184–186 °C, 2163.7 (c 0.59, H2O); lit.,17 184–186 °C, 2170 (c
0.86, H2O)} (Scheme 3).
We thank the Takeda Science Foundation for financial
support.
Notes and References
† E-mail: konol@mail.cc.tohoku.ac.jp
1
‡ All new compounds had spectroscopic (IR, H NMR, 13C NMR, Mass)
and analytical (combustion and/or high resolution mass) data consistent
with the assigned structure.
1 For example: E. Haslam, Progress in the Chemistry of Organic Natural
Products, ed. W. Herz, G. W. Kirby, R. E. Moore, W. Steglich and C.
Tamm, Springer-Verlag, Wien, New York, 1996, vol. 69, p. 158;
P. M. Dewick, Nat. Prod. Rep., 1998, 15, 17 and previous reports.
2 For example, M. C. Kozlowski, N. J. Tom, C. T. Seto, A. M. Sefler and
P. A. Bartlett, J. Am. Chem. Soc., 1995, 117, 2128; C. U. Kim, W. Lew,
M. A. Williams, H. Liu, L. Zhang, S. Swaminathan, N. Bischofberger,
M. S. Chen, D. B. Mendl, C. Y. Tai, W. G. Laver and R. C. Stevens,
J. Am. Chem. Soc., 1997, 119, 681.
3 Pertinent reviews for the synthesis of shikimic acid, see: M. M. Camp-
bell, M. Sainsbury and P. A. Seavle, Synthesis, 1993, 179; S. Jiang and
G. Singh, Tetrahedron, 1998, 54, 4697; Natural (2)-quinic acid has
been used as a versatile chiral building block: A. Barco, S. Benetti,
C. D. Risi, P. Marchetti, G. P. Pollini and V. Zanirato, Tetrahedron:
Asymmetry, 1997, 8, 3515.
4 An alternative enantiocontrolled synthesis developed by the present
group: T. Kamikubo and K. Ogasawara, Chem. Lett., 1996, 987.
5 R. Grewe, W. Lorenzen and L. Vining, Chem. Ber., 1954, 87, 793;
E. E. Smissman and M. A. Oxman, J. Am. Chem. Soc., 1963, 85, 2184;
J. Wolinsky, R. Novak and R. Vasileff, J. Org. Chem., 1964, 29,
3596.
6 Conversion from D-arabinose, H. J. Bestmann and H. A. Heid, Angew.
Chem., Int. Ed. Engl., 1971, 10, 336; see also R.-M. Meier and C.
Tamm, Helv. Chim. Acta., 1991, 79, 807; H. Suemune, K. Matsuno, M.
Uchida and K. Sakai, Tetrahedron: Asymmetry, 1992, 3, 297.
7 K. Hiroya, Y. Kurihara and K. Ogasawara, Angew. Chem., Int. Ed.
Engl., 1995, 34, 2287.
Scheme 3 Reagens and conditions: i, thiocarbonyl-1,1A-diimidazole, 50 °C,
14 h (100%); ii, Bu3SnH, toluene, reflux, 9 h (80%); iii, CBr4, MeOH,
reflux, 19 h (86%); iv, NaOH, H2O, roo temp., 13 h (100%); v, DBU,
MeOH, 220 °C, 20 h; vi, (MeO)2CHNMe2, room temp., 23 h; vii, Tf2O,
Pri2NEt, toluene, 50 °C, 1 h (80% from 11); viii, 2% HCl–MeOH, room
temp., 40 h (95%); ix, NaOH, THF–H2O (1:1), room temp., 1 h (96%)
8 S. Otsuka and K. Tani, Synthesis, 1991, 665.
9 K. Ogasawara, Pure Appl. Chem., 1994, 66, 2119.
10 G. Bu¨chi, R. Kulsa, K. Ogasawara and R. Rosati, J. Am. Chem. Soc.,
1970, 92, 999.
11 H. Irie, J. Katakawa, M. Tomita and Y. Mizuno, Chem. Lett., 1981,
637.
12 M. Miyashita, A. Yoshikoshi and P. A. Grieco, J. Org. Chem., 1977, 42,
3772.
13 D. H. R. Barton, W. B. Motherwell and A. Stange, Synthesis, 1981, 743;
J. R. Rasmussen, C. J. Slinger, R. J. Kordish and D. D. Newman-Evans,
J. Org. Chem., 1981, 46, 4843.
14 A. S.-Y. Lee, H.-C. Yeh and J.-J. Shie, Tetrahedron Lett., 1998, 39,
5249.
15 Merck Index, 1996, 12, 8243.
16 J. L. King, B. A. Posner, K.-T. Mak and N. C. Yang, Tetrahedron Lett.,
1987, 34, 3919.
17 G. W. Fleet, T. K. M. Shing and S. M. Warr, J. Chem. Soc., Perkin
Trans. 1, 1984, 905.
was carried out in one step by refluxing 13 with CBr4 in
MeOH14 to give methyl quinate 14, [a]3D0 231.6 (c 1.45,
MeOH), which was identical with authentic material derived
from natural (2)-quinic acid 1. Finally, 14 was hydrolyzed with
NaOH to give (2)-quinic acid 1, mp 167–168 °C, [a]3D0 243.6
(c 2.03, H2O) {lit.,15 162–163 °C, 242 to 244 (H2O)}.
On the other hand, to obtain (2)-shikimic acid 2, 11 was first
deacetylated to give the cis-1,2-diol 15, which afforded the
cyclohexene 17, [a]2D9 219.7 (c 1.12, CHCl3), via the cyclic
amino acetal 16 on treatment with N,N-dimethylformamide
dimethyl acetal followed by Tf2O.16 Exposure of 17 with dilute
HCl in MeOH allowed spontaneous desilylation and removal of
the acetonide group to give methyl shikimate 18, [a]2D9 2130.0
(c 0.91, EtOH), which was identical with authentic material.4
Finally, 18 was hydrolyzed with NaOH to give (2)-shikimic
acid 2, mp 184–185 °C, [a]2D5 2164.0 (c 0.59, H2O) {lit.,4
Received in Cambridge, UK, 23rd July 1998; 8/05775C
2034
Chem. Commun., 1998