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ing a 0.5 molar equivalent of NaBH4 per molar equivalent of eral specific reagents and some of them are now commer-
the aldehyde in 2 mL water and 30% power amplitude of mi- cially available.9
crowave oven (300 W) was the best for reduction reaction. In this context, we also investigated the possibility of
The reaction was completed in 30 sec and benzyl alcohol was 1,2-reduction of a,b-unsaturated aldehydes and ketones with
obtained in 96% yield. To show the further utility of this pro- NaBH4 in water under microwave irradiation. The irradiation
tocol, we applied the optimal conditions for the reduction of of cinnamaldehyde by microwave (700 W) in the presence of
structurally different aliphatic and aromatic aldehydes with one molar equivalent of NaBH4 in water (2 mL) was carried
sodium borohydride. The use of 0.5-1 molar equivalents of out exclusively in 1,2-reduction manner within 50 sec. In this
sodium borohydride was sufficient for the complete reduc- reaction, cinnamyl alcohol was obtained in 98% yield. This
tion of aldehydes and the corresponding primary alcohols achievement prompted us to evaluate the behavior of other
were obtained in 82-98% yields within 30-60 sec. The results enals and enones in respect to this transformation. Citral also
of these reductions are summarized in Table 1. showed the best efficiency and regioselectivity under micro-
In the next attempt, we turned our attention to the re- wave irradiation. Reduction of conjugated ketones such as
duction of ketones under the defined conditions. Reduction benzalacetone and b-ionone were achieved quickly and effi-
of ketones, because of their less reactivity relative to alde- ciently with 2 molar equivalents of NaBH4 in water under mi-
hydes, needs the use of 1.5-2 molar equivalents of NaBH4 un- crowave irradiation (700 W). The irradiation of benzalaceto-
der microwave irradiation (700 W). Different kinds of aro- phenone in 5 min gave only 70% yield; however, the 1,2-re-
matic and aliphatic ketones were subjected to NaBH4 in water duction product was obtained from the reaction mixture (Ta-
(2 mL) under microwave irradiation. The results also showed ble 4).
that the corresponding secondary alcohols were obtained in
excellent yields within 15-60 sec. In the case of benzophe-
none, probably because of its bulk hindrance, a reduction re- CONCLUSION
action required 4 molar equivalents of NaBH 4 , and benz-
hydrol was obtained in 90% yield after 5 min irradiation (Ta- In conclusion, we have shown that water as a green sol-
ble 2). The work-up procedure was easy: addition of distilled vent can effectively replace of the conventional volatile sol-
water to the reaction mixture and then extracting with diethyl vents in the reduction of a variety of carbonyl compounds
ether afforded the crude corresponding alcohol for further pu- with sodium borohydride under microwave irradiation. The
rification with short column chromatography on silica gel. reductions were completed within 15 sec-5 min with high to
The utility of this protocol was further examined with excellent yields of the corresponding alcohols. Reduction of
the reduction of a-diketones and acyloins. Their reductions a-diketones and acyloin compounds produced the corre-
were carried out with 2 molar equivalents of NaBH4 in water sponding vicinal diols in excellent yields. Conjugated car-
(2 mL) under microwave irradiation (700 W). The reactions bonyl compounds under the defined conditions showed an
were completed within 1-3 min and the corresponding vicinal excellent efficiency in an exclusive 1,2-reduction manner.
diols were obtained in 91-99% yields (Table 3). All attempts Therefore, we think that this protocol with the above advan-
to reduce a-diketones to acyloin compounds were unsatisfac- tages as well as the easy work-up procedure could be a useful
tory and only vicinal diols were obtained from the reactions. addition to the present methodologies.
Ally alcohols are important synthetic materials and
their preparations from the reduction of conjugated carbonyl
compounds are one of the easiest in organic synthesis.1 Re- EXPERIMENTAL SECTION
gioselective 1,2-reduction of a,b-unsaturated aldehydes and
ketones with metal hydride reducing agents due to competing All microwave assisted reactions were carried out in a
1,2- vs. 1,4-attack by the hydride is often difficult to achieve Yusch household microwave oven (1000 W). The instrument
in organic synthesis. In spite of the substantial evidence, the was modified for laboratory applications with an external re-
tendency for sodium borohydride to reduce enones or enals in flux condenser. All substrates and reagents were obtained
a conjugate sense is highly solvent-dependent and often ig- from commercial sources of the highest quality and were
nored; 8 however, the requirement for reduction to corre- used without further purification. The products were charac-
sponding allylic alcohols has led to the development of sev- terized by a comparison with authentic samples (melting or
Reduction in Water under Microwave Irradiation J. Chin. Chem. Soc., Vol. 52, No. 6, 2005 1181
1182 J. Chin. Chem. Soc., Vol. 52, No. 6, 2005 Zeynizadeh and Setamdideh
boiling points) and their 1H NMR or IR spectra. Organic lay- was applied for the purity determination of substrates, prod-
ers were dried with anhydrous sodium sulfate before concen- ucts and reaction monitoring over silica gel 60 F254 aluminum
tration in vacuo. All yields refer to isolated products. TLC sheets. Products were purified by column chromatography
Reduction in Water under Microwave Irradiation J. Chin. Chem. Soc., Vol. 52, No. 6, 2005 1183
packed with silica gel 60 (70-230 mesh ASTM). dehyde (0.106 g, 1 mmol) was then added dropwise to the re-
sulting solution. After fitting the flask to the external con-
A Typical Procedure for Microwave-Assisted Reduction denser at the inside of the oven, the mixture was irradiated
of Carbonyl Compounds with NaBH4 in Water with a microwave oven (30% power amplitude » 300 W) for
In a round-bottomed flask (10 mL) charged with dis- 30 sec. The progress of the reaction was monitored by TLC
tilled water (2 mL), NaBH4 (0.019 g, 0.5 mmol) was added (eluent; CCl4/Et2O: 5/2). At the end of the reduction, distilled
and swirling the flask makes a clear solution. Neat benzal- water (5 mL) was added to the reaction mixture and it was
1184 J. Chin. Chem. Soc., Vol. 52, No. 6, 2005 Zeynizadeh and Setamdideh
then extracted with Et2O (3 ´ 6 mL). The combined extracts 6. (a) Demir, A. S.; Akhmedov, I. M.; Sesenoglu, O. Turk. J.
were dried over anhydrous sodium sulfate. Evaporation of Chem. 1999, 23, 123. (b) Denis, C.; Laignel, B.; Plusquellec,
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37, 53. (c) Mitchell, D.; Doecke, C. W.; Hay, L. A.; Koening,
crude material over silica gel (eluent; CCl 4 /Et 2 O: 5/2) af-
T. M.; Wirth, D. D. Tetrahedron Lett. 1995, 36, 5335. (d)
forded the pure liquid benzyl alcohol (0.104 g, 96%, Table 1).
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