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LETTER
(6) For recent reports on phosphine-catalyzed reactions, see:
4. On the other hand, the intermediate 5 could deprotonate
the active methylene protons of 1,3-dicarbonyl com-
pounds as well, then underwent a-addition to provide
compound 3 as competing by-product.11b Actually, com-
pound 10 was not found when the reaction was carried out
in the absence of 1,3-dicarbonyl compound. The mecha-
nistic details of this reaction need further investigation.
(a) Zhu, X. F.; Schaffner, A. P.; Li, R. C.; Kwon, O. Org.
Lett. 2005, 7, 2977. (b) Jung, C. K.; Wang, J. C.; Krische,
M. J. J. Am. Chem. Soc. 2004, 126, 4118. (c) Du, Y.; Lu, X.
J. Org. Chem. 2003, 68, 6463. (d) Zhu, X. F.; Lan, J.;
Kwon, O. J. Am. Chem. Soc. 2003, 125, 4716. (e) Wang, J.
C.; Ng, S. S.; Krische, M. J. Angew. Chem. Int. Ed. 2003, 42,
5855. (f) Frank, S. A.; Mergott, D. J.; Roush, W. R. J. Am.
Chem. Soc. 2002, 124, 2404. (g) Wang, L. C.; Luis, A. L.;
Aqupiou, K.; Jang, H. Y.; Krische, M. J. J. Am. Chem. Soc.
2002, 124, 2402. (h) Lumbierres, M.; Moreno, M.;
Vallribera, A. Tetrahedron 2002, 58, 4061. (i) Kuroda, H.;
Tomita, I.; Endo, T. Org. Lett. 2003, 5, 129.
O
O
O
R2
R1
R2
Ph3P
R1CHO
R2
Ph3P
Ph3P
O
(7) (a) Trost, B. M.; Kazmaier, U. J. Am. Chem. Soc. 1992, 114,
7933. (b) Guo, C.; Lu, X. J. Chem. Soc., Chem. Commun.
1993, 394. (c) Guo, C.; Lu, X. J. Chem. Soc., Perkin Trans.
1 1993, 1921.
(8) (a) Grossman, R. B.; Varner, M. A.; Skaggs, A. J. J. Org.
Chem. 1999, 64, 340. (b) Grossman, R. B.; Comesse, S.;
Ranse, R. M.; Hattori, K.; Delong, M. N. J. Org. Chem.
2003, 68, 871.
(9) (a) Trost, B. M.; Li, C. J. J. Am. Chem. Soc. 1994, 116,
7595. (b) Trost, B. M.; Li, C. J. J. Am. Chem. Soc. 1994, 116,
10819. (c) Zhang, C.; Lu, X. Synlett 1995, 645. (d) Trost,
B. M.; Dake, G. R. J. Org. Chem. 1997, 62, 5670.
(e) Wang, J. C.; Ng, S. S.; Krische, M. J. J. Am. Chem. Soc.
2003, 125, 3682.
2
5
6
O
O
O
R2
R1
R2
R1
R2
R1
Ph3P
Ph3P
Ph3P
HO
HO
O
9
7
8
O
O
O
O
O
R2
R1
R1
R3
R2
R4
R3
R4
CH2
Ph3P
O
(10) (a) Du, Y.; Lu, X.; Yu, Y. J. Org. Chem. 2002, 67, 8901.
(b) Zhang, C.; Lu, X. J. Org. Chem. 1995, 60, 2906. (c)Xu,
Z.; Lu, X. Tetrahedron Lett. 1997, 38, 3461. (d) Zhu, G.;
Chen, Z.; Jiang, Q.; Xiao, D.; Cao, P.; Zhang, X. J. Am.
Chem. Soc. 1997, 119, 3836. (e) Xu, Z.; Lu, X. J. Org.
Chem. 1998, 63, 5031. (f) Xu, Z.; Lu, X. Tetrahedron Lett.
1999, 40, 549.
O
O
10
4
Scheme 3 A plausible mechanism in the reaction of aldehydes and
acetylides with 1,3-dicarbonyl moieties catalyzed by PPh3
(11) (a) Trost, B. M.; Dake, G. R. J. Am. Chem. Soc. 1997, 119,
7595. (b) Hanédanian, M.; Loreau, O.; Taran, F.;
Mioskowski, C. Tetrahedron Lett. 2004, 45, 7035.
(c) Hanédanian, M.; Loreau, O.; Sawicki, M.; Taran, F.
Tetrahedron 2005, 61, 2287.
In summary, we have described a new domino process
catalyzed by triphenylphosphine, which supplies an effi-
cient and facile way to synthesis multi-carbonyl com-
pounds from simple and commercially available starting
materials. The presented procedure leads to building
blocks, potential intermediates of organic materials.
Efforts are currently underway in our laboratories to
elucidate the mechanistic details of this reaction and to
disclose the scope and limitation of this reaction.
(12) Typical Procedure.
Benzaldehyde (0.3 mmol), 2,4-pentanedione (0.36 mmol)
and phenyl acetylenic ketone (0.36 Lmol) were dissolved in
3 mL CH2Cl2. The mixture was cooled to 0 °C, and 20 mol%
PPh3 was added. The resulting mixture was warmed to r.t.
and stirred for 6 h. After concentrated under reduced
pressure the residue was purified by flash chromatography
on silica gel (8:1 PE–EtOAc) to afford the corresponding
pure product.
Acknowledgment
Compound 4a: mp 126–128 °C (lit.14 mp 126–127 °C). 1H
NMR (300 MHz, CDCl3): d = 8.01 (d, J = 7.2 Hz, 4 H), 7.58
(m, 2 H), 7.46 (m, 4 H), 5.38 (t, J = 6.8 Hz, 1 H), 3.97 (t,
J = 6.8 Hz, 1 H), 2.51 (t, J = 6.8 Hz, 2 H), 2.27 (s, 6 H) ppm.
13C NMR (75 MHz, CDCl3): d = 204.4, 196.0, 135.6, 134.0,
129.1, 128.8, 64.8, 53.8, 29.8, 26.9 ppm. IR (neat): n = 1725,
1696, 1671, 1596, 1580, 1253, 1181 cm–1. HRMS (ESI):
m/z calcd for C21H20O4 [M + Na]+: 359.1254; found:
359.1255.
We thank the Natural Science Foundation of Anhui province (No.
050460302) for financial support.
References
(1) Carruthers, W.; Coldham, I. Modern Methods of Organic
Synthesis; Cambridge University Press: Cambridge, 2004,
1–71.
(2) Trost, B. M. Science 1991, 254, 1471.
(3) (a) Ho, T. L. Tandem Organic Reactions; Wiley-
Interscience: New York, 1992. (b) Tietze, L. F. Chem. Rev.
1996, 96, 115.
(4) Dong, V. M.; MacMillan, D. W. C. J. Am. Chem. Soc. 2001,
123, 2448.
(5) For a recent account on phosphine-catalyzed reactions, see:
(a) Lu, X.; Zhang, C.; Xu, Z. Acc. Chem. Res. 2001, 34, 535.
(b) Grossman, R. B.; Comesse, S.; Rasane, R. M.; Hattori,
K.; Delong, M. N. J. Org. Chem. 2003, 68, 871.
Compound 3a: 1H NMR (300 MHz, CDCl3): d = 16.66 (s, 1
H), 7.78 (m, 2 H), 7.53 (m, 1 H), 7.45 (m, 2 H), 6.08 (s, 1 H),
6.04 (s, 1 H), 2.01 (s, 6 H) ppm. 13C NMR (75 MHz, CDCl3):
d = 196.4, 191.1 (2 C), 143.5, 136.5, 133.4 133.3, 132.8,
130.7, 111.5, 23.9 (2 C) ppm. IR (neat): n = 1710, 1657,
1333, 1255, 1198 cm–1. HRMS (EI): m/z calcd for C14H14O3
[M+]: 230.0943; found: 230.0947.
(13) Li, C. Q.; Shi, M. Org. Lett. 2003, 5, 4273.
(14) Hellmann, H.; Dieterich, D. Justus Liebigs Ann. Chem.
1960, 632, 73.
Synlett 2005, No. 19, 2990–2992 © Thieme Stuttgart · New York