Oxidation of Alkynes in Aqueous Media Catalyzed by Diphenyl Diselenide

Abstract

In this communication we propose a convenient methodology to effect the oxidation of alkynes using ammonium persulfate and diphenyl diselenide as catalyst. The reactions effected in aqueous media lead to 1,2-unprotected dicarbonyl derivatives or to hemiacetals starting from terminal alkynes.

Key words

selenium - oxidation - catalysis - alkynes - water chemistry

References and Notes

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14

In a typical procedure (PhSe)₂ (0.1 mmol) and (NH₄)₂S₂O₈ (3 mmol) were suspended in H₂O (5 mL) (or in a 3:1 mixure of H₂O-MeCN) and heated at 60 ˚C for 15 min. To the resulting red-orange reaction mixture alkyne (1a-m, 1 mmol) was added and stirred for the time reported in Tables  [²] and  [³] . After the usual workup the crude was purified by a silica gel chromatography using CH₂Cl₂ or a mixture 1:99 R^²OH-CH₂Cl₂ as eluent.
All the compounds, after purification, were fully characterized by GC-MS, ^¹H NMR, and ^¹³C NMR experiments. Physical and spectral data for the products not previously described in literature are reported below.
2-Hydroxy-2-isopropoxy-1-phenylethanone (9g) Oil. ^¹H NMR (400 MHz, CDCl₃): δ = 8.07 (d, 2 H, J = 7.5 Hz), 7.64 (t, 1 H, J = 7.5 Hz), 7.51 (t, 2 H, J = 7.5 Hz), 5.79 (d, 1 H, J = 8.0 Hz), 4.57 (d, 1 H, J = 8.0 Hz), 4.27 (sept, 1 H, J = 6.4 Hz), 1.35 (d, 3 H, J = 6.4 Hz), 1.28 (d, 3 H, J = 6.4 Hz) ppm. ^¹³C NMR (100.62 MHz, CDCl₃): δ = 194.5, 134.9, 133.4, 130.0, 129.1, 90.9, 71.0, 24.2, 22.2 ppm. GC-MS: m/z (relative intensity) = 192 (1), 121 (51), 105 (100), 77 (58), 51 (29). 1-Hydroxy-1-methoxydecan-2-one (8h) Oil. ^¹H NMR (400 MHz, CDCl₃): δ = 4.86 (d, 1 H, J = 9.2 Hz), 4.10 (d, 1 H, J = 9.0 Hz), 3.50 (s, 3 H), 2.78-2.71 (m, 1 H), 2.57-2.45 (m, 1 H), 1.71-1.62 (m, 2 H), 1.30-1.28 (m, 10 H), 0.89 (t, 3 H, J = 6.0 Hz) ppm. ^¹³C NMR (100.62 MHz, CDCl₃): δ = 206.1, 95.5, 55.5, 37.9, 35.5, 31.7, 29.2, 23.0, 14.0 ppm. GC-MS: m/z (relative intensity) = 202 (1), 141 (100), 123 (33) 71 (94), 57 (94).
1-Hydroxy-1-methoxyhexan-2-one (8i) Oil. ^¹H NMR (400 MHz, CDCl₃): δ = 4.81 (d, 1 H, J = 9.0 Hz), 4.09 (d, 1 H, J = 9.0 Hz) 3.50 (s, 3 H), 2.78-2.65 (m, 1 H), 2.65-2.43 (m, 1 H), 1.65-1.53 (m, 2 H), 1.43-1.23 (m, 2 H), 0.90 (t, 3 H, J = 7.01 Hz) ppm. ^¹³C NMR (100.6 MHz, CDCl₃): δ = 206.1, 95.5, 55.5, 37.5, 25.1, 22.2, 13.7 ppm. GC-MS: m/z (relative intensity) = 146 (13), 119 (10), 97 (36), 85 (60), 77 (50), 70 (55), 57 (100).
2-Hydroxy-2-methoxy-1-(4′-bromophenyl)-ethanone (8l) Mp 109-110 ˚C. ^¹H NMR (400 MHz, CDCl₃): δ = 7.95-7.85 (m, 2 H), 7.65-7.55 (m, 2 H), 5.57 (d, 1 H, J = 9.0 Hz), 4.55 (d, 1 H, J = 9.0 Hz), 3.55 (s, 3 H) ppm. ^¹³C NMR (100.62 MHz, CDCl₃): δ = 193.6, 132.6, 131.8, 131.4, 130.4 93.4, 55.0 ppm. GC-MS: m/z (relative intensity) = 242 (1), 183 (100), 157 (83), 75 (60), 50 (51).
2-Hydroxy-2-methoxy-1-(4′-methoxyphenyl)-ethanone (8m) Mp 87-88 ˚C. ^¹H NMR (400 MHz, CDCl₃): δ = 8.10-8.05 (m, 2 H), 7.05-6.95 (m, 2 H), 5.59 (s, 1 H), 4.75 (br s, 1 H), 3.90 (s, 3 H) 3.53 (s, 3 H) ppm. ^¹³C NMR (100.62 MHz, CDCl₃): δ = 192.6, 165.0, 132.5, 126.0, 114.5, 93.1, 55.9, 54.7 ppm. GC-MS: m/z (relative intensity) = 196 (1), 134 (100), 107 (80), 92 (83), 77 (86), 63 (51), 50 (29).