Copper‐Catalyzed Direct Arylselenation of Anilines by CH Bond Cleavage

Abstract

Abstract:We describe here an efficient and regioselective synthesis of arylselanyl anilines by coppercatalyzed direct arylselenation of arylamines. Using a catalytic amount of copper iodide in dimethyl sulfoxide at 110 8C under an air atmosphere, a range of arylselanyl anilines was obtained directly from substituted diaryl diselenides in moderate to good yields via C À H bond cleavage of aryl amines.

An environmentally benign and efficient synthesis of 4‐Selanylpyrazoles catalyzed by haloid salts in water

“…of 1a with 1.0 equiv. for H 2 O 2 proved to be the best choices (entries 5, [16][17][18][20][21][22]. of oxidant H 2 O 2 and 15 mol% of NaCl in H 2 O for 6 hr at room temperature, the desired product, 3,5-dimethyl-1-phenyl-4--(phenylselanyl)-1H-pyrazole 3a was obtained in a good yield of 86% (Table 1, entry 1).…”

“…The difunctionalizations of alkenes is a main procedure for the synthesis of organoselinides, [13][14][15][16][17][18] and the senelynation of electron-rich aromatic compounds is another normal method for obtaining organoselinides. [19][20][21][22][23][24][25][26][27] Despite organoselinides being important in biological activities and in organic synthesis, there are few studies reported on selanyl-substituted pyrazoles, a kind of heteroaryl selinides, and the number of those pyrazoles is limited. Fritsky's group first reported a procedure for the preparation of symmetrical selanyl-substituted pyrazoles with substituted pyrazoles and selenium dioxide in pyridine, which provided the corresponding products in moderate yields.…”

Electrochemical Oxidative C(sp2)–H Bond Selenylation of Activated Arenes

“…There are few reports available in literature for the synthesis of these selenides via oxidative C–Se bond formation through the C(sp 2 )–H bond activation of arenes (Scheme ). [3d], Alves and co‐workers reported the selenylation of anilines using CuI in DMSO. [5a] The same group reported an alternative method using anilines and PhSeCl as substrates, in glycerol under an inert atmosphere.…”

“…[3d], Alves and co‐workers reported the selenylation of anilines using CuI in DMSO. [5a] The same group reported an alternative method using anilines and PhSeCl as substrates, in glycerol under an inert atmosphere. [5b] Recently, we reported the oxidative C–Se bond formation of arenes under different conditions: using I 2 /DMSO (under microwave irradiation), as well as KIO 3 / ethylene glycol (with conventional heating).…”

“…To the best of our knowledge, the electrochemical oxidative selenylation of arenes has not yet been explored. As part of our continued interest in designing and developing eco‐friendly processes, as well as in the C(sp 2 )–H bond selenylation of activated arenes,[3d], [5c], [5d] herein we report, for the first time, the use of an electrochemical oxidative approach to C–Se bond formation via the C(sp 2 )–H bond functionalization of arenes (Scheme d). With this new approach, using KI as an efficient electrolyte and source of iodine, in MeCN, we obtained the desired selenylated products regioselectivity in good to excellent yields.…”