Stereo- and Regioselective Zinc-Mediated Ring-Opening of Epoxides with Diselenides

Abstract

Two convenient rapid, efficient, stereoselective and highly regioselective methods for the synthesis of β-hydroxy selenides by the direct opening of epoxides with diselenides in acetonitrile in the presence of either Zn/AlCl₃ or zinc powder in aqueous sodium hydroxide solution are described. These methods appear to be competitive with the other methods previously reported.

Key words

β-hydroxy selenides - diselenides - epoxides - zinc - zinc selenolate

References

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18

General Experimental Procedure: Method A.
A stirred solution of the diselenide (0.5 mmol) in anhydrous MeCN (15 mL) was treated with activated zinc powder (2.5 mmol). The mixture was refluxed for 1.5 h, during which time the zinc powder was almost completely consumed. Then, finely ground anhydrous AlCl₃ (1.2 mmol) and the epoxide (1.5 mmol) were added to the solution and stirring was continued for the specified time (Table [1] ) without protection from the atmosphere. Progress of the reaction was monitored by TLC. After completion of the reaction, the solvent was evaporated and the residue was acidified to pH 4 with HCl (10%). The organic phase was extracted with Et₂O (2 × 15 mL), dried (Na₂SO₄), and concentrated. The pure products were obtained by preparative TLC (silica gel, eluent, CCl₄/Et₂O = 2:1) to afford the desired β-hydroxy selenides.

19

General Experimental Procedure: Method B. A mixture of diselenide (0.5 mmol) and activated zinc powder (2.5 mmol) was suspended in MeCN (15 mL). The mixture was refluxed, with stirring, for 10 min. To this mixture was added 25% NaOH (3 mL, 18.8 mmol), and the mixture was stirred for further 5 min, during which time the yellow solution turned to colorless. Then, the epoxide (1 mmol) was added in one portion to the solution and stirring was continued for the length of time indicated in Table [1] . When the reaction was complete, the organic solvent was evaporated, and the residue was acidified to pH 4 with HCl (10%). The organic layer was extracted with Et₂O (2 × 20 mL), dried (Na₂SO₄), and evaporated. Preparative TLC yielded the pure products.