2320
Q. Shao, C. Li
LETTER
O
O
O
O
+
S
O
O
X–
Se
O–
S+
O O
O
R1
R2
O
R2
R1
R1
R2
H
R2
R2
R1
H
2
S+
6a
S+
(Z)-3
S
O–
O
X–
7a
O
anti-betaine 5a
S
O
R2
O
OH–
SeO2
4
Se
R1
–O
OH
H
O
+
S
O
O
1
O
+
O
O
S
R1
S
X–
Se
O–
R2
O
R2
+
R1
H
R1
S
R1
R2
7b
(E)-3
O
O–
O
O
R2
O
syn-betaine 5b
6b
Scheme 3 Plausible mechanism of Na2SeO3 (SeO2 and Na2CO3)-catalyzed condensation of sulfonium salt and glyoxal hydrate
(5) (a) Aggarwal, V. K.; Hynd, G.; Picoul, W.; Vasse, J.-L.
J. Am. Chem. Soc. 2002, 124, 9964. (b) Johnson, C. R.;
Schroeck, C. W.; Shanklin, J. R. J. Am. Chem. Soc. 1973, 95,
7424.
(6) (a) Payne, G. B. J. Org. Chem. 1968, 33, 3517. (b) Trost,
B. M.; Arndt, H. C. J. Org. Chem. 1973, 38, 3140.
(7) (a) Johnson, A. W.; Amel, R. T. J. Org. Chem. 1969, 34,
1240. (b) Ratts, K. W.; Yao, A. N. J. Org. Chem. 1966, 31,
1689.
combination of SeO2 and Na2CO3 or mineral salt
Na2SeO3. The reaction conditions are milder than the pro-
cedures reported before. Additionally, to our knowledge,
this is the first use of selenium dioxide or sodium selenite
as a condensation catalyst.
Supporting Information for this article is available online at
(8) Gosselck, J.; Schmidt, G.; Béress, L.; Schenk, H.
Tetrahedron Lett. 1968, 9, 331.
(9) Typical Procedure for Preparing Compound 3
A mixture of 1a (152 mg, 1.0 mmol), 2a (261 mg, 1.0
mmol), SeO2 (4.4 mg, 0.04 mmol), and Na2CO3 (10.6 mg,
0.1 mmol) in MeCN (10 mL) was stirred for 4.5 h at r.t. After
complete consumption of starting material (TLC), MeCN
was removed in vacuum to give yellow syrup. The residue
was extracted with CH2Cl2 (2 × 30 mL). The combined
organic layers were washed with brine (10 mL) and dried
over anhyd Na2SO4. The extracts were then concentrated
under reduced pressure, and the residue was purified by
column chromatography (eluent: PE–EtOAc) on SiO2 to
give an 81% yield of 3a [(Z)-3a, 129 mg; (E)-3a, 100 mg].
Compound (Z)-3a: 1H NMR (400 MHz, CDCl3): d = 8.08 (d,
J = 8.5 Hz, 2 H), 7.95 (d, J = 8.5 Hz, 2 H), 7.69–7.44 (m, 6
H), 7.10 (s, 1 H), 2.17 (s, 3 H). 13C NMR (100 MHz, CDCl3):
d = 191.9, 188.2, 160.6, 137.8, 134.9, 134.8, 132.7, 130.0,
129.1, 128.6, 128.1, 116.0, 15.4. IR (KBr): n = 2926, 1670,
1635, 1596, 1537, 1246, 1023, 699 cm–1.
Acknowledgment
We thank NSFC (20572078) and TMSTC (05YFGPGX07500) for
financial support.
References and Notes
(1) (a) Chen, A.; Yin, G.; Gao, M.; Wang, Z.; Wu, A. Chin. J.
Org. Chem. 2007, 27, 220; suppl.. (b) Jiao, Y.; Da, S.; Xie,
Z.; Li, Y. Chin. J. Org. Chem. 2007, 27, 285; suppl.
(c) Mosterd, A.; Matser, H. J.; Bos, H. J. T. Tetrahedron
Lett. 1974, 15, 4179.
(2) (a) Akiyama, S.; Nakatsuji, S.; Hamamura, T.; Kataoka, M.;
Nakagawa, M. Tetrahedron Lett. 1979, 20, 2809.
(b) Dieter, R. K.; Silks, L. A. III. J. Org. Chem. 1986, 51,
4687. (c) Kang, W.; Sekiya, T.; Toru, T.; Ueno, Y. J. Chem.
Soc., Perkin Trans. 1 1990, 441.
Compound (E)-3a: 1H NMR (400 MHz, CDCl3): d = 8.00 (d,
J = 8.0 Hz, 2 H), 7.89 (d, J = 8.0 Hz, 2 H), 7.57–7.43 (m, 6
H), 7.04 (s, 1 H), 2.45 (s, 3 H). 13C NMR (100 MHz, CDCl3):
d = 193.7, 185.1, 160.8, 137.2, 134.9, 133.6, 133.0, 128.8,
128.7, 128.6, 128.4, 115.8, 14.9. IR (KBr): n = 3413, 1674,
1637, 1540, 1220, 781, 703, 632 cm–1. Spectral data were in
agreement with those previously reported.3
(3) (a) Yin, G.; Zhou, B.; Meng, X.; Wu, A.; Pan, Y. Org. Lett.
2006, 8, 2245. (b) Furukawa, N.; Akasaka, T.; Aida, T.;
Oae, S. J. Chem. Soc., Perkin Trans. 1 1977, 7, 372.
(4) (a) Aggarwal, V. K.; Winn, C. L. Acc. Chem. Res. 2004, 37,
611. (b) Li, A.; Dai, L.; Aggarwal, V. K. Chem. Rev. 1997,
97, 2341. (c) Edwards, D. R.; Du, J.; Crudden, C. M. Org.
Lett. 2007, 9, 2397. (d) Aggarwal, V. K.; Harvey, J. N.;
Richardson, J. J. Am. Chem. Soc. 2002, 124, 5747.
Synlett 2008, No. 15, 2317–2320 © Thieme Stuttgart · New York