solution. The enzyme-catalyzed procedure is simple, mild, efficient
and environmentally friendly. The research will facilitate the
understanding of the microbial degradation of nitroaromatic
compounds and the mechanism of nitroreductase-mediated pro-
drug therapy. Further studies to optimize reaction conditions and
to expand the substrate scope as well as to synthesize new
biologically active compounds via arylhydroxylamines are currently
under way in our laboratory.
Table 2 Chemoselective reduction of various aromatic nitro com-
pounds using bakers’ yeasta
Entry Subtrate
1
Product
Time/h Conv.b(%)
c : db
0.5
100
95 : 5
Financial support by the National Key Project for Basic
Research (2003CB114400) and under the auspices of the National
Natural Science Foundation of China is greatly appreciated.
2
3
2
2
86
90
89 : 11
71 : 29
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88
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a Reduction conditions: bakers’ yeast 5.0 g, subtrate 100 mg, 0.2 M
phosphate buffer (pH 6.5) 100 ml, glucose 2.5 g, 30 uC. b The con-
version and the ratio were determined by 1H NMR. c Also isolated
1-(4-nitrophenyl)ethanol (7%).
strengthened by electron-withdrawing groups. Therefore, the rate
of reduction of hydroxylamine to amine is slower than the rate of
formation of hydroxylamine, which permits its isolation over a
period of time.
In all cases, apart from amines, only a few side products (v2%)
were detected by the 1H NMR spectrum of the crude products. It
was noteworthy that many readily reducible or labile functional
groups such as cyano, imide, ester and halide did not undergo any
change under the reaction conditions. The only exception was the
carbonyl group; reduction of 4a proceeded to give 7% of 1-(4-
nitrophenyl)ethanol (Table 2, entry 4).
8 P. D. Arrigo, G. P. Fantoni and S. Servi, Adv. Appl. Microbiol., 1997, 44,
81.
9 (a) J. C. Spain, Annu. Rev. Microbiol., 1995, 49, 523; (b) R. L. Koder,
C. A. Haynes, M. E. Rodgers, D. W. Rodgers and A. F. Miller,
Biochemistry, 2002, 4, 14197; (c) I. T. Reeve and M. G. Miller, Chem.
Res. Toxicol., 2002, 15, 352.
In summary, we have described a novel method for the
preparation of arylhydroxylamines using bakers’ yeast in aqueous
C h e m . C o m m u n . , 2 0 0 4 , 2 3 3 8 – 2 3 3 9
2 3 3 9