Computational Study of SmI₂-Catalyzed Intermolecular Couplings of Cyclopropyl Ketones: Links between the Structure and Reactivity.

ABSTRACT: SmI₂-catalyzed intermolecular coupling reactions of cyclopropyl ketones with alkenes or alkynes offer an efficient strategy for furnishing diverse five-membered ring-containing molecular architectures. This study presents a systematic computational investigation to reveal the structure-reactivity relationships in these reactions. The reactivity of aryl cyclopropyl ketones is enhanced by the stabilized ketyl radical and cyclopropyl fragmentation, arising from the conjugation effect of the aryl ring, despite an obstacle emerging from the gauche styrene intermediate that elevates the energy barrier for radical trapping. By contrast, alkyl cyclopropyl ketones lack conjugation and exhibit high barriers for reduction and fragmentation but undergo facile radical trapping due to

SUBMITTER: Yu S 

PROVIDER: S-EPMC11536359 | biostudies-literature | 2024 Nov

REPOSITORIES: biostudies-literature