T. Moriuchi et al. / Tetrahedron Letters 48 (2007) 2667–2670
2669
a
Table 2. Oxidative bromination of stilbenes in water in the presence of an additive
NH4VO3 (10 mol%)
H2O2 (2.0 equiv)
HBr (2.0 equiv)
KBr (3.0 equiv)
additive
Br
Br
or
H2O, Ar, rt, 24 h
+
Br
OH
A
B
Additive
NMR yields/% (erythro/threo)
From trans-stilbene
From cis-stilbene
A + B
A
B
A + B
A
B
1
51
37
71
10
{33(88/12)/18(100/0)}
{21(58/42)/16(81/19)}
{44(93/7)/27(100/0)}
{7(93/7)/3(100/0)}
94
94
98
86
{67(13/87)/27(26/74)}
{71(47/53)/23(26/74)}
{77(17/83)/21(33/67)}
{62(32/68)/24(25/75)}
SDS
DTAB
None
OSO3— Na+
SDS: 40 mol%
O
O
O
O
O
O
N Me3Br—
+
O
O
OH
HO
OH
HO
: 10 mol%
DTAB: 40 mol%
1
a
The reaction was carried out by using stilbene, 10 mol % of NH
0 mol % of an additive in H O at room temperature for 24 h.
4 3 2 2
VO , 2.0 equiv of H O , 2.0 equiv of HBr, 3.0 equiv of KBr, and 10 mol % or
4
2
In conclusion, the present procedure provides an effi-
cient method for the catalytic oxidative bromination in
aqueous media. The more efficient bromination was
attained in the presence of the cationic surfactant. Stud-
ies on the reaction mechanism and synthetic application
are now in progress.
Rev. 1999, 187, 17–35; (f) Butler, A.; Carter, J.; Simpson,
M. In Handbook on Metalloproteins; Bertini, I., Sigel, A.,
Sigel, H., Eds.; Marcel Dekker: New York, 2001; pp 153–
1
79; (g) Wever, R.; Hemrika, W. In Handbook of Metal-
loproteins; Messerschmidt, A., Huber, R., Poulos, T.,
Wieghardt, K., Eds.; Wiley: Chichester, 2001; pp 1417–
1
428; (h) Ligtenbarg, A. G. J.; Hage, R.; Feringa, B. L.
Coord. Chem. Rev. 2003, 237, 89–101.
3
. (a) Bhattacharjee, M. Polyhedron 1992, 11, 2817–2818; (b)
Conte, V.; Di Furia, F.; Moro, S. Tetrahedron Lett. 1994,
Acknowledgments
3
5, 7429–7432; (c) Dinesh, C. U.; Kumar, R.; Pandey, B.;
Kumar, P. J. Chem. Soc., Chem. Commun. 1995, 611–612;
d) ten Brink, H. B.; Tuynman, A.; Dekker, H. L.;
This work was financially supported in part by a Grant-
in-Aid for Scientific Research on Priority Areas from the
Ministry of Education, Culture, Sports, Science, and
Technology, Japan. Thanks are also due to the Analyt-
ical Center, Graduate School of Engineering, Osaka
University for the use of their facilities.
(
Hemrika, W.; Izumi, Y.; Oshiro, T.; Schoemaker, H. E.;
Wever, R. Inorg. Chem. 1998, 37, 6780–6784; (e) Bora, U.;
Bose, G.; Chaudhuri, M. K.; Dhar, S. S.; Gopinath, R.;
Khan, A. T.; Patel, B. K. Org. Lett. 2000, 2, 247–249; (f)
Rothenberg, G.; Clark, J. H. Org. Process Res. Dev. 2000,
4, 270–274; (g) Martinez, J. S.; Carroll, G. L.; Tschirret-
Guth, R. A.; Altenhoff, G.; Little, R. D.; Butler, A. J. Am.
Chem. Soc. 2001, 123, 3289–3294; (h) Carter-Franklin, J.
N.; Parrish, J. D.; Tschirret-Guth, R. A.; Little, R. D.;
Butler, A. J. Am. Chem. Soc. 2003, 125, 3688–3689; (i)
Maurya, M. R.; Saklani, H.; Agarwal, S. Catal. Commun.
2004, 5, 563–568; (j) Greb, M.; Hartung, J.; K o¨ hler, F.;
References and notes
1
. (a) Srivastava, S. K.; Chauhan, P. M. S.; Bhaduri, A. P.
Chem. Commun. 1996, 2679–2680; (b) Clark, J. H.; Ross, J.
C.; Macquarrie, D. J.; Barlow, S. J.; Bastock, T. W. Chem.
Commun. 1997, 1203–1204; (c) Barhate, N. B.; Gajare, A.
S.; Wakharkar, R. D.; Bedekar, A. V. Tetrahedron Lett.
ˇ
Spehar, K.; Kluge, R.; Csuk, R. Eur. J. Org. Chem. 2004,
3799–3812; (k) Conte, V.; Floris, B.; Galloni, P.; Silvagni,
A. Pure Appl. Chem. 2005, 77, 1575–1581; (l) Khan, A. T.;
Goswami, P.; Choudhury, L. H. Tetrahedron Lett. 2006, 47,
2751–2754.
1
998, 39, 6349–6350.
2
. (a) Butler, A. In Bioinorganic Catalysis; Reedijk, J., Ed.;
Marcel Dekker: New York, 1992; pp 425–445; (b) Sigel, H.;
Sigel, A.. In Metal Ions in Biological Systems; Marcel
Dekker: New York, 1995; Vol. 31; (c) Butler, A.; Walker, J.
V. Chem. Rev. 1993, 93, 1937–1944; (d) Rehder, D. Coord.
Chem. Rev. 1999, 182, 297–322; (e) Butler, A. Coord. Chem.
4. General procedure of the catalytic oxidative bromination:
To a stirred mixture of a substrate (0.20 mmol), NH VO
4
3
(2.34 mg, 0.02 mmol), and KBr (71.4 mg, 0.60 mmol) in
O (5 mL) were added 48% HBr (45.5 lL, 0.40 mmol)
H
2