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We describe herein a novel, general, and robust approach to structurally diversified alkenyl nitriles through a Rh-catalyzed cyano transfer reaction between alkynyl-malononitrile derivatives and aryl/alkenyl boronic acids. This reaction exhibits high chemo- and regioselectivity and a broad substrate scope. The tetrasubstituted alkenyl dinitriles (34 examples, average 58% yield) are obtained through substrate tuning and ligand control.

Phenanthridinone is a significant moiety in pharmaceutical and material science; thus, it is highly desirable to develop an efficient and robust method to construct phenanthridinone from readily available starting materials. Herein, we report a Ru-catalyzed C-H arylation of aromatic carboxylic acids with ortho -haloanilines, followed by intramolecular dehydration to afford phenanthridinones in high yields.

Herein, we report a light-driven, radical-type cyano migration in the absence of a photocatalyst, enabling a chemo-divergent synthesis of ( Z )-alkenyl nitriles and ketones. Trifluoromethyl thianthrenium salt (TT-CF 3 + OTf - ) plays multiple roles: (a) absorbing light to generate trifluoromethyl radicals to initiate the reaction and (b) forming α-thianthrenium cyano species by in situ capture of TT •   + . ( Z )-Alkenyl nitriles were formed through the elimination of thianthrenium salts, and aryl ketones were obtained via the nucleophilic substitution of thianthrenium salts.

Shown herein is the first time that the sulfilimine is utilized as a directing group for Rh(III)-catalyzed C-H activation/annulation with intermolecular and intramolecular alkyne compounds. Sulfilimine serves as a transformable directing group, an internal oxidant, in the annulation with an alkyne moiety via N-S bond cleavage. Notably, the retention of sulfilimine as a directing group is also achieved in the Rh(III)-catalyzed ortho -alkynylation with alkyne bromides.

A LiCl-mediated and palladium(II)-catalyzed oxidative cyclization of furan-ynes via dearomatizing alkoxyalkenylation of furan is reported to afford polyfunctionalized spiro-dihydrofurans with diastereospecification and high Z / E selectivity. This protocol is likely to involve chloropalladation of alkynes, subsequent intramolecular dearomatizing alkenylation of furan, and final O -allylation. The density functional theory (DFT) calculations demonstrated that the coordination of furan with dissolved Li + weakens its nucleophilicity and promoted the Heck insertion, and dissolved Cl - promoted chloropalladation of alkynes.

An efficient PhIO-mediated oxidative C═C bond cleavage and reassembly of enaminone toward oxazolone with high regioselectivity has been reported. DFT calculations revealed that the reaction proceeded through an oxygen atom transfer, C═C bond cleavage, alkylthio migration, and reassembly cascade. This strategy is highlighted by high atom and step economy with formation of five bonds in one pot and generation of a high-valued oxazolone skeleton under mild conditions.