Abstract
Under microwave irradiation conditions the tandem nucleophilic
substitution-Wittig reaction of α-hypervalent iodine functionalized
phosphonium ylide can occur readily to afford α-heteroatom
substituted-α,β-unsaturated enoates in good yields
stereoselectively.
Keywords
microwave irradiation conditions - α-hypervalent
iodine functionalized phosphonium ylide - umpolung ylides - tandem reaction
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Typical procedure
for the synthesis of α-bromo-substituted phosphonium ylide
3 under microwave irradiation conditions:
To a solution
of α- hypervalent iodine functionalized phosphonium
ylide in DMF was added Bu4 NBr, and the mixture was irradiated
in a modified domestic microwave oven (National, power max. 750
W) for 3 min. The reaction mixture was poured into ice-cold water
and extracted with benzene (4 × 20 mL), the organic layer
was dried with Na2 SO4 . The solvent was evaporated
to obtain a solid. Crystallization of this solid from acetone-hexane
gave the pure α-bromosubstituted phosphonium ylide 3 . mp155-156 °C (lit.
[13 ]
Mp 157-158 °C)
<A NAME="RU06102ST-10">10 </A>
General procedure
for the synthesis of product under microwave irradiation conditions : To
a solution of α-hypervalent iodine functionalized phosphonium
ylide (2.0 mmol) and aldehyde (2.0 mmol) in anhydrous DMF was added
the anions of nuleophiles (2.5 mmol), and the mixture was irradiated
in a modified domestic microwave oven for a few minutes. The reaction mixture
was poured into ice-cold water and extracted with ethyl acetate
(3 × 20 mL), the organic layer was dried with Na2 SO4 .
Removal of the solvent followed by column chromatography (ethyl
acetate/hexane) of the crude product yielded (Z )-α-heteroatom-α,β-unsaturated
enoates.
General procedure under conventional
conditions: Under N2 , to a solution of α-hypervalent
iodine functional-ized phosphonium ylide (2.0 mmol) (2.5 mmol) and aldehyde
(2.0 mmol) in anhydrous DMF was added the anions of nuleophiles,
the mixture was reacted under room temperature for 8-32
hours. After completion of the reaction, the following procedure
was the same as above.
[14 ]
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The ratio of Z/E was
determined by the 1 H NMR spectra. It was reported
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were in lower field than that of the corresponding E compounds.
For example, 1 H NMR spectrum shows that the chemical
shifts of vinyl and the methyl in ester proton of
Z -type ethyl 2-bromo-3-(4-methoxyphenyl)-2-propenoate are
7.80 ppm and 1.35 ppm, respectively. While the corresponding chemical
shifts of the E -type ethyl 2-bromo-3-(4-methoxyphenyl)-2-
propenoate compound are 7.07 ppm and 1.23 ppm, respectively.
[12 ]
The result
is in accordance with our research.
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