Selenophilicity of Copper in Selenium-Carbon Bond Formation from Selenous Acid Using Cu(II)/Sn(II) Reagent

Abstract

A selenium transfer reaction from selenous acid to benzyl and alkyl halides is initiated in the presence of stannous chloride and a catalytic amount of cupric chloride resulting in the formation of the corresponding diorganoselenides and/or diorganodiselenides as the major products as indicated by 1 H, 13 C, 77 Se NMR, and MS. The reaction is characterized by a dual-metal effect at the selenium activation and transfer step. Thus, initial reaction of stannous chloride, cupric chloride, and selenous acid gives rise to α-Cu 2 Se. Selenium transfer from the latter to the organic halide takes place with additional assistance of stannous chloride.

Dinuclear copper(i) complexes with N-heterocyclic thione and selone ligands: synthesis, characterization, and electrochemical studies

“…14 Although coordination complexes of the Bmm Me ligand with rhenium(I), 3 iron(II), 15 cobalt(II), 11 rhodium(I), 1,16 iridium(I), 17 nickel(II), 11 silver(I), 18,19 gold(I/III), 19 zinc(II), 20 tin(II), 21 lead(II) 22,23 and antimony(III) 8 have been isolated, it is rather surprising that only one report of copper(I) derivatives has been published, 19 particularly given the reported affinity of copper for sulfur-and selenium-containing ligands. 24 In this work, we report the synthesis and crystal structures of a series of dinuclear, three-and four-coordinate copper(I) complexes with the aim of understanding the effect of the methylene linkers and chalcogenone donor groups on the redox potentials of the Cu(I)/Cu(II) couple. These reduction potentials are highly dependent upon S/Se ligand coordination and can be tuned in a wide potential range using a variety of monodentate and bidentate thione and selone ligands.…”

Peptide Functionalization Through the Generation of Selenocysteine Electrophile

“…4‐Phenyl‐2‐(pyridin‐2‐yl)but‐3‐yn‐2‐ol ( 1a ) and diphenyl diselenide ( 2a ) were chosen for 5‐endo‐dig cyclization reaction (Scheme ). It is known that transition metal salts, especially halides, may form complexes with diselenides . Therefore, several Lewis acids [such as FeCl 3 , FeBr 2 , FeBr 3 , CoCl 2 , NiCl 2 , CuCl 2 , CuBr 2 , Cu(OAc) 2 , RuCl 3 , In(OTf) 3 , and Bi(OTf) 3 ] were evaluated for their ability to activate Se–Se bond and promote the cyclization.…”

Facile Deoxygenation of Telluroxides, Tellurones and Selenones with Nickel Boride at Ambient Temperature

“…[30][31][32][33][34] All the products, except di(4-carbomethoxyphenyl)telluride, are known and were identified by co-TLC with authentic samples and by mp, IR and NMR spectra which are in good agreement with reported literature. [14][15][16][17][18][19][20][21][22][23][24][25][26][27][28][29] General Procedure of Deoxygenation of Telluroxides. In a typical experiment, di(4-tolyl)telluroxide (1 mmol, 0.325 g), anhydrous nickel chloride (1 mmol, 0.129 g) and dry THF (10 mL) with a stir bar and were placed in a 50 mL RB flask, fitted with a condenser and calcium chloride guard tube.…”