An electrochemical deborylative selenylation of arylboronic acids has been developed to produce aryl selenoethers in good yields, whose practicability has been highlighted through the synthesis of bioactive molecules and gram-scale preparation.
An electrochemical method for the synthesis of (poly)phenols via deborylative hydroxylation of arylborons has been well established under metal‐free conditions, whose practicability and advantage has been highlighted by the preparation of drug molecules and preformation of scalable transformation. Mechanistic studies have demonstrated that superoxide anion radical was involved in the conversion followed by the reaction with arylboronic acid substrate.
Electrochemical N-cyanation of secondary amines and α C-cyanation of tertiary amines have been established under transition metal-free conditions, which provide cyanamides and nitriles with good functional group tolerance from simple systems.
Since C-H bond is the basic unit of organic compounds, it's considered to be a concise synthesis method to implement direct functionalization of C-H bond. As carboxylic acids are widely found in nature, carboxyl group can act as both directing group and leaving group to drive transition metal-catalyzed controllable transformation of ortho-C-H bond functionalization of carboxylic acid that not only avoids the extra introduction and removal of the directing group in the process of C-H bond activation, but also highlights the simplicity of C-H bond activation and green of decarboxylation with "one stone and two birds" strategy of the carboxyl group. Therefore, basing on the strategy of "two birds with one stone", ortho-C-H bond functionalization of carboxylic acid using carboxyl as a traceless directing group can provide a new strategy and method for controllable and directional synthesis, which has considerable significance in synthetic chemistry. According to the types of coupling partners involved in the transformations, transition metal-catalyzed ortho-C-H bond activations of carboxylic acids with multiple-bond-containing reagents, arylating compounds and heteroatom-containing chemicals are reviewed respectively based on the strategy of "two birds with one stone", and the relevant reaction mechanisms are discussed.
A metal-free electrochemical method for vicinal difunctionalization of various alkenes with dibromomethane in alcohol solvent has been well established to synthesize corresponding β-bromo-α-alkyloxyalkanes with good functional group tolerance under ambient conditions. Preliminary mechanistic studies indicate the oxidation of bromine source occurs prior to that of alkene substrate with the involvement of bromine radical during electrolysis.
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