Abstract
The Michael reaction of a dialkyl malonate with a cyclic enone
using a chiral diamine-acid combination catalyst gave the
desired Michael adduct in high yield with excellent enantiomeric
excess in a protic solvent such as methanol and ethanol. The methanol molecule
participates in a proton relay system in which the dialkyl malonate
is activated through hydrogen bonding to afford the Michael adduct
with excellent enantioselectivity.
Key words
enone - malonate - Michael addition - organocatalysis - proton relay
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Typical Procedure
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14 Using Catalyst 12 (Table 3, entry 1): A catalyst stock solution
(1.0 M in MeOH) was prepared as a mixture of (S)-(+)-1-(2-pyrrolidinyl-methyl)pyrrolidine
(11, 0.5 mmol) and trifluoroacetic acid (0.5
mmol) in anhyd MeOH (0.5 mL) before use. 2-Cyclopentenone (14c, 0.5 mmol) was dissolved in MeOH (0.45
mL) and dibenzyl malonate (15a, 0.6 mmol)
was added. To the mixture the catalyst stock solution (1.0 M in MeOH,
50 µL, 0.05 mmol) was added at 25 ˚C. After stirring for
48 h, the reaction mixture was directly purified by column chromatography
(silica gel 5 g, hexanes-EtOAc, 90:10) to afford the Michael
product 16a (98% yield, 94% ee).
The enantiomeric excess (ee) of Michael products was determined
by chiral-phase HPLC analysis and/or ¹³C
NMR (see Supporting Information). The absolute configuration of Michael
products was determined by comparison of the reported specific optical
rotation and HPLC data.
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