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Updated: May 10, 2025

Isolating Free Carbenes, their Mixed Dimers and Organic Radicals
Published on: April 19, 2019
Singlet Carbenes Are Stereoinductive Main Group Ambiphiles
Jan Lorkowski1,2, Patrick Yorkgitis1, Fanny Morvan2
1UCSD-CNRS Joint Research Laboratory (IRL 3555), Department of Chemistry and Biochemistry, University of California, San Diego, La Jolla, California 92093, United States.
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 (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 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.
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