Singlet Carbenes Are Stereoinductive Main Group Ambiphiles
Stereogenic units are a critical source of molecular complexity, but their stereoselective formation via main group ambiphiles─which are suitable for derivatizing a wide scope of functionalities─is largely unexplored. Herein, using chiral cyclic (alkyl)(amino)carbenes (<i><sup>Chi</sup></i>CAACs), we study stereoinduction during the oxidative addition of E-H σ-bonds (E = C, N, O, Si, P). Through computational modeling, the relationship between stereochemical outcome and mechanism is elucidated, providing insight into when and why <i><sup>Chi</sup></i>CAACs exhibit excellent stereoselectivities. Altogether, these results demonstrate the potential for chiral main group ambiphiles to generate stereogenic units in a highly controlled manner opening avenues for applying "metal-like" reactivity in metal-free asymmetric syntheses.
Authors
- Jennifer Morvan (ORCID: https://orcid.org/0000-0003-1210-7975)
- Milan Gembický (ORCID: https://orcid.org/0000-0002-3898-1612)
- Guy Bertrand (ORCID: https://orcid.org/0000-0003-2623-2363)
- Thierry Roisnel (ORCID: https://orcid.org/0000-0002-6088-4472)
- Marc Mauduit (ORCID: https://orcid.org/0000-0002-7080-9708)
- Jan Lorkowski (ORCID: https://orcid.org/0000-0003-3436-1296)
- Rodolphe Jazzar (ORCID: https://orcid.org/0000-0002-4156-7826)
- Nicolas Vanthuyne (ORCID: https://orcid.org/0000-0003-2598-7940)
- Frédérique Morvan (ORCID: https://orcid.org/0000-0001-5517-6263)
- Patrick Yorkgitis
Institutions
- Centre National de la Recherche Scientifique (FR)
- University of California San Diego (US)
- École Nationale Supérieure de Chimie de Rennes (FR)
- Centrale Méditerranée (FR)
- Université de Rennes (FR)
Publication Details
- Journal
- Journal of the American Chemical Society
- Published
- 2025-04-21
- DOI
- https://doi.org/10.1021/jacs.5c03845
- Citations
- 6
- Primary Topic
- N-Heterocyclic Carbenes in Organic and Inorganic Chemistry
- Type
- article
- Field-Weighted Citation Impact
- 5.62
Funders
- National Science Foundation
- W. M. Keck Foundation
- Agence Nationale de la Recherche
- Centre National de la Recherche Scientifique
- University of California, San Diego
- Division of Chemistry