Photocatalyzed site-selective C-H to C-C conversion of aliphatic nitriles
β- or γ-Site-selective C-H alkylation of aliphatic nitriles has been achieved using a decatungstate salt as the photocatalyst. The observed site selectivity was justified by a radical polar effect in transition states for hydrogen abstraction.
A photosensitizing decatungstate-based MOF as heterogeneous photocatalyst for the selective C-H alkylation of aliphatic nitriles
The efficient photosensitizing of decatungstate-based MOF with 1D channels was achieved via in situ synthesis under solvothermal conditions for light driven acceleration of β- or γ-site C-H alkylation of aliphatic nitriles. The high catalytic efficiency, excellent size selectivity, high stability and good recyclability of the photocatalyst offer an environmentally-friendly route for widening the scope of accessible nitriles in both laboratory and industry.
A breathing MOF: Direct crystallographic observation of the site-selective C(sp3)-H functionalization
A 3D breathing MOF was synthesized by hierarchical methods for light-driven acceleration of the site-selective C(sp3)-H activation. The 1D channels of the assembled MOF can encapsulate the reaction substrates via a breathing process that was observed by single-crystal X-ray analyses. The weak interactions between the encapsulated substrate and the photoactive center facilitated the in situ generation of the active alkyl radicals.