves enantioselective carbometalation to give cyclobutyl-rhodium intermediates, followed by β-oxygen elimination to afford enantioenriched enol ethers.
View Article and Find Full Text PDFAcc Chem Res
October 2022
Schulich Faculty of Chemistry, Technion-Israel Institute of Technology, Technion City, Haifa 32000 Israel.
The various facets of the chemistry of cyclopropane derivatives, the smallest carbocycle, are amazingly diverse and continue to fascinate theoreticians, synthetic or structural chemists having interest in fundamental physical, medicinal chemistry, and natural product synthesis. The challenges generated by this intriguing cyclic arrangement of only three tetravalent carbons represent a wide area of the chemical spectrum. From fundamental aspects of bonding through the synthesis of highly strained molecules, the understanding of the mode of action in biological systems to the selective cleavage into acyclic substrates makes the chemistry of these small rings fascinating.
View Article and Find Full Text PDFChem Commun (Camb)
July 2021
International Research Center for Elements Science, Institute for Chemical Research (ICR), Kyoto University, Uji, Kyoto 611-0011, Japan and Department of Energy and Hydrocarbon Chemistry, Graduate School of Engineering, Kyoto University, Nishikyo-ku, Kyoto 615-8510, Japan.
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