COMMUNICATIONS
phenoxide concentration was determined from UV/Vis spectroscopy at
288 nm (phenol), 390 nm (3-nitrophenol), 400 nm (4-nitrophenol), or
420 nm (2,4-dinitrophenol), within the linear Beerꢁs Law regime as
determined by a four-point calibration curve. For quantitation in THF,
the matrix was heated at reflux in the absence of air with 1 equiv of
nitrophenol in THF (4 mL) for 2 h. The concentration of phenoxide was
measured spectroscopically as above.
[19] V. Ramesh, H.-S. Chien, M. M. Labes, J. Phys. Chem. 1987, 91, 5937 ±
5940.
[20] F. G. Bordwell, Acc. Chem. Res. 1988, 21, 456 ± 463.
[21] D. H. Gray, D. L. Gin, Chem. Mater. 1998, 10, 1827 ± 1832.
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2523.
[23] A. C. O. Hann, A. Lapworth, J. Chem. Soc. 1904, 85, 46 ± 56.
Size-exclusion experiments. The cross-linked LLC matrix (10 mg) was
stirred with 1 equiv, by cation content, of either Alcian Blue (pyridine
variant) or gallamine triethiodide in D2O (2 mL) in the absence of air.
After one day of stirring, the suspensions were centrifuged and an aliquot
was analyzed. Alcian Blue (pyridine variant) was analyzed quantitatively
by UV/Vis spectroscopy at 615 nm. Measurements were taken within the
linear regime for Beerꢁs Law. Gallamine triethiodide concentrations were
analyzed by integration of 1H NMR signals using DMSO as an internal
standard.
Atom-Efficient Oxidation of Alkenes with
Molecular Oxygen: Synthesis of Diols**
Received: May 17, 1999 [Z13430IE]
German version: Angew. Chem. 1999, 111, 3206 ± 3210
Christian Döbler, Gerald Mehltretter, and
Matthias Beller*
Keywords: heterogeneous catalysis ´ liquid crystals ´ nano-
structures ´ zeolite analogues
Dedicated to Professor Manfred Baerns
on the occasion of his 65th birthday
The selective oxidation of alkenes with molecular oxygen
involving the participation of both oxygen atoms is one of the
most significant challenges in modern catalysis research. In
spite of the advantages of oxygen over ªclassicalº stoichio-
metric oxidizing agents (e.g. peracids, chlorates, periodates),
only one oxygen atom is generally incorporated into the
molecule in the oxidation of alkenes with molecular oxygen.
The second oxygen atom reacts with a reducing agent present
to form by-products, which are thus formed in stoichiometric
amounts. Such processes are found in enzymatic oxidations,[1]
transition metal catalyzed reactions with O2/H2, and stoichio-
metric reactions with O2/RCHO or O2/alkylarenes.[2] Groves
et al. have been able for the first time to show that both
oxygen atoms of molecular oxygen are used during epoxida-
tion in the presence of a porphyrin ± ruthenium catalyst.[3]
Because of the industrial importance of diols, both as bulk
chemicals (in particular propylene glycol)[4] and as fine
chemicals, we are interested in carrying out dihydroxylations
with molecular oxygen as oxidant (Scheme 1).
[1] J. M. Thomas, R. G. Bell, C. R. Catlow, Handbook of Heterogeneous
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Nature 1992, 359, 710 ± 712; b) J. S. Beck, J. C. Vartuli, W. J. Roth,
M. E. Leonowicz, C. T. Kresge, J. Am. Chem. Soc. 1992, 114, 10834 ±
10843.
[4] a) A. Sayari, Chem. Mater. 1996, 8, 1840 ± 1852; b) J. Y Ying, C. P.
Mehnert, M. S. Wong, Angew. Chem. 1999, 111, 58 ± 82; Angew. Chem.
Int. Ed. Engl. 1999, 38, 56 ± 77.
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London, 1985.
[8] D. H. Gray, S. Hu, E. Juang, D. L. Gin, Adv. Mater. 1997, 9, 731 ± 736.
[9] The very low water content in the mixture is consistent with an inverse
mesophase, and addition of water leads to the expected lamellar
structure. See also reference [8].
[10] J. M. Seddon, Biochim. Biophys. Acta 1990, 1031, 1 ± 69. Based on the
known water content, approximate densities of the materials, and the
interchannel distances (from X-ray diffraction), the pore diameters
for IH1 and IH2 were calculated to be about 10 ± 15 and the wall
thicknesses about 30 .
OH
catalyst
R2
R2
1/2 O2
H2O
+
+
R1
R1
OH
[11] G. Jones, Org. React. 1967, 15, 204 ± 599.
Scheme 1. Metal-catalyzed dihydroxylation with molecular oxygen.
[12] a) S. Patai, Y. Israeli, J. Chem. Soc. 1960, 2020 ± 2024; b) S. Patai, Y.
Israeli, J. Chem. Soc. 1960, 2024 ± 2030; c) S. Patai, J. Zabicky, J. Chem.
Soc. 1960, 2030 ± 2038; d) S. Patai, J. Zabicky, Y. Israeli, J. Chem. Soc.
1960, 2038 ± 2044.
Osmium(viii) compounds have proved to be the most
reliable metal catalysts for dihydroxylations. On the basis of
the pioneering work of Sharpless et al.[5] it has been possible
to demonstrate the preparative potential of the method,
Â
[13] A. Corma, V. Fornes, R. M. Martín-Aranda, H. García, J. Primo, Appl.
Catal. 1990, 59, 237 ± 248.
[14] K. R. Kloetstra, H. van Bekkum, J. Chem. Soc. Chem. Commun. 1995,
1005 ± 1006.
[15] D. J. McQuarrie, D. B. Jackson, Chem. Commun. 1997, 1781 ± 1782.
[16] a) M. S. Fernandez, P. Fromherz, J. Phys. Chem. 1977, 81, 1755 ± 1761;
b) F. Greiser, C. J. Drummond, J. Phys. Chem. 1988, 92, 5580 ± 5593;
c) O. A. El Seoud, Adv. Colloid Interface Sci. 1989, 30, 1 ± 30.
[17] a) S. R. Holmers-Farley, R. H. Reamey, T. J. McCarthy, J. Deutch,
G. M. Whitesides, Langmuir 1985, 1, 725 ± 740; b) S. R. Holmes-Farley,
C. D. Bain, G. M. Whitesides, Langmuir 1988, 4, 921 ± 927; c) J. Wang,
L. M. Frostman, M. D. Ward, J. Phys. Chem. 1992, 96, 5224 ± 5228.
[18] J. E. Frommer, R. G. Bergman, J. Am. Chem. Soc. 1980, 102, 5227 ±
534.
[*] Prof. Dr. M. Beller, Dr. C. Döbler, Dipl.-Chem. G. Mehltretter
Institut für Organische Katalyseforschung (IfOK)
Buchbinderstrasse 5 ± 6, D-18055 Rostock (Germany)
Fax: (49)381-46693-24
[**] This work was supported by the Bildungsministerium des Landes
Mecklenburg-Vorpommern and Bayer AG (Leverkusen). We thank I.
Stahr for experimental support, and K. Kortus and Dr. C. Fischer for
the GC and HPLC investigations.
3026
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1433-7851/99/3820-3026 $ 17.50+.50/0
Angew. Chem. Int. Ed. 1999, 38, No. 20