Carboxylate anions, dianions and ester enolates provide simultaneous protection and activation for directed carbometalation reactions. Advantage can be taken of the bis-carbanionic character of the intermediate for further controlled C-C bond forming reactions.
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Regio- and Diastereoselective Carbometalation Reaction of Cyclopropenes.
Acc Chem Res
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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 PDFStereoselective Synthesis of Polysubstituted Spiropentanes.
J Am Chem Soc
September 2022
Schulich Faculty of Chemistry, Technion - Israel Institute of Technology, Technion City, Haifa, 32000, Israel.
A new approach to polysubstituted spiropentanes is developed through a regio- and diastereoselective carbometalation of sp-disubstituted cyclopropenes. The control of selectivity originates from a combined -facial diastereoselective carbometalation with a regio-directed addition. The regio-controlling element subsequently serves as a leaving group in an intramolecular nucleophilic substitution.
View Article and Find Full Text PDFEfficient Synthesis of Orphaned Cyclopropanes Using Sulfones as Carbene Equivalents.
J Am Chem Soc
August 2022
Department of Chemistry, The University of North Carolina at Chapel Hill, Chapel Hill, North Carolina 27599-3290, United States.
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View Article and Find Full Text PDFIron-catalysed enantioselective carbometalation of azabicycloalkenes.
Chem 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.
Article Synopsis
- A new method has been developed for creating chiral organozinc intermediates using iron catalysis and azabicycloalkenes in an enantioselective carbometalation reaction.
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Rh(ii)-catalyzed branch-selective C-H alkylation of aryl sulfonamides with vinylsilanes.
Chem Sci
January 2020
Department of Applied Chemistry , Faculty of Engineering , Osaka University, Suita , Osaka 565-0871 , Japan . Email:
Rhodium(ii)-catalyzed unusual branch-selective -C-H alkylation of aryl sulfonamides with vinylsilanes was achieved using an 8-aminoquinoline directing group. Notably, the -substituted aryl sulfonamides gave mono-(branched)alkylated products exclusively without the formation of any double C-H alkylated byproducts. The results of deuterium labeling experiments suggest that both hydrometalation and carbometalation pathways are involved in this conversion.
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