ORGANIC
LETTERS
2
005
Vol. 7, No. 17
633-3635
Catalytic Asymmetric Desymmetrization
of Cyclic meso-1,3- and 1,4-Diols by a
Phosphinite Derivative of Quinidine
3
Shinya Mizuta, Takeo Tsuzuki, Tetsuya Fujimoto,* and Iwao Yamamoto
Department of Functional Polymer Science, Shinshu UniVersity,
Tokida Ueda 386-8567, Japan
Received May 15, 2005
ABSTRACT
Asymmetric monobenzoylation reactions of cyclic meso-1,3- and 1,4-diols were catalyzed by a phosphinite derivative of quinidine to afford the
corresponding monobenzoylated diol with good yield and enantioselectivity.
Enantioselective monoacylation of meso-diols is a powerful
methodology for the preparation of useful chiral building
blocks. In recent years, several successful examples of
nonenzymatic catalysts for the desymmetrization of meso-
diols by asymmetric acylation have been reported. In
and effective nonenzymatic catalysts for them have been
recently reported. In 2000, Oriyama et al. reported the
impressive catalytic asymmetric monobenzoylation of cis-
4-cyclopentene-1,3-diol by chiral diamine organocatalysts.2b
The reaction was catalyzed by only 0.5 mol % of the chiral
diamines to afford the monobenzoylated product with excel-
lent enantioselectivity (98% ee), but the yield of the product
decreased because of the formation of the dibenzoylated
product.
particular, some effective nonenzymatic catalysts for meso-
1
1
,2-diols have been realized. However, in comparison to
the promising results of the meso-1,2-diols, only a few
examples of the nonenzymatic asymmetric acylation catalysts
2
We have recently designed a bifunctional organocatalyst4,5
bearing both Lewis basic phosphinite and Brφnsted basic
tertiary amine functional groups for asymmetric acylation
for 1,3- or 1,4-diols have been reported. In particular, the
asymmetric desymmetrization of cyclic meso-1,3- or 1,4-
3
diols was mainly carried out using an enzymatic procedure,
(
1) (a) Vedejs, E.; Daugulis, O.; Diver, S. T. J. Org. Chem. 1996, 61,
(3) For some examples, see: (a) Johnson, C. R.; Bis, S. J. Tetrahedron
Lett. 1992, 33, 7287-7290. (b) Ghorpade, S. R.; Kharul, R. K.; Joshi, R.
R.; Kalkote, U. R.; Ravindranathan, T. Tetrahedron: Asymmetry 1999, 10,
891-899. (c) Hilpert, H.; Wirz, B. Tetrahedron 2001, 57, 681-694. (d)
Betts, R. L.; Murphy, S. T.; Johnson, C. R. Tetrahedron: Asymmetry 2004,
15, 2853-2860.
(4) For some recent examples of bifunctional organocatalysts, see: (a)
Okino, T.; Hoashi, Y.; Takemoto, Y. J. Am. Chem. Soc. 2003, 125, 12672-
12673. (b) Mase, N.; Tanaka, F.; Barbas, C. F., III. Org. Lett. 2003, 5,
4369-4372. (c) Okino, T.; Nakamura, S.; Furukawa, T.; Takemoto, Y. Org.
Lett. 2004, 6, 625-627. (d) Berkessel, A.; Cleemann, F.; Mukherjee, S.;
M u¨ ller, T. N.; Lex, J. Angew. Chem., Int. Ed. 2005, 44, 807-811. (e) Matsui,
K.; Takizawa, S.; Sasai, H. J. Am. Chem. Soc. 2005, 127, 3680-3681. (f)
Li, B.-J.; Jiang, L.; Liu, M.; Chen, Y.-C.; Ding, L.-S.; Wu, Y. Synlett 2005,
603-606. (g) Berkessel, A.; Mukherjee, S.; Cleemann, F.; M u¨ ller, T. N.;
Lex, J. Chem. Commun. 2005, 1898-1900.
4
30-431. (b) Oriyama, T.; Imai, K.; Hosoya, T.; Sano, T. Tetrahedron
Lett. 1998, 39, 397-400. (c) Oriyama, T.; Imai, K.; Sano, T.; Hosoya, T.
Tetrahedron Lett. 1998, 39, 3529-3532. (d) Matsumura, Y.; Maki, T.;
Murakami, S.; Onomura, O. J. Am. Chem. Soc. 2003, 125, 2052-2053. (e)
Vedejs, E.; Daugulis, O.; Tuttle, N. J. Org. Chem. 2004, 69, 1389-1392.
(
2) (a) Duhamel, L.; Herman, T. Tetrahedron Lett. 1985, 26, 3099-
3
1
2
2
102. (b) Oriyama, T.; Hosoya, T.; Sano, T. Heterocycles 2000, 52, 1065-
069. (c) Oriyama, T.; Taguchi, H.; Terakado, D.; Sano, T. Chem. Lett.
002, 26-27. (d) Trost, B. M.; Mino, T. J. Am. Chem. Soc. 2003, 125,
410-2411. (e) Kawabata, T.; Stragies, R.; Fukaya, T.; Nagaoka, Y.;
Schedel, H.; Fuji, K. Tetrahedron Lett. 2003, 44, 1545-1548. (f) K u¨ ndig,
E. P.; Lomberget, T.; Bragg, R.; Poulard, C.; Bernardinelli, G. Chem.
Commun. 2004, 1548-1549. (g) For an asymmetric desymmetrization of a
meso-1,5-diol, see: Ruble, J. C.; Tweddell, J.; Fu, G. C. J. Org. Chem.
1
998, 63, 2794-2795.
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0.1021/ol051129m CCC: $30.25
© 2005 American Chemical Society
Published on Web 07/27/2005