Year: 2025
Type: article
Abstract: 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 ( Chi 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 Chi 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.
DOI: 10.1021/jacs.5c03845
Institutions: Centre National de la Recherche Scientifique, University of California San Diego, Institut des Sciences Chimiques de Rennes, École Nationale Supérieure de Chimie de Rennes, UCSD-CNRS Joint Research Chemistry Laboratory, Université de Rennes, Aix-Marseille Université, Centrale Méditerranée
Language: English
Subfield: Organic Chemistry
Field: Chemistry
Domain: Physical Sciences
Open Access status: green
OpenAlex ID: W4409627108