Abstract
Diarylprolinol silyl ethers immobilized onto polystyrene have
been employed as catalysts in the enantioselective domino Michael-Knoevenagel
reaction of dimethyl 3-oxoglutarate and 3-substituted acrolein derivatives,
including aliphatic ones. The best catalyst allows the preparation
of highly functionalized cyclohexane derivatives in a straightforward
and efficient manner, both under batch and continuous flow conditions.
Key words
asymmetric organocatalysis - domino process - Michael addition - Knoevenagel condensation - flow reactors
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16
General Procedure
for the Domino Michael-Knoevenagel Process of α,β-Unsaturated
Aldehydes and Dimethyl 3-Oxopentanedioate : Benzoic acid (0.05
mmol), the corresponding aldehyde (0.25 mmol) and dimethyl 3-oxopentanedioate
(0.275 mmol) were added to catalyst 5 (0.025
mmol) previously swollen in CH2 Cl2 (1 mL).
The suspension was shaken at r.t. for the time indicated in Table
[² ]
and then directly filtered.
The resin was rinsed with CH2 Cl2 (3 × 1
mL) and the organic filtrate was concentrated under reduced pressure.
MeOH (1 mL) and NaBH4 (0.25 mmol) were added to a solution
of the resulting crude in CH2 Cl2 (0.5 mL)
at 0 ˚C, which was stirred at that temper-ature for 20 min.
After addition of the pH 7 phosphate buffer, the organic materials
were extracted with CH2 Cl2 and the combined organic
phase was dried over Na2 SO4 , and then concentrated under
reduced pressure. The residue was purified by flash chromatography
on silica gel (CH2 Cl2 -EtO2 )
to afford 7 .
17 The deposition number at the Cambridge
Crystallographyc Data Centre is CCDC 804763.
18 These recycling experiments show the
results obtained in six consecutive runs. After each run, the reaction
mixture was filtered and the solid-supported catalyst was washed
with CH2 Cl2 and directly reused.