Pd(II)-Catalysed Oxidative Rearrangement of Propargylic Acetates
UPDATE
1
Preparation of Enol Acetates 2a ± 2h
ether); H NMR: d 2.19 (s, 3H), 3.70 (s, 3H), 6.70 ± 7.20 (3H,
13
arom.), 9.55 (s, 1H); C NMR: d 16.3, 20.4, 24.3, 26.7, 27.0,
Propargylic acetates 1a ± 1h (3.0 mmol) were dissolved in
absolute toluene (35 mL) and bis(acetonitrile)palladium(II)
chloride (147 mg, 0.57 mmol) was added to this solution under
inert conditions. Water was added to this brown, clear solution
2
1
3
7.0, 29.7, 35.0, 38.1, 43.4, 47.4, 55.2, 111.6, 113.8, 126.2, 132.0,
37.7, 138.6, 157.6, 162.3, 169.0, 184.1; MS (70 eV): m/z (%)
68 (50), 326 (80), 267 (45), 173 (100), 147 (60); anal. calcd for
C H O : C 74.97, H 7.66; found: C 74.80, H 7.87.
2
3
28
4
(
54 mL, 3 mmol). The reaction was monitored by TLC (4 ± 6 h,
room temperature). The reaction mixture was extracted 3
times with ether (50 mL) and with water (20 mL). The organic
layers were separated, dried(Na SO ), and filtered. Thefiltrate
was evaporated under vacuum and the residue was purified by
flash chromatography.
Acknowledgements
2
4
This research was supported by the Deutsche Forschungsge-
meinschaft. The author wishes to thank Prof. V. Rautenstrauch
(Firmenich, Genf) for providing 3-hydroxy-3-methylbut-1-yne.
6
-Oxo-4-dodecen-5-yl Acetate (2a): colourless oil;
1
H NMR: d 0.82 (t, J 7.1 Hz, 3H), 0.86 (t, J 7.1 Hz, 3H),
2
.20 (s, 3H), 2.48 (t, J 7.5 Hz, 2H), 6.38 (t, J 10.0 Hz, 1H);
13
C NMR: d 13.7, 14.0, 20.3, 22.4, 22.6, 25.9, 29.3, 29.4, 30.4,
3
1
1.9, 131.6, 146.3, 168.6, 193.9; MS (70 eV): m/z (%) 240 (20), References
83 (8), 141 (20), 99 (30), 71 (35), 55 (100); anal. calcd. (%) for
C H O : C 69.96, H 10.07; found: C 71.07, H 10.85.
14
24
3
[1] J. Tsuji, T. Mandai, Angew. Chem. 1995, 107, 2830 ± 2854;
Angew. Chem. Int. Ed. Engl. 1995, 34, 2830 ± 2854.
1
-Phenyl-3-oxo-1-nonen-2-yl Acetate (2b): colourless oil;
1
H NMR: d 0.82 (t, J 7.3 Hz, 3H), 2.03 (s, 3H), 2.64 (t, J
[
2] H. Schick, J. Spanig, R. Mahrwald, M. Bohle, T. Reiher,
T. Tetrahedron, 1992, 48, 5579 ± 5586 and references cited
therein.
1
3
7
1
1
.8 Hz, 2H), 7.10 (s, 1H), 7.10 ± 7.50 (5H, arom.); C NMR: d
4.0, 20.6, 22.5, 23.1, 28.9, 31.6, 63.5, 126.8, 128.7, 129.9, 130.1,
32.3, 144.9, 168.3, 194.5; MS (70 eV): m/z (%) 232 (35), 162
[
3] R. Mahrwald, H. Schick, H. Angew. Chem. 1991, 103,
(
58), 113 (98), 91 (100); anal. calcd. (%) for C H O : C 74.42, H
17 22 3
5
5
77 ± 578; Angew. Chem. Int. Ed. Engl. 1991, 30, 593 ±
94.
8.08; found: C 74.03, H 8.28.
1
,3-Diphenyl-3-oxo-1-propen-2-yl Acetate (2c): colourless
1
[4] H. Kataoka, K. Watanabe, K. Goto, Tetrahedron Lett.
1990, 31, 4181 ± 4184; H. Kataoka, K. Watanabe, K.
Miyazaki, S. Tahara, K. Ogu, R. Matsuoaka, K. Goto,
Chem. Lett. 1990, 1705.
oil; H NMR: d 2.24 (s, 3H), 6.80 (s, 1H), 7.20 ± 7.90 (10H,
arom.); 13C NMR: d 20.6, 128.4, 128.8, 129.4, 129.9, 130.2,
1
2
32.2, 132.4, 137.0, 144.7, 168.3, 190.5; MS (70 eV): m/z (%)
66 (10), 224 (35), 118 (10), 105 (100); anal. calcd. (%) for
[
[
5] V. Rautenstrauch, J. Org. Chem. 1984, 49, 950 ± 952.
6] T. Tabuchi, J. Inaga, M. Yamaguchi, Tetrahedron Lett.
1986, 27, 5237 ± 5240.
C H O : C 76.68, H 5.30; found: C 76.15, H 5.05.
17
14
3
1
-Phenyl-3-oxo-1-buten-2,4-diyl Diacetate (2d): colourless
1
oil; H NMR: d 2.10 (s, 3H), 2.24 (s, 3H), 5.00 (s, 2H), 7.02 (s,
1
3
1
1
H), 7.20 ± 7.60 (m, 5H, arom.); C NMR: d 20.4, 20.5, 64.9,
[7] E. P. Kohler, R. P. Barnes, J. Am. Chem. Soc. 1934, 56,
28.1, 128.9, 130.4, 130.4, 131.7, 142.4, 168.1, 170.1, 187.4; MS
211 ± 214.
(
70 eV): m/z (%) 262 (4), 220 (32), 178 (60), 91 (100); anal.
[8] P. Rona, P. Crabbe, J. Am. Chem. Soc. 1969, 91, 3289 ±
calcd. (%) for C H O : C 64.12, H 5.38; found: C 64.55, H 5.13.
3292.
14
14
5
1
-Cyclopentyliden-2-oxooctan-1-yl Acetate (2e): colourless
[
9] D. Vijaykumar, W. Mao, K. S. Kirschbaum, J. A. Katze-
1
oil; H NMR: d 0.80 (t, J 7.2 Hz, 3H), 2.10 (s, 3H), 2.32 (t,
J 8.0 Hz, 2H); C NMR: d 14.0, 20.5, 22.5, 23.4, 25.2, 27.2,
9.0, 31.7, 32.3, 32.5, 39.2, 138.6, 151.4, 169.1, 195.9; MS (70 eV):
nellenbogen, J. Org. Chem. 2002, 67, 4904 ± 4910.
13
[
[
[
[
10] R. Mahrwald, S. Quint, Tetrahedron 2000, 56, 7463 ±
468.
11] H. Fiesselmann, K. Sasse, Chem. Ber. 1956, 89, 1775 ±
791.
12] K. Miki, K. Ohe, S. Uemura, J. Org. Chem. 2003, 68,
505 ± 8513.
2
7
m/z (%) 252 (12), 210 (100), 140 (30); anal. calcd. (%) for
C H O : C 71.39, H 9.59; found: C 70.89, H 9.68.
1
5
24
3
1
15]
3
-Methyl-2-acetoxy-2-butenal (2f):[
colourless oil;
1
H NMR: d 2.01 (s, 3H), 2.07 (s, 3H), 2.12 (s, 3H), 9.61 (s,
8
1
H); 13C NMR: d 17.9, 20.0, 20.1, 142.7, 146.2, 168.6, 181.7;
13] P. H. Dixneuf, Chem. Commun. 1997, 2083 ± 2084; K.
Burgess, L. D. Jennings, J. Am. Chem. Soc. 1991, 113,
6129 ± 6139.
14] E. Velarde, P. Crabbe, A. T. Christensen, L. Tokes, J. W.
Murphy, J. H. Fried, Chem. Commun. 1970, 725 ± 726;
R. M. Kanojia, L. Yarmchuck, I. Scheer J. Org. Chem.
MS (70 eV): m/z (%) 142 (17), 100 (100), 88 (30); anal. calcd.
(
%) for C H O : C 59.14, H 7.09; found: C 58.97, H 7.33.
7 10 3
1
4
-Oxo-2-octen-3-yl Acetate (2 g): colourless oil; H NMR:
[
d 0.84 (t, J 7.2 Hz, 3H), 1.71 (d, J 6.8, 3H), 2.20 (s, 3H),
1
3
2
1
(
.54 (t, J 7.2 Hz, 2H), 6.47 (q, J 6.8 Hz, 1H); C NMR: d
1.7, 13.8, 20.2, 22.2, 26.2, 36.7, 126.9, 147.1, 168.6, 193.7; MS
1
974, 39, 2304 ± 2306; R. S. Bly, S. U. Koock, J. Am.
70 eV): m/z (%) 184 (15), 142 (80), 124 (100); anal. calcd.
(
%) for C H O : C 65.19, H 8.75; found C 64.78, H 8.62.
Chem. Soc. 1969, 91, 3289 ± 3292.
10
16
3
20-Acetoxy-20-formyl-3-methoxy-19-norpregna-1,3,5,17-
[15] V. Rautenstrauch, Tetrahedron Lett. 1984, 25, 3845 ±
tetraene (2 h): pale solid; mp 117 ± 1198C (hexane/diethyl
3846.
Adv. Synth. Catal. 2004, 346, 483 ± 485
asc.wiley-vch.de
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485