LETTER
Practical Asymmetric Epoxidation of Olefins with H O under Phosphate-Buffered Conditions
2447
2
2
thalene oxide in 92% yield. The ee value was determined by HPLC
(3) (a) Matsumoto, K.; Sawada, Y.; Saito, B.; Sakai, K.;
analysis (DAICEL CHIRALCEL OB-H, hexane–i-PrOH = 99:1,
Katsuki, T. Angew. Chem. Int. Ed. 2005, 44, 4935.
1
.0 mL/min).
(b) Sawada, Y.; Matsumoto, K.; Katsuki, T. Angew. Chem.
Int. Ed. 2007, 46, 4559.
4) (a) Juliá, S.; Masana, J.; Vega, J. C. Angew. Chem., Int. Ed.
Engl. 1980, 19, 929. (b) Colonna, S.; Molinari, H.; Banfi, S.;
Juliá, S.; Masana, J.; Alvalez, A. Tetrahedron 1983, 39,
To a solution of salan ent-1 (4.64 g, 8.6 mmol) in CH Cl (189 mL),
Ti(Oi-Pr) (2.56 mL, 8.6 mmol) was added under nitrogen atmo-
sphere, and the resulting solution was stirred at r.t. After 1 h, CH Cl
2
2
(
4
2
2
(
(
943 mL), indene (50.5 mL, 430 mmol), and phosphate buffer
153 g, 0.05 M, pH 8.0) were added and the mixture was warmed to
1635. (c) Pietikäinen, P. Tetrahedron 1994, 50, 941.
(
(
d) Irie, R.; Hosoya, N.; Katsuki, T. Synlett 1994, 255.
e) Berkessel, A.; Frauenkron, M.; Schwenkreis, T.;
4
0 °C. Then, 30% H O (71.3 g) was added dropwise. After 8 h, aq
2 2
Na S O (215 mL, 1.0 M) was added to the reaction mixture. The
organic phase was separated and then washed with H O (100 mL).
2
2
3
Steinmetz, A.; Baum, G.; Fenske, D. J. Mol. Catal. A: Chem.
2
1996, 113, 321. (f) Pietikäinen, P. Tetrahedron 1998, 54,
4319. (g) Arai, S.; Tsuge, H.; Shioiri, T. Tetrahedron Lett.
1998, 39, 7563. (h) Francis, M. B.; Jacobsen, E. N. Angew.
The resultant organic phase was concentrated under reduced pres-
sure and the crude product was purified by distillation to give in-
dene oxide in 75% yield. The ee value was determined by HPLC
analysis (DAICEL CHIRALCEL OJ, hexane–i-PrOH = 80:20, 0.8
mL/min).
Chem. Int. Ed. 1999, 38, 937. (i) Shu, L.; Shi, Y.
Tetrahedron 2001, 57, 5213. (j) Kureshy, R. I.; Khan, N. H.;
Abdi, S. H. R.; Singh, S.; Ahmed, I.; Shunkla, R. S.; Jasra,
R. V. J. Catal. 2003, 219, 1. (k) Tse, M. K.; Döbler, C.;
Bhor, S.; Klawonn, M.; Mägerlein, W.; Hugl, H.; Beller, M.
Angew. Chem. Int. Ed. 2004, 43, 5255. (l) Marigo, M.;
Franzén, J.; Poulsen, T. B.; Zhuang, W.; Jørgensen, K. A. J.
Am. Chem. Soc. 2005, 127, 6964. (m) Colladon, M.; Scarso,
A.; Sgarbossa, P.; Michelin, R. A.; Strukul, G. J. Am. Chem.
Soc. 2006, 128, 14006. (n) Tse, M. K.; Bhor, S.; Klawonn,
M.; Anilkumar, G.; Jiao, H.; Spannenberg, A.; Döbler, C.;
Mägerlein, W.; Hugl, H.; Beller, M. Chem. Eur. J. 2006, 12,
Caution! It is recommended that unreacted H O be decomposed
with an appropriate reductant in large-scale reactions.
2
2
Caution! It is recommended that small amounts of crude product be
analyzed by DSC (differential scanning calorimetry) or ARC
(accelerating rate calorimetry).
Acknowledgment
This study was partly supported by a Grant-in-Aid for Scientific Re-
search (Specially Promoted Research 18002011) from the Ministry
of Education, Science, and Culture, Japan. K.M. is grateful for the
JSPS Research Fellowship for Young Scientists.
1875. (o) Colladon, M.; Scarso, A.; Sgarbossa, P.; Michelin,
R. A.; Strukul, G. J. Am. Chem. Soc. 2007, 129, 7680.
5) Sawada, Y.; Matsumoto, K.; Kondo, S.; Watanabe, H.;
Ozawa, T.; Suzuki, K.; Saito, B.; Katsuki, T. Angew. Chem.
Int. Ed. 2006, 45, 3478.
(
(
(
6) Matsumoto, K.; Sawada, Y.; Katsuki, T. Synlett 2006, 3545.
7) The main byproducts are hydroperoxyalcohols and diols.
References and Notes
(
1) (a) Jacobsen, E. N.; Wu, M. H. In Comprehensive
Asymmetric Catalysis, Vol. 2; Jacobsen, E. N.; Pfaltz, A.;
Yamamoto, H., Eds.; Springer: Heidelberg, 1999, Chap. 21,
(8) A phospate buffer of pH 7.4–8.0 can be used for the purpose
of suppressing the decomposition of epoxides.
(9) Other buffers such as acetate, citrate, and borate buffers were
also effective.
649–677. (b) Katsuki, T. In Comprehensive Coordination
Chemistry II, Vol. 9; McCleverty, J., Ed.; Elsevier Science:
Oxford, 2003, Chap. 9.4, 207–264.
2) (a) Saito, B.; Katsuki, T. Tetrahedron Lett. 2001, 42, 3873.
(10) (a) Lane, B. S.; Vogt, M.; DeRose, V. J.; Burgess, K. J. Am.
Chem. Soc. 2002, 124, 11946. (b) Grigoropoulou, G.; Clark,
J. H. Tetrahedron Lett. 2006, 47, 4461.
(
(
(
4
b) Saito, B.; Katsuki, T. Tetrahedron Lett. 2001, 42, 8333.
c) Tanaka, T.; Saito, B.; Katsuki, T. Tetrahedron Lett. 2002,
3, 3259. (d) Saito, B.; Katsuki, T. Chirality 2001, 15, 24.
(11) Unfortunately, reactions of aliphatic olefins were low
productive in view of both yield and enantioselectivity, even
under the optimized conditions.
(
12) In a large-scale synthesis, the addition of an excess amount
of ligand was not required, while the excess ligand was
added in a small scale in order to obtain reproducibility.
Synlett 2007, No. 15, 2445–2447 © Thieme Stuttgart · New York