R. R. Ferrett et al. / Tetrahedron Letters 44 (2003) 2573–2576
2575
Typical procedure13
75.39, 36.4, 35.8, 35.6, 34.5, 31.4, 31.2, 31.1, 30.9, 30.6,
21.4, 21.2.
Anhydrous copper sulfate (0.20 g, 1.3 mmol), mandelic
acid (0.20 g, 1.3 mmol), and aldehyde or ketone (2.0
mmol, 1.5 equiv.) were placed in a 10×150 mm test
tube. A rubber septum pierced by an open-ended capil-
lary tube was loosely fitted into the mouth of the tube.
The test tube (upright in a beaker) was placed into a
domestic microwave oven and irradiated according to
the data given in Table 1 with 1–2 min intervals
between irradiations. Caution: the test tube and con-
tents can become very hot! After cooling to room
temperature, the mixture was dissolved in 3 mL of
acetone, filtered through a short column of neutral
alumina, and the column washed with an additional 4.0
mL of acetone. The solvent and volatiles were removed
under vacuum, and the crude product was then purified
by flash column chromatography (ꢀ5% ethyl acetate/
hexane) if necessary.
(5S-1i): Two minor diastereomers: Anal. calcd for
C15H18O3: C, 73.15; H, 7.37. Found: C, 73.45; H, 7.38.
1H NMR (CDCl3): l 7.50–7.34 (m, 10 H), 5.44 (s, 1H),
5.42 (s, 1H), 2.04–1.31 (m, 18H), 1.030 (d, J=6.7 Hz,
3H), 1.035 (d, J=6.7 Hz, 3H); 13C NMR (CDCl3): l
171.7, 171.6, 135.5, 128.6, 126.8, 125.81, 125.77, 114.0,
113.7, 76.9, 76.5, 40.9, 40.1, 38.0, 37.0, 31.5, 31.0, 24.3,
24.1, 23.5, 22.9, 13.7. Two major diastereomers: Anal.
calcd for C15H18O3: C, 73.15; H, 7.37. Found: C, 73.14;
1
H, 7.58. H NMR (CDCl3): l 7.49–7.38 (m, 10H), 5.39
(s, 1H), 5.33 (s, 1H), 2.20–1.20 (m, 18H), 1.05 (d,
J=6.7 Hz, 3H), 1.01 (d, J=6.7 Hz, 3H); 13C NMR
(CDCl3): l 171.8, 171.7, 134.1, 133.9, 128.9, 128.6,
126.9, 126.8, 112.8, 112.7, 75.3, 75.0, 38.8, 38.6, 35.3,
34.3, 31.6, 30.7, 24.2, 24.1, 23.3, 23.2, 14.0, 13.8.
Analytical data for new compounds
References
All new compounds given below were derived from
(S)-(+)-mandelic acid.
1. Grover, P. T.; Bhongle, N. N.; Wald, S. A.; Senanayake,
C. H. J. Org. Chem. 2000, 65, 6283–6287.
2. Heckmann, B.; Mioshowski, C.; Lumin, S.; Falck, J. R.;
Wei, S.; Capdevila, J. H. Tetrahedron Lett. 1996, 37,
1425–1428.
3. (a) Barbaro, G.; Battaglia, A.; Guerrini, A.; Bertucci, C.
Tetrahedron: Asymmetry 1997, 8, 2527–2531; (b) Barbaro,
G.; Battaglia, A.; Guerrini, A. J. Org. Chem. 1999, 64,
4643–4651.
4. Mase, T.; Houpis, I. N.; Akao, A.; Dorziotis, I.; Emer-
son, K.; Hoang, T.; Iida, T.; Itoh, T.; Kamei, K.; Kato,
S.; Kato, Y.; Kawasaki, M.; Lang, F.; Lee, J.; Lynch, J.;
Maligres, P.; Molina, A.; Nemoto, T.; Okada, S.;
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Chem. 2001, 66, 6775–6786.
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6394–6395.
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49, 2513–2516.
7. Heckmann, B.; Mioskowski, C.; Bhatt, R. K.; Falck, J.
R. Tetrahedron Lett. 1996, 37, 1421–1424.
(2S,5S)-2-Butyl-5-phenyl-1,3-dioxolan-4-one (1a): Anal.
calcd for C13H16O3: C, 70.89; H, 7.32. Found: C, 71.25;
1
H, 7.43. H NMR (CDCl3): l 7.44–7.39 (m, 5H), 5.68
(t, J=4.8 Hz, 1H), 5.23 (s, 1H), 1.95 (dt, J=8.7, 4.9
Hz, 2H), 1.59–1.37 (m, 4H), 0.95 (t, J=7.2 Hz, 3H);
13C NMR (CDCl3): l 171.7, 133.6, 129.1, 128.7, 126.8,
104.5, 76.7, 33.7, 24.8, 22.3, 13.8.
(Mixture of 2R,5S and 2S,5S)-2-hexyl-5-phenyl-1,3-
dioxolan-4-one: Anal. calcd for C15H20O3: C, 72.55; H,
8.12. Found: C, 71.28; H, 8.06. (2S,5S cis-1c): 1H
NMR (CDCl3): l 7.43–7.39 (m, 5H), 5.68 (t, J=4.7 Hz,
1H), 5.22 (s, 1H), 1.99–1.90 (m, 2H), 1.57–1.32 (m, 8H),
0.90 (t, J=6.5 Hz, 3H); 13C NMR (CDCl3): l 171.7,
133.6, 129.1, 128.7, 126.8, 104.5, 76.7, 34.0, 31.5, 28.8,
1
22.7, 22.4, 14.0. (2R,5S trans-2c): H NMR (CDCl3): l
7.44–7.38 (m, 5H), 5.78 (t, J=4.8 Hz, 1H), 5.38 (s, 1H),
1.98–1.85 (m, 2H), 1.59–1.30 (m, 8H), 0.89 (t, J=6.3
Hz, 3H).
8. Heckmann, B.; Mioskowski, C.; Yu, J.; Falck, J. R.
Tetrahedron Lett. 1992, 33, 5201–5204.
(Mixture of 2R,5S and 2S,5S)-2-(z-3-hexenyl)-5-
phenyl-1,3-dioxolan-4-one: Anal. calcd for C15H18O3:
C, 73.15; H, 7.37. Found: C, 73.16; H, 7.51. (2S,5S
9. (a) Hoye, T. R.; Peterson, B. H.; Miller, J. D. J. Org.
Chem. 1987, 52, 1351–1353; (b) Pearson, W. H.; Cheng,
M.-C. J. Org. Chem. 1987, 52, 1353–1355; (c) Gorla, F.;
Venanzi, L. M. Helv. Chim. Acta 1990, 73, 690–697; (d)
Ott, J.; Tombo, G. M. R.; Schmid, B.; Venanzi, L. M.;
Wang, G.; Ward, T. R. Tetrahedron Lett. 1989, 30,
6151–6154; (e) Noyori, R.; Tsunoda, T.; Suzuki, M.
Tetrahedron Lett. 1980, 21, 1357.
10. (a) Farines, M.; Soulier, J. Bull. Soc. Chim. Fr. 1970,
332–340; (b) Chapel, N.; Greiner, A.; Ortholand, J.-Y.
Tetrahedron Lett. 1991, 32, 1441–1442.
11. For recent reviews, see: (a) Perreux, L.; Loupy, A. Tetra-
hedron 2001, 57, 9199–9223; (b) Lidstrom, P.; Tierney, J.;
Wathey, B.; Westman, J. Tetrahedron 2001, 57, 9225–
9283; (c) de la Hoz, A.; Diaz-Ortis, A.; Moreno, A.;
Langa, F. Eur. J. Org. Chem. 2000, 3659–3673; (d)
1
cis-1e): H NMR (CDCl3): l 7.44–7.36 (m, 5H), 5.70 (t,
J=4.7 Hz, 1H), 5.41–5.20 (m, 2H) 5.13 (s, 1H), 2.20 (q,
J=7.5 Hz, 2H), 2.02–1.85 (m, 4H), 0.87 (t, J=7.5 Hz,
3H); 13C NMR (CDCl3): l 171.6, 133.6, 133.4, 129.1,
128.7, 126.8, 126.5, 104.0, 76.7, 34.1, 20.7, 20.4, 14.2.
1
(2R,5S trans-2e): H NMR (CDCl3): l 7.47–7.35 (m,
5H), 5.78 (t, J=4.9 Hz, 1H), 5.50–5.26 (m, 2H), 5.40 (s,
1H).
(5S-1h): Mixture of two diastereomers: Anal. calcd for
C15H18O3: C, 73.15; H, 7.37. Found: C, 73.17; H, 7.47.
1H NMR (CDCl3): l 7.48–7.35 (m, 10 H), 5.40 (s, 1H),
5.36 (s, 1H), 2.09–1.74 (m, 12H), 1.51–1.32 (m, 6H),
0.96 (d, J=6.0 Hz, 6H); 13C NMR (CDCl3): l 171.4,
134.6, 128.8, 128.6, 126.32, 126.28, 111.7, 111.5, 75.43,