7330
J. H. Lee / Tetrahedron Letters 46 (2005) 7329–7330
OH
O
O
O
References and notes
i
+
NH4OAc
OR
OR
1
. Sih, C. J.; Chen, C.-S. Angew. Chem., Int. Ed. Engl. 1984,
23, 570.
3
3
a, R = Me
b, R = Et
2. Csuk, R.; Gl a¨ nzer, B. I. Chem. Rev. 1991, 91, 49.
3
. (a) Kitazume, T.; Ishikawa, N. Chem. Lett. 1983, 237; (b)
Utaka, M.; Konishi, S.; Takeda, A. Tetrahedron Lett.
Scheme 2. Reagents: (i) bakersÕ yeast, yeast extract, sucrose, phos-
phate buffer (pH 7.0).
1
986, 27, 4737; (c) Ohta, H.; Kobayashi, N.; Ozaki, K. J.
Org. Chem. 1989, 54, 1802.
4
. (a) Fuganti, C.; Grasselli, P.; Servi, S.; Spreafico, F.;
Zirotti, C. J. Org. Chem. 1984, 49, 4087; (b) Fuganti, C.
Pure Appl. Chem. 1990, 62, 1449.
HOH2C
H3C
O
O
HO
OH
5. (a) Bossert, F.; Vater, W. Naturwissenschaften 1971, 68,
578; (b) Bossert, F.; Vater, M. Med. Res. Rev. 1989, 9, 291;
(c) Nakayama, H.; Kasoaka, Y. Heterocycles 1996, 42,
901.
O-
HO
OH
pyruvate
D-Glucose
6
7
. Hantsch, A. Justus Liebigs Ann. Chem. 1882, 1, 215.
. (a) Gordeev, M. F.; Patel, D. V.; Gordon, E. M. J. Org.
Chem. 1996, 61, 924; (b) Breitenbucher, J. G.; Figliozzi, G.
Tetrahedron Lett. 2000, 41, 4311; (c) Ohberg, L.; West-
man, J. Synlett 2001, 1296; (d) Anderson, A. G., Jr.;
Berkelhammer, G. J. Am. Chem. Soc. 1958, 80, 992; (e)
Maquestiau, A.; Maeyence, A.; Eynde, J.-J. V. Tetra-
hedron Lett. 1991, 32, 3839.
acetaldehyde
H3C
O
O
O
O
O
H
OR
OR
RO2C
CO2R
H3C
8
. (a) Khadikar, B. M.; Gaikar, V. G.; Chitnavis, A. A.
Tetrahedron Lett. 1995, 36, 8083; (b) Agarwal, A.;
Chauhan, P. M. S. Tetrahedron Lett. 2005, 46, 1345.
N
NH2 O
O
O
H
NH3
OR
OR
9. (a) Ji, S.-J.; Jiang, Z.-Q.; Lu, J.; Loh, T.-P. Synlett 2004,
8
2
31; (b) Sridhar, R.; Perumal, P. T. Tetrahedron 2005, 61,
465.
Figure 1. Chemdraw of the proposed reaction pathway of Hantsch
type reaction by bakersÕ yeast.
1
0. (a) Singh, H.; Chimni, D. S. S.; Kumar, S. Tetrahedron
995, 51, 12775; (b) Liang, J.-C.; Yeh, J.-L.; Wang, C.-S.;
Liou, S.-F.; Tasi, C.-H.; Chen, I.-J. Bioorg. Med. Chem.
002, 10, 719; (c) Miri, R.; Niknahad, H.; Vesal, Gh.;
1
A typical procedure is described as follows: To a solu-
tion of 100 mL of pH 7.0 phosphate buffer, 5.0 g of D-
glucose, and 2.0 g of yeast extract, warmed at 35 °C,
was added 5.0 g of dry active bakersÕ yeast and the
mixture was stirred at 30 °C for 30 min, after which, ace-
toacetic ester (1.0 mmol) and ammonium acetate or 3-
amino crotonitrile were added. The mixture was shaken
at room temperature for 24 h and then extracted with
diethyl ether. The organic layer was dried and concen-
trated in vacuo and the resulting crude products were
2
Shafiee, A. IL Farmaco 2002, 57, 123; (d) Dondoni, A.;
Massi, A.; Minghini, E.; Sabbatini, S.; Bertoasi, V. J. Org.
Chem. 2003, 68, 6172; (e) Dondoni, A.; Massi, A.;
Minghini, E.; Bertoasi, V. Tetrahedron 2004, 60, 2311;
(
f) Tewari, N.; Dwivedi, N.; Tripathi, R. P. Tetrahedron
Lett. 2004, 45, 9011; (g) Moseley, J. D. Tetrahedron Lett.
2005, 46, 3179.
11. Sabitha, G.; Reddy, G. S. K. K.; Reddy, Ch. S.; Yadav, J.
S. Tetrahedron Lett. 2003, 44, 4129.
1
1
1
2. Wang, L.-M.; Sheng, J.; Zhang, L.; Han, J.-W.; Fan, Z.;
Tian, H.; Qian, C.-T. Tetrahedron 2005, 61, 1539.
3. Ko, S.; Sastry, M. N. V.; Lin, C.; Yao, C.-F. Tetrahedron
Lett. 2005, 46, 5771–5774.
recrystallized using ether–n-hexane to afford pure prod-
ucts 1 and 2 in 46–70% yields.14
However, (S)-b-hydroxyesters are obtained by the
bakersÕ yeast reduction in use of sucrose instead of
D-glucose under the same condition (Scheme 2).
1
4. Data for selected compounds; 1a: H NMR (80 MHz,
CDCl
6
3
) d 0.95 (d, J = 6.49 Hz, 3H), 2.27 (s, 6H), 3.71 (s,
H), 3.81 (q, J = 6.49 Hz, 1H), 6.04 (br s, 1H); C NMR
13
(
80 MHz, CDCl
3
) d 19.25, 22.22, 28.44, 58.87, 104.35,
À1
The glycolytic pathway from D-glucose to pyruvate is one
of the most universal metabolic pathway known. In yeast,
glycolysis is supposed to be the main pathway for the
catabolism of glucose. According to the classical concept
of glycolysis, metabolic acetaldehyde, resulting in the
formation of acetoin, should be released from pyruvate
144.71, 168.26; IR (KBr) 3320, 1705 cm ; MS m/z 239,
224, 106; mp 155 °C, 67% yield 1b: H NMR (80 MHz,
CDCl ) d 0.95 (d, J = 6.50 Hz, 3H), 1.29 (t, 6H), 2.26 (s,
1
3
6
1
2
1
2
3
1
H), 3.75 (q, J = 6.50 Hz, 1H), 4.18 (q, 4H), 5.51 (br s,
H); C NMR (80 MHz, CDCl ) d 14.28, 19.10, 22.11,
3
13
8.40, 58.43, 104.26, 144.66, 167.88; IR (KBr) 3320,
À1
705 cm ; MS m/z 267, 252, 106; mp 130 °C, 70% yield
1
5
in aerobic conditions. It is assumed that this acetalde-
hyde is involved in this Hantsch-type reaction (Fig. 1).
1
a: H NMR (80 MHz, CDCl
3
) d 1.29 (d, J = 8.06 Hz,
H), 2.04 (s, 3H), 3.35 (q, J = 8.06 Hz, 1H), 6.78 (br s,
À1
1
H); IR (KBr) 3320, 1705 cm , 46% yield 2b: H NMR
(
2
(
80 MHz, CDCl ) d 0.95 (d, J = 6.48 Hz, 3H), 1.29 (t, 3H),
3
Acknowledgements
.26 (s, 6H), 3.75 (q, J = 6.48 Hz, 1H), 4.18 (q, 2H), 6.47
À1
br s, 1H); IR (KBr) 3320, 1705 cm , 49% yield.
I wish to thank Dr. Youn Young Lee and Dr. Yang Mo
Goo for valuable comments and helpful discussions.
15. Sergienko, E. A.; Jordan, F. Biochemistry 2001, 40,
7369.