Photocatalytic Alkyl Radical Addition Tandem Oxidation of Alkenyl Borates

Photocatalytic oxidation is a popular transformation way for organic synthesis and is widely applied in academia and industry. Herein, we report a blue light-induced alkylation–oxidation tandem reaction for the synthesis of diverse ketones by combining alkyl radical addition and oxidation of alkenyl borates. This reaction shows excellent functional group compatibility in acceptable yields, and diversity of radical precursors is applicable

Rh(III)-Catalyzed C–H Activation with Allenes To Synthesize Conjugated Olefins

Rh^III-catalyzed C–H activation with allenes produces highly unsaturated conjugated olefins. The reaction is applicable to both olefin and arene C­(sp²)–H and is compatible with a variety of functional groups. The products can be further transformed into other important skeletons through Diels–Alder reaction and intramolecular transesterification

Rhodium-Catalyzed Directed C–H Cyanation of Arenes with <i>N-</i>Cyano‑<i>N</i>‑phenyl‑<i>p</i>‑toluenesulfonamide

A Rh-catalyzed directed C–H cyanation reaction was developed for the first time as a practical method for the synthesis of aromatic nitriles. <i>N</i>-Cyano-<i>N</i>-phenyl-<i>p</i>-toluenesulfonamide, a user-friendly cyanation reagent, was used in the transformation. Many different directing groups can be used in this C–H cyanation process, and the reaction tolerates a variety of synthetically important functional groups

Rhodium-Catalyzed Directed C–H Cyanation of Arenes with <i>N-</i>Cyano‑<i>N</i>‑phenyl‑<i>p</i>‑toluenesulfonamide

A Rh-catalyzed directed C–H cyanation reaction was developed for the first time as a practical method for the synthesis of aromatic nitriles. <i>N</i>-Cyano-<i>N</i>-phenyl-<i>p</i>-toluenesulfonamide, a user-friendly cyanation reagent, was used in the transformation. Many different directing groups can be used in this C–H cyanation process, and the reaction tolerates a variety of synthetically important functional groups

Nickel-Catalyzed Defluorinative Reductive Cross-Coupling of <i>gem</i>-Difluoroalkenes with Unactivated Secondary and Tertiary Alkyl Halides

Herein, we described a nickel-catalyzed monofluoroalkenylation through defluorinative reductive cross-coupling of <i>gem</i>-difluoroalkenes with alkyl halides. Key to the success of this strategy is the combination of C–F cleavage with alkyl halides activation. This reaction enables the convenient synthesis of a large variety of functionalized monofluoroalkenes under mild reaction conditions with broad functional group compatibility and excellent <i>Z</i>-selectivity. The combination of Ni catalysis with (Bpin)₂/K₃PO₄ as terminal reductant promoted the efficient C­(sp²)–C­(sp³) formation especially the generation of all-carbon quaternary centers with high chemoselectivity

Rhodium(III)-Catalyzed Directed C–H Coupling with Methyl Trifluoroacrylate: Diverse Synthesis of Fluoroalkenes and Heterocycles

An example of Rh-catalyzed C–H activation with methyl trifluoroacrylate for the synthesis of fluoroolefins and heterocycles (benzoindolizines) is reported. The types of products were determined by the directing group. The benzoindolizines and fluoroolefins were obtained by using pyridine and pyrazole as the directing group, correspondingly. These transformations present a number of advantages, such as oxidant-free reaction conditions and broad functional group tolerance. Moreover, this reaction greatly extends the application of fluoroolefins