RESUMO
A fully heterogeneous metallaphotocatalytic C-C cross-coupling of aryl/vinyl halides with alkyl/allyltrifluoroborates has been developed by employing integrated bipyridyl-Ni(II)-carbon nitride as a stable and recyclable bifunctional catalyst. This visible-light-mediated heterogeneous protocol allows for the sustainable synthesis of diverse valuable diarylmethanes and allylarenes in high efficiency.
Assuntos
2,2'-Dipiridil , Compostos de Vinila , Estrutura Molecular , CatáliseRESUMO
The development of heterogeneous metallaphotocatalysis is of great interest for sustainable organic synthesis. The rational design and controllable preparation of well-defined (site-isolated) metal/photo bifunctional solid catalysts to meet such goal remains a critical challenge. Herein, we demonstrate the incorporation of privileged homogeneous bipyridyl-based Ni-catalysts into highly ordered and crystalline potassium poly(heptazine imide) (K-PHI). A variety of PHI-supported cationic bipyridyl-based Ni-catalysts (LnNi-PHI) have been prepared and fully characterized by various techniques including NMR, ICP-OES, XPS, HAADF-STEM and XAS. The LnNi-PHI catalysts exhibit exceptional chemical stability and recyclability in diverse C-P, C-S, C-O and C-N cross-coupling reactions. The proximity and cooperativity effects in LnNi-PHI significantly enhances the photo/Ni dual catalytic activity, thus resulting in low catalyst loadings and high turnover numbers.
RESUMO
A novel aza-Piancatelli rearrangement triggered cascade reaction has been developed by utilizing methyl furylacrylates as a new type of functionalized furanoxonium ion precursor, permitting rapid and flexible construction of diverse cyclopenta[b]pyrrolidinone derivatives. The unprecedented and highly efficient bicyclic γ-lactam product formation is originated from an unusual retro-aza-Piancatelli rearrangement of the major cis-fused multifunctionalized cyclopentenone to the minor trans-fused one followed by a lactamization reaction.