The Importance of 1,5‐Oxygen⋅⋅⋅Chalcogen Interactions in Enantioselective Isochalcogenourea Catalysis

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  • Claire M. Young
    EaStCHEM School of Chemistry University of St Andrews North Haugh St Andrews KY16 9ST UK
  • Alex Elmi
    EaStCHEM School of Chemistry University of Edinburgh Joseph Black Building David Brewster Road Edinburgh EH9 3FJ UK
  • Dominic J. Pascoe
    EaStCHEM School of Chemistry University of Edinburgh Joseph Black Building David Brewster Road Edinburgh EH9 3FJ UK
  • Rylie K. Morris
    Chemistry Department Ripon College 300 W. Seward St. Ripon WI 54971 USA
  • Calum McLaughlin
    EaStCHEM School of Chemistry University of St Andrews North Haugh St Andrews KY16 9ST UK
  • Andrew M. Woods
    EaStCHEM School of Chemistry University of St Andrews North Haugh St Andrews KY16 9ST UK
  • Aileen B. Frost
    EaStCHEM School of Chemistry University of St Andrews North Haugh St Andrews KY16 9ST UK
  • Alix de la Houpliere
    EaStCHEM School of Chemistry University of St Andrews North Haugh St Andrews KY16 9ST UK
  • Kenneth B. Ling
    Syngenta Jealott's Hill International Research Centre Bracknell Berkshire RG42 6EY UK
  • Terry K. Smith
    EaStCHEM School of Chemistry University of St Andrews North Haugh St Andrews KY16 9ST UK
  • Alexandra M. Z. Slawin
    EaStCHEM School of Chemistry University of St Andrews North Haugh St Andrews KY16 9ST UK
  • Patrick H. Willoughby
    Chemistry Department Ripon College 300 W. Seward St. Ripon WI 54971 USA
  • Scott L. Cockroft
    EaStCHEM School of Chemistry University of Edinburgh Joseph Black Building David Brewster Road Edinburgh EH9 3FJ UK
  • Andrew D. Smith
    EaStCHEM School of Chemistry University of St Andrews North Haugh St Andrews KY16 9ST UK

抄録

<jats:title>Abstract</jats:title><jats:p>The importance of 1,5‐O⋅⋅⋅chalcogen (Ch) interactions in isochalcogenourea catalysis (Ch=O, S, Se) is investigated. Conformational analyses of <jats:italic>N</jats:italic>‐acyl isochalcogenouronium species and comparison with kinetic data demonstrate the significance of 1,5‐O⋅⋅⋅Ch interactions in enantioselective catalysis. Importantly, the selenium analogue demonstrates enhanced rate and selectivity profiles across a range of reaction processes including nitronate conjugate addition and formal [4+2] cycloadditions. A gram‐scale synthesis of the most active selenium analogue was developed using a previously unreported seleno‐Hugerschoff reaction, allowing the challenging kinetic resolutions of tertiary alcohols to be performed at 500 ppm catalyst loading. Density functional theory (DFT) and natural bond orbital (NBO) calculations support the role of orbital delocalization (occurring by intramolecular chalcogen bonding) in determining the conformation, equilibrium population, and reactivity of N‐acylated intermediates.</jats:p>

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