Radikalische enantioselektive C(sp³)‐H‐Funktionalisierung

Abstract

Radikaler Stil: Bei der enantioselektiven C(sp3)‐H‐Funktionalisierung durch radikalische Aktivierung sind in letzter Zeit einige Durchbrüche zu verzeichnen. Neue Strategien demonstrieren das Potenzial der Radikalchemie, Alkane zu funktionalisierten chiralen Molekülen umzusetzen (siehe Schema; HAT=H‐Atomtransfer).

Anionic Bisoxazoline Ligands Enable Copper‐Catalyzed Asymmetric Radical Azidation of Acrylamides

“…To address this issue, we became interested in developing efficient asymmetric radical azidation reaction based on our recent works on the copper-catalyzed asymmetric radical transformations. [10,11] Distinct from our previous reactions involving a proposed Cu III intermediates, however, the azidation reaction are proposed to undergo the radical group transfer (outer sphere) pathway for the C-N 3 bond formation. More importantly, Stahl and co-workers recently reported a radical azidation of benzylic C À H bond, in which a copper-azide dimer having neutral bisoxazoline (Box) ligands was involved, and both bridging and terminal azides can be attacked by the carbon centered radical to lead to two opposite azidation enantiomers, which compromise the enantioselectivity and result in poor er values (Scheme 1 B, for details, see the supporting information of ref.…”