Nickel‐Catalyzed Electrochemical Synthesis of (Hetero)Aryl Trifluoromethyl Selenides

Abstract

A convenient and efficient approach for the construction of aryl trifluoromethyl selenoethers from aryl iodides under mild conditions is reported. Electrochemical activation of stable and inexpensive NiBr2bipy (bipy – bipyridine) complex instead of labile Ni(COD)2 (COD – cyclooctadiene) catalyst. [NMe4][SeCF3] is employed as shelf‐stable source of SeCF3 fragment. The reaction tolerates a wide range of substrates, including modification of drug‐like molecules. Cyclic voltammetry studies allow insight into the reaction mechanism.

Direct Trifluoromethylselenolation and Fluoroalkylselenolation of C−H Bonds: Recent Advances in Reagents Development and Reactions

“…Comparatively, the field of electrophilic and transition‐metal‐involved transformations has been well‐developed and has contributed significantly to synthetic chemistry. However, the application of emerging techniques such as photocatalysis and electrosynthesis in trifluoromethylselenolation and fluoroalkylselenolation reactions has shown promise but is relatively limited [45–47] . This limitation may be attributed to the availability of suitable reagents required for these transformations.…”

Photocatalytic Perfluoroalkylation of Disulfides and Diselenides. Syntheses of Perfluoroalkyl Thio- and Seleno-ethers

“…Nevertheless, akin to the R F S- reagents, the procedures for synthesizing R F Se- reagents are not always direct or cost-effective. Indirect protocols (where the Se and R F moieties are joined from different scaffolds) for the synthesis of aryltrifluoromethyl seleno-ethers rely on prefunctionalized substrates. − …”

Nickel-Catalyzed Trifluoromethylselenolation of Aryl and Alkenyl-Triflates: Scope and Mechanism

“…On the one hand, an NHC-Ni­(I) dimer proved to be an efficient catalyst for the trifluoromethylselenolation of aryl iodides . On the other hand, the use of the Ni(0)/Bpy catalytic system revealed its efficiency toward the synthesis of Ar-SeCF 3 starting from aryl iodides or bromides. , Aryl chlorides can also be used as starting electrophiles, but they require the use of Ni(0)/Dppf catalytic loadings of up to 40 mol % . To date, the trifluoromethylselenolation of activated phenol derivatives has not been reported.…”