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DOI: 10.1055/s-2003-38366
Sodium Borohydride Reduction and Selective Transesterification of β-Keto Esters in a One-pot Reaction under Mild Conditions
Publication History
Publication Date:
28 March 2003 (online)
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Abstract
An efficient and simple one-pot method of preparing β-hydroxy esters by sodium borohydride reduction cum selective transesterification of β-keto esters under mild conditions is described.
Key words
transesterification - β-keto esters - β-hydroxy esters - sodium borohydride - one-pot reaction
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References
Experimental:
Typical Reduction cum Transesterifcation Reaction: Ethyl
benzoylacetate, 1 mL (5.78 equiv) in methanol, 15mL was treated
with sodium borohydride, 110 mg (2.89 equiv) at 0 °C to
r.t. The reaction was carried out for 18 h. Routine workup gave
a reaction mixture which was purified by column chromatography and
characterized by 1H NMR.
Large excess of alcohol improves the
yield of the reaction. The isolated yield in these reactions is
limited because of two reasons: a) during work up of the reaction
a loss of
10-15% was observed due to
the formation of the corresponding hydroxy acid and b) separation
by column chromatography of two similar compounds (two β-hydroxy esters),
is challenging and leads to a loss of 10-12%.
The spectral data (for the product
of entry 15): 1H NMR (CDCl3): δ = 2.50
(s, 1 H), 2.70 (double dd, 2 H), 3.30 (br s, 1 H), 4.67 (s, 2 H),
5.10 (m, 1 H), 7.33 (s, 5 H). 13C NMR:
δ = 171.27
(C1), 142.48 (C4, arom.), 125.60, 127.30, 129.30 (arom.), 77.70
(C3), 76.60 (C2′), 70.20 (C3′), 50.70 (C1′), 43.20
(C2).
During the course of above experiment an aliquot of (1mL) was always taken at equal intervals of time (15 min), neutralized and extracted. Each of them was monitored by 1H NMR.
20Sodium borohydride catalyzed borohydride reducing systems, Thiokol/ventron division, 150 Andover street, Danvers, Massachusetts, 01923, U.S.A., +1(617)7743100, 3.
21Methyl 3-hydroxy butyrate was treated with sodium ethoxide in presence of large excess of dry ethanol and the reaction was allowed to run for more than 2 h.