Zinc-Mediated Cleavage of Diselenides: A Novel Synthesis of Unsymmetrical Diorganyl Selenides in Aqueous Media

Abstract

A convenient synthetic method has been developed for the preparation of unsymmetrical selenides through a one-pot zinc-mediated reaction of diselenides and active organic halides in ­aqueous media.

Key words

diselenides - selenides - zinc - zinc selenolate - halides

References

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11

General Experimental Procedure. In a 50 mL round-bottom flask, fitted with a reflux condenser, were placed zinc powder (0.5 mmol), diorganyl diselenide (4 mmol), and MeCN (14 mL). (In the case of dibenzyl diselenide, AlCl₃ (1.5 mmol) was also added at this stage.) The mixture was stirred at 65 °C for 1 h until the zinc powder was almost consumed and the solution became turbid; organic halide (1.8 mmol) and H₂O (2 mL) were then added at once to the solution and stirring was continued for the specified time (Table [1] ) at 65 °C. Progress of the reaction was monitored by TLC. When the reaction was complete, MeCN was evaporated, Et₂O (30 mL) was added, the mixture washed with H₂O (3 × 20 mL), and the organic layer was dried over anhyd Na₂SO₄. The solvent was evaporated in vacuo to give the corresponding selenide which was purified by preparative TLC (silica gel, eluent petroleum ether-CCl₄ = 1:1 or petroleum ether-Et₂O = 9:1 or CCl₄-Et₂O = 4:1).