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  • Title: Rhodium-Catalyzed Ring-Opening Hydroacylation of Alkylidenecyclopropanes with Chelating Aldehydes for the Synthesis of γ,δ-Unsaturated Ketones.
    Author: Li HS, Lu SC, Chang ZX, Hao L, Li FR, Xia C.
    Journal: Org Lett; 2020 Jul 02; 22(13):5145-5150. PubMed ID: 32610932.
    Abstract:
    The first intermolecular ring-opening hydroacylation of alkylidenecyclopropanes with chelating aldehydes through a rhodium-catalyzed acrylamide-promoted protocol is reported. This highly efficient catalytic system enables the direct synthesis of a diverse range of linear γ,δ-unsaturated ketones. Good functional group compatibility is demonstrated for the completely atom-economical and remarkably selective proximal C-C bond cleavage process. Mechanistic studies reveal that the bidentate coordination of N,N-dimethylmethacrylamide (L1) to the acylrhodium intermediates might facilitate the cyclopropane ring fragmentation and isomerization.
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