Zn/RuCl₃-Promoted Cleavage of Diselenides: An Efficient Michael Addition of Zinc Selenolates to Conjugated Alkenes in Aqueous Media

Abstract

A simple and highly efficient one-pot route to β-selenocarbonyl compounds and nitriles has been developed by Zn/RuCl₃-catalyzed cleavage of diselenides and subsequent Michael addition of zinc selenolates to conjugated alkenes in aqueous media.

Key words

zinc selenolates - Michael addition - α,β-unsaturated carbonyl compounds - zinc - diselenides

References and Notes

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9

4-(4-Chlorophenylseleno)butan-2-one - Typical Procedure In a typical experiment, a mixture of bis(4-chloro-phenyl)diselenide (190 mg, 0.5 mmol), zinc dust (229 mg, 3.5 mmol), and ruthenium(III) chloride hydrate (13 mg, 0.05 mmol) was suspended in MeCN (8 mL) and H₂O (2 mL). The mixture was stirred at 80 °C for 1.5 h, during which time the zinc powder was almost completely consumed. Then, methyl vinyl ketone (73 mg, 1.05 mmol) was added at once to the mixture and stirring was continued at that temperature for 1 h in air. After completion of the reaction, the solution was filtered, the solvent was evaporated, and the residue was subjected to preparative TLC (silica gel, eluent, n-hexane-EtOAc = 4:1) to afford pure 4-(4-chlorophenylseleno)butan-2-one (255 mg, 98%, Table [1] , entry 11) as a pale yellow oil. IR (neat): 1720, 1478, 739 cm^-1. ¹H NMR (300 MHz, CDCl₃): δ = 2.14 (s, 3 H), 2.84 (t, 2 H, J = 7.2 Hz), 3.05 (t, 2 H, J = 7.2 Hz), 7.25 (d, 2 H, J = 8.5 Hz), 7.42 (d, 2 H, J = 8.5 Hz) ppm. ¹³C NMR (75 MHz, CDCl₃): δ = 20.8, 30.0, 43.9, 127.9, 129.3, 133.3, 134.3, 206.8 ppm. MS: m/z (%) = 264 (46) [(M + 4]⁺ , 262 (90) [M + 2]⁺, 260 (49) [M⁺], 219 (15), 191 (20), 151 (24), 71 (55), 43 (100). Anal. Calcd for C₁₀H₁₁ClOSe: C, 45.91; H, 4.24. Found: C, 46.30; H, 4.51.
Spectroscopic Data for Entry 12, Table 1
IR (neat): 1710, 1478, 738 cm^-1. ¹H NMR (500 MHz, CDCl₃): δ = 2.13 (s, 3 H), 2.69-2.71 (m, 2 H), 2.74-2.77 (m, 2 H), 3.84 (s, 2 H), 7.24-7.33 (m, 5 H) ppm. ¹³C NMR (125 MHz, CDCl₃): δ = 17.0, 28.1, 30.4, 44.7, 127.2, 128.9, 129.3, 139.7, 207.6 ppm. MS: m/z (%) = 242 (30) [M + 2]⁺, 240 (16) [M⁺], 181 (10), 91 (100), 65 (22), 43 (51). Anal. Calcd for C₁₁H₁₄OSe: C, 54.78; H, 5.85. Found: C, 54.51; H, 5.64.