´
A. Arcadi, M. Chiarini, F. Marinelli, Z. Berente, L. Kollar
FULL PAPER
α-(3-Trifluoromethylbenzyl)-γ-butyrolactone (5f): 0.380 g; 78%; oil. NMR (400 MHz CDCl3): δ ϭ 7.0 (d, J ϭ 8.0 Hz, 1 H), 6.65 (dd,
1
Ϫ IR (neat): ν ϭ 1770 cmϪ1. Ϫ H NMR (400 MHz CDCl3): δ ϭ J ϭ 8, 2 Hz, 1 H), 6.58 (d, J ϭ 2.0 Hz, 1 H), 4.30 (m, 1 H,
˜
7.38Ϫ7.50 (m, 4 H, Ar-H), 4.24 (dt, J ϭ 2.4, 8.8 Hz, 1 H, OCHaHb), 4.12 (m, 1 H, OCHaHb), 3.70 (s, 3 H, OCH3), 1.6Ϫ2.9
OCHaHb), 4.15 (dt, J ϭ 6.4, 9.2 Hz, 1 H, OCHaHb), 3.28 (dd, (m, 12 H). Ϫ MS: m/z (%) ϭ 260 (10) [Mϩ], 174(100), 161 (70). Ϫ
J ϭ 3.2, 12.8 Hz, 1 H, ArCHaHb), 2.82 (m, 2 H, ArCH2CH ϩ C16H20O3 calcd. C 73.82, H 7.74; found C 74.11, H 7.96.
ArCHaHb), 2.25 (m, 1 H, OCH2CHaHb), 1.95 (m, 1 H, OCH2-
CHaHb). Ϫ 13C NMR (100.58 MHz CDCl3): δ ϭ 178.1 (CO-O),
139.4, 132.3, 131.0 (q, 1J(13C,19F) ϭ 32 Hz), 129.2, 125.5, 123.6,
Acknowledgments
We thank the CNR and Murst, as well as OTKA (T023525) for
providing financial support.
122.7, 66.4 (OCH2), 40.8 (COCH), 35.8 (ArCH2), 28.0
(OCH2CH2). Ϫ MS: m/z (%) ϭ 244 (65) [Mϩ], 216 (95), 215 (78),
172 (30), 159 (100). Ϫ C12H11F3O2: calcd. C 59.02, H 4.54; found
C 58.48, H 5.06.
[1] [1a]
α-(4-Methoxybenzyl)-γ-butyrolactone (5g): 0.288 g; 70%; m.p.
I. P. Beletskaya, A. V. Cheprakov, Chem. Rev. 2000, 100,
[1b]
40Ϫ41 °C. Ϫ IR (KBr): ν ϭ 1780, 1610, 800, 715 cmϪ1. Ϫ 1H
3009Ϫ3066. Ϫ
M. Beller, T. H. Riermeier, G. Stark In
˜
Transition Metals for Organic Synthesis (Eds.: M. Beller, C.
Bolm), VCH, Weinheim, Germany, 1998, p 208. Ϫ
Palladium Reagents and Catalysts, Wiley, Chichester, U. K.,
NMR (400 MHz CDCl3): δ ϭ 7.12 (d, J ϭ 8.4 Hz, 2 H, Ar-H),
6.82 (d, J ϭ 8.4 Hz, 2 H, Ar-H), 4.15 (dt, J ϭ 2.8, 8.8 Hz, 1 H,
OCHaHb), 4.09 (dt, J ϭ 6.8, 8.8 Hz, 1 H, OCHaHb), 3.74 (s, 3 H,
OCH3), 3.12 (dd, J ϭ 4.0, 13.4 Hz, 1 H, ArCHaHb), 2.76 (m, 1 H,
J ϭ 3.6, 8.4 Hz, 18.0 Hz, ArCH2CH), 2.68 (dd, J ϭ 8.8, 13.4 Hz,
1 H, ArCHaHb), 2.20 (dddd, 1 H, OCH2CHaHb), 1.94 (m, 1 H,
OCH2CHaHb). Ϫ 13C NMR (100.58 MHz CDCl3): δ ϭ 178.9 (CO-
O), 158.3, 130.3, 129.8, 113.9, 66.5 (OCH2), 55.1 (OCH3), 41.1
(COCH), 35.0 (ArCH2), 27.7 (OCH2CH2). Ϫ MS: m/z (%) ϭ 206
(25) [Mϩ], 178 (7), 121 (100). Ϫ C12H14O3: calcd. C 69.88, H 6.84;
found C 69.57, H 6.89.
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J. Tsuji,
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427Ϫ436. Ϫ
28, 2Ϫ7.
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[3a] A. Arcadi, S. Cacchi, G. Fabrizi, F. Marinelli, Synlett 2000,
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vath, Z. Tuba, J. Org. Chem. 1999, 64, 5921Ϫ5925.
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[4b]
α-(1-Naphthylmethyl)-γ-butyrolactone (5h): 0.267 g; 59%; m.p.
5034Ϫ5036. Ϫ
S. Rousset, J. Thibonnet, M. Abarbri, A.
1
75Ϫ77 °C. Ϫ IR (KBr): ν ϭ 1770, 1595, 760 cmϪ1. Ϫ H NMR
˜
ˆ
Duchene, J.-L. Parrain, Synlett 2000, 260Ϫ262.
[5] [5a]
E. A. K. Gebbing, G. A. Stork, J. M. Jansen, A. de Groot,
(400 MHz CDCl3): δ ϭ 8.04 (d, J ϭ 8.4 Hz, 1 H, Ar-H), 7.86 (d,
1 H, J ϭ 9.2 Hz. Ar-H), 7.76 (d, J ϭ 8.4 Hz, 1 H, Ar-H), 7.50 (m,
2 H, Ar-H), 7.4 (t, J ϭ 7.2 Hz, 1 H, Ar-H), 7.32 (d, J ϭ 6.8 Hz,
1 H, Ar-H), 4.30 (dt, J ϭ 2.8, 9.0 Hz, 1 H, OCHaHb), 4.10 (dt, J ϭ
9.0, 6.4 Hz, 1 H, OCHaHb), 3.92 (dd, J ϭ 2.8, 13.2 Hz, 1 H,
ArCHaHb), 3.00 (m, 1 H, ArCH2CH), 2.96 (dd, J ϭ 13.2, 10.4 Hz,
1 H, ArCHaHb), 2.11 (m, 1 H, OCH2CHaHb), 2.0 (m, 1 H,
OCH2CHaHb). Ϫ 13C NMR (100.58 MHz CDCl3): δ ϭ 178.8 (CO-
O), 134.7, 134.0, 131.5, 129.0, 127.6, 126.7, 126.4, 125.8, 125.4,
123.3, 66.6 (OCH2), 40.4 (COCH), 33.5 (ArCH2), 28.8
(OCH2CH2). Ϫ MS: m/z (%) ϭ 226 (15) [Mϩ], 181 (100). Ϫ
C15H14O2: calcd. C 79.62, H 6.24; found C 79.37; H 6.07.
[5b]
Tetrahedron 1999, 55, 11077Ϫ11094. Ϫ
J. Mulzer In Com-
prehensive Organic Synthesis (Eds.: I. Fleming, B. M. Trost),
Pergamon, Oxford, 1991, vol. 6, p. 323. Ϫ [5c] S. Steuer, J. Pod-
[5d]
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S. Rousset, M. Abar-
[5e]
1, 701Ϫ703. Ϫ
Y. S. Rao, Chem. Rev. 1976, 76, 625Ϫ694.
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[6a] H. N. M. Hoffmann, Angew. Chem. Int. Ed. Engl. 1985, 24,
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G. A. Howie, J. Med. Chem. 1974, 17, 840Ϫ843. Ϫ
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[7] [7a]
R. Sharma, J. Lee, S. Wang, G. W. A. Milne, N. E. Lewin,
P. M. Blumberg, V. E. Marquez, J. Med. Chem. 1996, 39,
[7b]
19Ϫ28. Ϫ
J. Lee, S. Wang, G. W. A. Milne, R. Sharma, N.
α-(17-Oxo-5α-androstan-3β-ylmethyl)-γ-butyrolactone (5l): 0.595 g;
E. Lewin, P. M. Blumberg, V. E. Marquez, J. Med. Chem. 1996,
39, 29Ϫ35. Ϫ
1
80%; m.p. 142Ϫ144 °C. Ϫ IR (KBr): ν ϭ 1770, 1745 cmϪ1. Ϫ H
[7c]
˜
J. Lee, R. Sharma, S. Wang, G. W. A. Milne,
NMR (400 MHz CDCl3): δ ϭ 4.26 (dt, 1 H, OCHaHb), 4.12 (dt, 1
H, OCHaHb), 2.6 (m, 1 H,), 2.35 (m, 2 H, 16-CH2), 0.78 (s, 3 H,
18-CH3), 0.72 (s, 3 H, 19-CH3). Ϫ 13C NMR (50.3 MHz CDCl3):
δ ϭ 221.5 (CO), 180.1 (CO-O), 67.0 (OCH2), 51.1, 47.7, 46.4, 46.3,
38.3, 37.2, 36.2, 35.8, 35.0, 34.4, 31.5, 30.8, 30.5, 29.2, 28.3, 27.7,
24.8, 20.7, 20.5, 13.7, 12.1. Ϫ MS: m/z (%) ϭ 372 (22) [Mϩ], 357
(16), 354 (34), 328 (62), 301 (61), 269 (68), 86 (100). Ϫ C24H36O3:
calcd. C 77.38, H 9.74; found C 77.26, H 9.37.
N. E. Lewin, Z. Szallasi, P. M. Blumberg, C. George, V. E.
Marquez, J. Med. Chem. 1996, 39, 36Ϫ45.
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W.-Y. Yu, C. Bensimon, H. Alper, Chem. Eur. J. 1997, 3,
417Ϫ423 and references therein.
´
A. Arcadi, M. Chiarini, F. Marinelli, Z. Berente, L. Kollar,
Org. Lett. 2000, 2, 69Ϫ72.
[10] [10a] A. Arcadi, S. Cacchi, G. Fabrizi, F. Marinelli, P. Pace, Eur.
[10b]
J. Org. Chem. 1999, 3305Ϫ3313. Ϫ
A. Arcadi, S. Cacchi,
G. Fabrizi, F. Marinelli, Synlett 1993, 65Ϫ68. Ϫ [10c] A. Arcadi,
B. Burini, S. Cacchi, M. Delmastro, F. Marinelli, B. R. Pie-
troni, J. Org. Chem. 1992, 57, 976Ϫ982. Ϫ
Bernocchi, S. Cacchi, F. Marinelli, Tetrahedron 1991, 47,
α-(5α-Cholestan-3β-ylmethyl)-γ-butyrolactone (5m): 0.771 g; 82%;
[10d]
A. Arcadi, E.
m.p. 143Ϫ144 °C. Ϫ IR (KBr): ν ϭ 1775 cmϪ1. Ϫ 1H NMR
˜
(400 MHz CDCl3): δ ϭ 4.32 (dt, 1 H, OCHaHb), 4.16 (m, 1 H,
OCHaHb), 2.6 (m, 1 H, COCH), 2.36 (m, 1 H, 3-CH), 0.63 (s, 3 H,
18-CH3), 0.74 (s, 3 H, 19-CH3), 0.85 (d, 6 H, 26-CH3 ϩ 27-CH3);
0.9 (d, 3 H, 21-CH3). Ϫ 13C NMR (50.3 MHz CDCl3): δ ϭ 180.0
(CO-O), 66.4 (OCH2), 46.5 (COCH), 46.4, 42.5, 40.5, 40.1, 38.4,
36.9, 35.9, 35.7, 35.4, 34.5, 32.1, 30.1, 29.2, 28.9, 28.2, 27.9, 24.1,
23.9, 23.8, 22.5, 21.3, 21.0, 18.0, 12.0. Ϫ MS: m/z (%) ϭ 470 (13)
[Mϩ], 455 (20), 330 (10), 315 (100), 301 (28), 247 (75). Ϫ C32H54O2:
calcd. C 81.64, H 11.56; found C 81.36, H 11.24.
1525Ϫ1540.
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A. Arcadi, S. Cacchi, F. Marinelli, E. Morera, G. Ortar,
Tetrahedron 1990, 46, 7151Ϫ7164. Ϫ [11b] S. Cacchi, P. G. Ciat-
tini, E. Morera, G. Ortar, Tetrahedron Lett. 1987, 28,
3039Ϫ3042.
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C. Amatore, A. Jutand, M. A. M‘Barki, Organometallics
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1992, 11, 3009Ϫ3013. Ϫ
F. Ozawa, A. Kubo, T. Hayashi,
Chem. Lett. 1992, 11, 2177Ϫ2180.
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[14] [14a]
H. M. R. Hoffmann, B. Schmidt, S. Wolff, Tetrahedron
[14b]
α-[6-Methoxytetrahydronaphth-1-yl)methyl]-γ-butyrolactone (5n):
1989, 45, 6113Ϫ6126. Ϫ
1987, 28, 3179Ϫ3182.
G. E. Stokker, Tetrahedron Lett.
1
0.395 g; 76%; m.p. 90Ϫ92 °C. Ϫ IR (KBr): ν ϭ 1767 cmϪ1. Ϫ H
˜
3172
Eur. J. Org. Chem. 2001, 3165Ϫ3173