Y. Uozumi et al. / Tetrahedron Letters 42 (2001) 411–414
413
Scheme 4.
HCl and extracted with toluene to give the crude 2. The
crude methyl ester acid 2 was dissolved in ether/hexane
(1:15) and the insoluble materials were filtered off. The
filtrate was concentrated and chromatographed on sil-
ica gel to give 2 in 72% yield. The enantiomeric purity
of 2 was determined by HPLC analysis of the anilide 4
to be 89% ee. The absolute configuration of 2 was
assigned to be (1S,2R) by comparison of the order of
retention time in the HPLC analysis of the anilide 4 to
that of an authentic sample prepared from (1S,2R)-6.5
1984, 779–781. (d) Hiratake, J.; Inagaki, M.; Yamamoto,
Y.; Oda, J. J. Chem. Soc., Perkin Trans. 1 1987, 1053–
1058. (e) Hiratake, J.; Yamamoto, Y.; Oda, J. J. Chem.
Soc., Chem. Commun. 1985, 1717–1719. (f) Theisen, P. D.;
Heathcock, C. H. J. Org. Chem. 1993, 58, 142–146. (g)
Suda, Y.; Yago, S.; Shiro, M.; Taguchi, T. Chem. Lett.
1992, 389–392. (h) Das, J.; Haslanger, M. F.; Gougoutas,
J. Z.; Malley, M. F. Synthesis 1987, 1100–1103. (i) Albers,
T.; Biagini, S. C. G.; Hibbs, D. E.; Hursthouse, M. B.;
Malik, K. M. A.; North, M.; Uriarte, E.; Zagotto, G.
Synthesis 1996, 393–398. (j) Ward, R. S.; Pelter, A.;
Edwards, M. I.; Gilmore, J. Tetrahedron: Asymmetry 1995,
6, 843–844. (k) Shimizu, M.; Matsukawa, K.; Fujisawa, T.
Bull. Chem. Soc. Jpn. 1993, 66, 2128–2130. (l) Seebach,
D.; Jaeschke, G.; Wang, Y. M. Angew. Chem., Int. Ed.
Engl. 1995, 34, 2395–2396. (m) Seebach, D.; Jaeschke, G.;
Gottwald, K.; Matsuda, K.; Formisano, R.; Chaplin, D.
A.; Breuning, M.; Bringmann, G. Tetrahedron 1997, 53,
7539–7556.
The mono ester acid 11, which is a synthetic intermedi-
ate for (−)-PGE1,9 and 12 were readily obtained in their
enantiomerically enriched form via asymmetric
methanolysis of (3-methyl)tetrahydrophthalic anhy-
dride 10. A racemic mixture of 10 (rac-10) was sub-
jected to the methanolysis catalyzed by 3e to give 80%
ee of (1R,2S,3S)-11 in 12% yield and 71% ee of
(1S,2R,3R)-12 in 29% yield. A Curtius rearrangement
of the methyl ester acids 11 and 12 gave the corre-
sponding N-protected b-amino acids (Scheme 4).
4. Recently, a highly enantioselective catalytic ring opening
of norbornenedicarboxylic anhydride using Ti-TADDO-
Late/Al(OiPr) system has been reported: Jaeschke, G.;
Seebach, D. J. Org. Chem. 1998, 63, 1190–1197.
Acknowledgements
5. It has been reported that Cinchona alkaloids promote
methanolysis of meso cyclic anhydrides with high enan-
tioselectivity of up to 98% ee in CCl4: Bolm, C.; Gerlach,
A.; Dinter, C. L. Synlett 1999, 195–196.
6. Risk data of carbon tetrachloride are given on the web
data base of IRIS, see: http://www.epa.gov/ngispgm3/iris/
subst/0020.htm? and references cited therein. Selected risk
data of carbon tetrachloride are as follows: RfDo(mg/kg/
d)=0.0007; CpSo (kg d/mg)=0.13; CpSi(kg d/mg)=
0.0525; Tap Water (mg/l: carcinogenic effects)=0.16;
Ambient Air (mg/m3: carcinogenic effects)=0.12.
This work was supported by a Grant-in-Aid for Scien-
tific Research, the Ministry of Education, Japan. Y.U.
thanks the Kowa Foundation for Life Science and
Technology and the Naito Foundation for partial
financial support of this work.
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