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DOI: 10.1055/s-0029-1219817
Oxidation of Alkynes in Aqueous Media Catalyzed by Diphenyl Diselenide
Publication History
Publication Date:
13 April 2010 (online)
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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
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1a
Santi C.Tiecco M.Testaferri L.Tomassini C.Santoro S.Bizzoca G. Phosphorus, Sulfur Silicon Relat. Elem. 2008, 183: 956 -
1b
Santoro S.Santi C.Sabatini M.Testaferri L.Tiecco M. Adv. Synth. Catal. 2008, 350: 2881 - 2
Freudendahl DM.Santoro S.Shahzad SA.Santi C.Wirth T. Angew. Chem. Int. Ed. 2009, 48: 8409 - 3
Tiecco M.Testaferri L.Tingoli M.Chianelli D.Bartoli D. J. Org. Chem. 1991, 56: 4529 -
4a
Hillis LR.Ronald RC. J. Org. Chem. 1985, 50: 470 -
4b
Mattay J.Runsik J. J. Org. Chem. 1985, 50: 2815 - 5
Zuliani V.Cocconcelli G.Fantini M.Ghiron C.Rivara M. J. Org. Chem. 2007, 72: 4551 ; and references cited therein - 6
Ahmad S.Iqbal J. J. Chem. Soc., Chem. Commun. 1987, 692 -
7a
Wolt S.Ingold CF. J. Am. Chem. Soc. 1983, 105: 7755 -
7b
Gopal H.Gordon AJ. Tetrahedron Lett. 1971, 12: 2941 - 8
Girard P.Counffignal R.Kagan HB. Tetrahedron Lett. 1981, 22: 3959 - 9
Yamashita M.Suemitsu RJ. J. Chem. Soc., Chem. Commun. 1977, 691 - 10
Iwahama T.Sakaguchi S.Nishiyama Y.Ishii Y. Tetrahedron Lett. 1995, 36: 1523 -
11a
Schroder M. Chem. Rev. 1980, 80: 187 -
11b
Muller P.Godey J. Helv. Chim. Acta 1981, 64: 2531 -
11c
Chang C.-L.Kumar MP.Liu R.-S. J. Org. Chem. 2004, 69: 2793 -
11d
Kashimura S.Murai Y.Washika C.Yoshihara D.Kataoka Y.Murase H.Shono T. Tetrahedron Lett. 1997, 38: 6717 -
11e
Crich D.Zou Y. J. Org. Chem. 2005, 70: 3309 -
11f
Srinivasan NS.Lee DG. J. Org. Chem. 1979, 44: 1574 -
11g
Dayan S.Ben-David I.Rozen S. J. Org. Chem. 2000, 65: 8816 -
12a
Santi C.Santoro S.Battistelli B.Testaferri L.Tiecco M. Eur. J. Org. Chem. 2008, 5387 -
12b
Santoro S.Battistelli B.Testaferri L.Tiecco M.Santi C. Eur. J. Org. Chem. 2009, 4921 - 13
Fix JA, andPogany SA. inventors; US 4, 440,740.
References and Notes
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 R²OH-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).