Chemistry of Natural Compounds, Vol. 47, No. 1, March, 2011 [Russian original No. 1, January–February, 2011]
PRODUCTION OF A SYNTHON FOR OPTICAL ANTIPODS
OF Drosophila mulleri AND Mayetiola destructor PHEROMONES
USING Aspergillus FUNGUS STRAINS
1
2
G. S. Shakirzyanova, A. P. Khuzhakulov,
UDC 547.313+632.936.2+576.8
2
1*
S. I. Kukanova, and V. S. Abdukakharov
The key synthon for synthesizing sex pheromones of Drosophila mulleri and Mayetiola destructor is ethyl-3S-
hydroxybutanoate, which is synthesized by reduction of acetoacetic ester by enzymes and various types of microorganisms
[1, 2].
We studied the reduction of acetoacetic ester using various micromycete strains of Aspergillus to prepare optical
antipods of D. mulleri and M. destructor pheromones.
Mycelium of microscopic fungi is known produce the dehydrogenase enzyme complex, which is involved in redox
reactions [3]. We used this property in our experiments.
Soil samples of typical serozems were used to isolate the microorganisms. Fungi were isolated by the known
microbiological method with inoculation on solid agar Czapek–Dox medium [4]. The following microorganism species were
selected and determined as before [5]: Aspergillus oryzae strain Pro-1; A. niger strain 50; A. flavus strain 48; and A. flavus
strain 4.
Microorganisms were grown on the following media (g/L): a) Czapek medium (saccharose, 20.0; NaNO , 2.0; KH PO ,
3
2
4
1.0; MgSO ·7H O, 0.5; KCl, 0.5; FeSO , 0.01; distilled H O, 1000 mL); b) starch medium (starch, 20; KCl, 1.0; MgSO , 0.5;
4
2
4
2
4
CaCl , 0.1); c) Anderkofler medium (corn starch, 30; KNO ; CaCO , 5.0; KH PO , 0.8; KCl, 0.4; FeSO , ZnSO , CuSO ,
2
3
3
2
4
4
4
4
0.0035).
22
Acetoacetic ester was biotransformed into ethyl-3R-hydroxybutyrate, [ꢀ] –39.3 (c 0.1, CHCl ).
D
3
Acetoacetic ester was processed by the filtered biomass and stirred for 72 h in a thermostat at 35°C. A small amount
of culture medium was added to the reaction mixture in order to activate the transformation. Active growth of the microorganisms
was observed during the experiments. When the experiment was finished, the reaction mixture was extracted with Et O. The
2
extract was filtered and dried over MgSO . Solvent was removed at reduced pressure. The solid was analyzed by GC.
4
According to the chromatographic analysis, the best result (80%) was obtained with A. flavus strain 4 (Table 1).
OH
O
C
H C
3
CH CO Et
H C CH CH CO Et
2
2
3
2
2
Table 1. Reduction of Acetoacetic Ester Using Aspergillus Fungus Strains
Amount, g
Fungus strain
Yield, %
Optical purity of product, %
biomass
substrate
– 50
34.6
14.4
33.7
50
0.8 (6.15 mmol)
0.5 (3.84 mmol)
0.65 (5.0 mmol)
3.45 (26.5 mmol)
0.5 (3.84 mmol)
30
28
64
62
80
95.5
95.6
95.8
95.8
96.0
Aspergillus niger
– Pro-1
Aspergillus oryzae
– 48
Aspergillus flavus
Aspergillus flavus
Aspergillus flavus
– 48
– 4
18.8
1) A. S. Sadykov Institute of Bioorganic Chemistry, Academy of Sciences of the Republic of Uzbekistan, Tashkent,
fax (99871) 262 70 71; e-mail: abdukakharov@mail.ru; 2) Institute of Microbiology, Academy of Sciences of the Republic of
Uzbekistan, Tashkent, fax (99871) 244 25 19; e-mail: imbasru@uzsci.net. Translated from Khimiya Prirodnykh Soedinenii,
No. 1, p. 142, January–February, 2011. Original article submitted June 7, 2010.
©
0009-3130/11/4701-0161 2011 Springer Science+Business Media, Inc.
161
Shakirzyanova
