SO2F2-Mediated Fluorination of P(O)-H and P(O)-OH Compounds under Mild Conditions.

With the increasing relevance of organophosphorus fluorine compounds in the pharmaceutical industry, their synthesis has attracted great attention. Herein, we report an efficient fluorination strategy for P(O)-H and P(O)-OH compounds using sulfuryl fluoride as the fluorination reagent. Avoiding the use of expensive or complex prepreparation reagents for fluoridation, this strategy could conveniently construct a variety of fluorophosphonates and phosphonofluoridates under mild conditions and without additional oxidants.

Nickel-Catalyzed Selective C-H Cyanation via Aromatic Thianthrenium Salts.

Here, we report the first case of nickel-catalyzed C-H cyanation via arylthianthrenium salts. The reaction features the use of air-stable and inexpensive NiCl2·6H2O as a catalyst for the highly selective construction of cyanation products by aromatic pre-thianthrenation. The mechanism study shows that the formation of aryl radicals is involved. Also, this protocol can be applied to the late-stage functionalization of bioactive molecules and is readily scalable, further showcasing the synthetic utility.

A late-stage functionalization tool: sulfonyl fluoride mediated deoxymethylation of phenols.

The late-stage functionalization of drugs and natural products has been identified as a promising approach to accelerate the discovery of new bioactive compounds. Due to the presence of the "Magic Methyl Effect", the direct deoxymethylation of phenolic hydroxyl groups, which are widespread in natural molecules, is a challenging task. A mild and rapid strategy for direct phenol deoxymethylation under metal catalysis using SO2F2 is described in this paper, while good functional group tolerance and high chemoselectivity allow this strategy to be one of the powerful tools for LSF. The power of this new platform is showcased through gram-scale and orthogonal experiments.

Palladium-Catalyzed Direct Decarbonylative Cyanation of Aryl Carboxylic Acids.

The direct transformation of aryl carboxylic acids to aryl nitrile compounds is an interesting topic because carboxylic acids are not only abundant in nature but are also inexpensive and stable. Here, the synthesis of a series of aryl nitriles by palladium-catalyzed decarbonylative cyanation of carboxylic acids without base has been achieved. The successful decarbonylative cyanation of drug molecules and Gram-scale reaction to verify the practicality and operability of this method are analyzed.