Enantioselective Rhodium(I) Donor Carbenoid-Mediated Cascade Triggered by a Base-Free Decomposition of Arylsulfonyl Hydrazones

Òscar Torres, Teodor Parella, Miquel Solà, Anna Roglans, Anna Pla-Quintana

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    26 Citations (Scopus)

    Abstract

    © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim. The reaction of diyne arylsulfonyl hydrazone substrates under rhodium(I)/BINAP catalysis gives access to sulfonated azacyclic frameworks in a highly enantioselective manner. This new cascade process considerably increases the molecular complexity by generating two C-C bonds, one C-S bond, and one C-H bond. Theoretical calculations, competitive experiments, and deuterium labeling have jointly been used to propose a mechanism that accounts for the reaction. The mechanism involves the formation of vinyl rhodium carbenoids, hydride migratory insertion, and intermolecular stereoselective nucleophilic attack. The last two steps are the key to the stereoselectivity of the process.
    Original languageEnglish
    Pages (from-to)16240-16245
    JournalChemistry - A European Journal
    Volume21
    Issue number45
    DOIs
    Publication statusPublished - 1 Nov 2015

    Keywords

    • carbenoids
    • cascade
    • cyclization
    • density functional calculations
    • rhodium

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  • Cite this

    Torres, Ò., Parella, T., Solà, M., Roglans, A., & Pla-Quintana, A. (2015). Enantioselective Rhodium(I) Donor Carbenoid-Mediated Cascade Triggered by a Base-Free Decomposition of Arylsulfonyl Hydrazones. Chemistry - A European Journal, 21(45), 16240-16245. https://doi.org/10.1002/chem.201502909