8788
Z. Shen et al. / Tetrahedron Letters 46 (2005) 8785–8788
2. Howard, A. S.; Meerholz, C. A.; Michael, J. P. Tetra-
12. A typical procedure for the reaction of acyl cyanides with
acetone is as follows: L-proline (70 mg, 0.6 mmol) was
stirred in acetone (10 mL) for 30 min. To this was added
acyl cyanide (2.0 mmol) at room temperature while
stirring for the desired time given in Table 1 (checked by
TLC, ether/ethyl acetate = 4:1, v/v). The solid was
removed by filtration and the filtrate was evaporated
under reduced pressure. The residue was stirred in a
mixture of CH2Cl2 (10 mL) and 5% NaOH (5 mL) for
30 min, extracted with CH2Cl2 (3 · 5 mL). The combined
organic phases were dried over anhydrous Na2SO4 and
concentrated in vacuum. The residue was purified by
column chromatography on silica gel (petroleum ether/
ethyl acetate = 20:1, v/v) yielding the 1,3-diketone in the
yields given in Table 1. All diketones obtained were fully
characterized by IR, 1H NMR, 13C NMR, and HRMS
spectroscopy.
hedron Lett. 1979, 15, 1339–1340.
3. Stork, G.; Brizzolara, A.; Landesman, H.; Szmuszkovicz,
J.; Terrell, R. J. Am. Chem. Soc. 1963, 85, 207–222.
4. (a) Mao, C. L.; Frostick, F. C.; Man, E. H.; Manyik, R.
M.; Wells, R. L.; Hauser, C. R. J. Org. Chem. 1969, 34,
1425–1429; (b) Manyik, R. M.; Frostick, F. C.; Sanderson,
J. J.; Hauser, C. R. J. Am. Chem. Soc. 1953, 75, 5030–5032.
5. Le Roux, C.; Mandrou, S.; Dubac, J. J. Org. Chem. 1996,
61, 3885–3887.
6. Wiles, C.; Watts, P.; Haswell, S. J.; Pombo-Villar, E.
Tetrahedron Lett. 2002, 43, 2945–2948.
7. (a) March, J. Advanced Organic Chemistry, 3rd ed.; John
Wiley & Sons: New York, 1985; p 436; (b) Jones, R. A.;
Nokkeo, S.; Singh, S. Synth. Commun. 1977, 7, 195–199;
(c) Taylor, E. C.; Hawks, G. H.; Mckillop, A. J. Am.
Chem. Soc. 1968, 90, 2421–2422.
8. Katritzky, A. R.; Wang, Z.; Wang, M.; Wilkerson, C. R.;
Hall, C. D.; Akhmedov, N. G. J. Org. Chem. 2004, 69,
6617–6622.
13. This had been demonstrated by the separation of N-
1
benzoyl-(S)-proline from the reaction mixture. H NMR
(400 MHz, CDCl3): d 1.87–1.94 (m, 1H), 2.00–2.09 (m,
1H), 2.23–2.29 (m, 1H), 2.33–2.39 (m, 1H), 3.59 (t,
J = 6.8Hz, 2H), 4.56 (br s, 1H), 4.76 (dd, J = 7.6,
4.8Hz, 1H), 7.38–7.58(m, 5H).
9. List, B. Tetrahedron 2002, 58, 5573–5590.
10. 1H NMR of 5g (400 MHz, CDCl3): d 2.31 (s, 3H), 2.85 (d,
J = 18.4 Hz, 1H), 3.93 (d, J = 18.4 Hz, 1H), 5.83 (s, 1H),
7.33–7.40 (m, 2H), 7.44 (d, J = 7.2 Hz, 1H), 7.83 (d,
J = 7.6 Hz, 1H).
14. Sakthivel, K.; Notz, W.; Bui, T.; Barbas, C. F., III. J. Am.
Chem. Soc. 2001, 123, 5260–5267.
15. Tang, Z.; Jiang, F.; Yu, L.-T.; Cui, X.; Gong, L.-Z.; Mi,
A. Q.; Jiang, Y.-Z.; Wu, Y.-D. J. Am. Chem. Soc. 2003,
125, 5262–5263.
11. 1H NMR of acetylated 5a (400 MHz, CDCl3): d 2.13–2.15
(m, 6H), 3.25 (d, J = 17.2 Hz, 1H), 3.45 (d, J = 17.2 Hz,
1H), 7.38–7.44 (m, 3H), 7.54 (d, J = 7.6 Hz, 2H).