2 C. C. Ramão, F. E. Kühn and W. A. Herrmann, Chem. Rev., 1997,
7, 3197 and references cited therein.
(a) W. A. Herrmann, R. W. Fischer, M. U. Rauch and W. Scherer,
J. Mol. Catal., 1994, 86, 221; (b) W. A. Herrmann, D. W. Marz,
W. Wagner, J. G. Kuchler, G. Weichselbaumer and R. W. Fischer,
Ger. Pat. 3902357, 1989 to Hoechst AG; (c) G. L. Grocco, W. F.
Shum, J. G. Zajacek and H. S. Kesling, Jr., US Pat. 5166372, 1992 to
Arco.
requires 713.9633), 695 (33%), 501 (26), 407 (92), 319 (56), 288
100).
9
(
3
General procedure for epoxidation at room temperature
A 10 ml flask was charged with 5 mmol substrate, 1 mmol of
internal standard (n-alkane), 10 mmol of 60% H O , the
2
2
approriate amount of HReO4 and cocatalyst and 5 ml of
solvent. The flask was stirred at room temperature with a
magnetic stirring bar (1000 rpm). Aliquots of the reaction
mixture (~0.05 ml) were diluted with 2 ml ethyl acetate. 10 mg
of MnO was added to the solution to decompose the H O .
4 (a) J. Rudolph, K. L. Reddy, J. P. Chiang and K. B. Sharpless, J. Am.
Chem. Soc., 1997, 119, 6189; (b) C. Copéret, H. Adolfsson and
K. B. Sharpless, Chem. Commun., 1997, 1565.
5
6
7
8
W. A. Herrmann, R. M. Kratzer, H. Ding, W. R. Thiel and H. Glas,
J. Organomet. Chem., 1998, 555, 293; see also M. Nakajima,
Y. Sasaki, H. Iwamoto and S. Hashimoto, Tetrahedron Lett., 1998,
2
2
2
The suspension was filtered and analysed by GLC.
3
9, 87.
(a) W. A. Herrmann, F. E. Kühn, R. W. Fischer, W. R. Thiel and
C. C. Romão, Inorg. Chem., 1992, 31, 4431; (b) W. A. Herrmann,
R. M. Kratzer and R. W. Fischer, Angew. Chem., Int. Ed. Engl.,
General procedure for epoxidation at a higher temperature
A 10 ml round-bottom flask, equipped with a reflux condenser
and maintained under an inert atmosphere, was charged with
1
997, 36, 2652.
Hydrogen peroxide is manufactured as an aqueous solution of
35–70% concentration and can be considered safe at concentrations
up to 70%. Higher concentrations (>85%) can decompose with
detonation.
5
mmol substrate, 1 mmol of internal standard (n-alkane or
dibutyl ether), 10 mmol of 60% H O , the approriate amount
2
2
of HReO and cocatalyst and 10 ml of solvent. The reaction
4
(a) S. Warwel, M. R. Klaas and M. Sojka, J. Chem. Soc., Chem.
Commun., 1991, 1578; (b) S. Warwel, M. R. Klaas and M. Sojka, US
Pat. 5344946, 1994 to Solvay Interox; (c) L. Kim, US Pat. 4418203,
mixture was heated with an oil bath to the indicated temper-
ature and stirred with a magnetic stirring bar at 1000 rpm.
Aliquots of the reaction mixture (~0.05 ml) were diluted with 2
1
983 to Shell Oil.
ml ethyl acetate. 10 mg of MnO was added to the solution to
9 (a) D. Had zˇ i, J. Chem. Soc., 1962, 5128; (b) U. Böhner and
G. Zundel, J. Phys. Chem., 1985, 89, 1408.
2
decompose the H O . The suspension was filtered and analysed
2
2
1
1
0 A. M. Rozen, A. S. Skotnikov and E. G. Teterin, Zh. Neorg. Khim.,
by GLC.
1
982, 27, 739; Chem. Abstr., 1982, 96, 206282j.
1 J. Sobczak and J. J. Ziółkowski, J. Mol. Catal., 1981, 13, 11.
Acknowledgements
This research is sponsored by the Dutch Innovation Oriented
Research Program on Catalysis (IOP Catalysis, IKA 96018).
12 (a) R. A. W. Johnstone en Francsicsné-Czinege, WO 98/17640, 1998
to Solvay Interox Limited; (b) M. C. A. van Vliet, I. W. C. E. Arends
and R. A. Sheldon, Tetrahedron Lett., 1999, 40, 5239.
13 D. K. Srivastava, L. K. Krannich and C. L. Watkins, Inorg. Chem.,
1
990, 29, 3502.
1
4 F. F. Blicke and E. L. Cataline, J. Am. Chem. Soc., 1938, 60,
419.
References
1
1
5 W. R. Cullen and P. E. Yates, Can. J. Chem., 1963, 41, 1625.
6 A. L. Rheingold, D. L Staley and M. E. Fountain, J. Organomet.
Chem., 1989, 365, 123.
1
(a) S. E. Jacobson, F. Mares and P. M. Zambri, J. Am. Chem. Soc.,
1
1
979, 101, 6946; (b) H. J. Reich, F. Chow and S. L. Peake, Synthesis,
978, 299; (c) G. Strukul and R. A. Michelin, J. Chem. Soc., Chem.
1
1
1
7 W. Steinkopf, H. Donat and P. Jaeger, Chem. Ber., 1922, 55,
Commun., 1984, 1538; (d) C. Venturello and R. D’Aloisio, J. Org.
Chem., 1988, 53, 1553; (e) Y. Ishii, K. Yamawaki, T. Ura, H.
Yamada, T. Yoshida and M. Ogawa, J. Org. Chem., 1988, 53, 3587;
2
597.
8 W. J. Jones, W. J. C. Byke, G. Davies, D. C. Griffiths and J. H. E.
Webb, J. Chem. Soc., 1932, 2284.
9 E. R. N. Bornancini, S. M. Palacios, A. B. Peñéñory and R. A.
Rossi, J. Phys. Org. Chem., 1989, 2, 255.
(
(
f ) R. Neumann and M. Gara, J. Am. Chem. Soc., 1995, 117, 5066;
g) K. Sato, M. Aoki, M. Ogawa, T. Hashimoto and R. Noyori,
J. Org. Chem., 1996, 61, 8310; (h) T. Kamiyama, M. Inoue,
20 E. W. Abel and G. W. Farrow, J. Chem. Res. (S), 1979, 278.
21 J. Chatt and F. G. Mann, J. Chem. Soc., 1939, 1622.
22 H. H. Anderson, J. Am. Chem. Soc., 1961, 83, 547.
H. Kashiwagi and S. Enomoto, Bull. Chem. Soc. Jpn., 1990, 63,
1
559; (i) P. L. Anelli, S. Banfi, F. Montanari and S. Quici, J. Chem.
Soc., Chem. Commun., 1989, 779; (j) D. de Vos and T. Bein, Chem.
Commun., 1996, 917; (k) M. G. Clerici and P. Ingallina, J. Catal.,
1
993, 140, 71.
Paper a907975k
3
80
J. Chem. Soc., Perkin Trans. 1, 2000, 377–380