4
Tetrahedron
19. Sakaguchi, S.; Kikuchi, D.; Ishii, Y. Bull. Chem. Soc. Jpn. 1997,
70, 2561−2566.
H
O
H
H
H
R1
R2
R1
R2
O Br
OH
20. Bierenstiel, M.; D’Hondt, P. J.; Schlaf, M. Tetrahedron 2005, 61,
−4917.
4911
Br+
−H+
−HBr
21. General procedure for selective oxidation of 1,2-diols: To a
solution of 1,2-diol 1a (1.0 mmol) in water (4 mL), KBrO3 (0.5
mmol) was added followed by addition of KHSO4 (1.0 mmol).
The reaction was conducted at room temperature under shielding
from light until 1a disappeared, as monitored by TLC. After the
reaction completion, aqueous saturated Na2S2O3 solution (10 mL)
was added. The organic portion was extracted with AcOEt (3 x 40
mL) and then dried over MgSO4. The solvent was removed under
vacuum and the residue was subjected to silica gel column
chromatography (n-hexane/AcOEt 5:1) to afford (134 mg, 94%
yield) of product 2a.
O
H
intermediate
H
less nucleophilic
than hydroxy group
R1
R2
O
R1
R2
O
Br+
Br+
O
H
OH
H
lower chance of
formation of intermediate
22. Takase, K.; Masuda, H.; Kai, O.; Nishiyama, Y.; Sakaguchi, S.;
−872.
Ishii, Y. Chem. Lett. 1995, 871
23. Field, R. J.; Koros, E.; Noyes, R. M. J. Am. Chem. Soc. 1972, 94,
8649−8664.
24. Noyes, R. M. J. Phys. Chem. 1990, 94, 4404−4412.
Scheme 1. Selective oxidation of 1,2-diols
−2723.
25. Toth, Z.; Fabian, I. Inorg. Chem. 2004, 43, 2717
26. Toth, Z.; Fabian, I. Inorg. Chem. 2000, 39, 4608−4614.
Acknowledgments
27. Beckwith, R. C.; Wang, T.
This research was supported by a Grant-in-Aid for Scientific
Research on Innovative Areas "Advanced Molecular
Transformations by Organocatalysts" from The Ministry of
Education, Culture, Sports, Science and Technology, JSPS
KAKENHI Grant Number 24590012 as a Grant-in-Aid for
Scientific Research (C) from The Japan Society for the
Promotion of Science.
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