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DOI: 10.1055/s-0030-1258040
Asymmetric Organocatalytic Michael Addition of α,β-Unsaturated Ketone with 1,2,4-Triazole
Publication History
Publication Date:
12 August 2010 (online)
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Abstract
The Michael addition of α,β-unsaturated ketone with triazole was efficiently catalyzed by the primary amine thiourea catalyst and the desired products were formed in high yields with moderate to excellent enantioselectivities.
Key words
asymmetric catalysis - 1,2,4-triazole - Michael addition - enone
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- Supporting Information
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References and Notes
General Procedure
for the Asymmetric Michael Addition of 1,2,4-Triazole to Cyclic
Enones Catalyzed by 1
To a solution of cyclic enones
(0.3 mmol) in toluene (2.0 mL) was added catalyst (19.2 mg, 0.04
mmol), 2-methoxy-benzoic acid (4.5 mg, 0.03 mmol), and 1,2,4-triazole
(13.8 mg, 0.2 mmol). The reaction mixture was stirred at 15 ˚C
for the time indicated in Table
[²]
,
and then the solvent was removed under vacuum. The residue was purified
by silica gel chromatography to yield the desired addition product.
General Procedure
for the Asymmetric Michael Addition of 1,2,4-Triazole to Open-Chain
Enones Catalyzed by 1
To a solution of benzalacetone
derivates (0.3 mmol) in CH2Cl2 (0.5 mL) was
added catalyst (19.2 mg, 0.04 mmol), 4-nitrobenzoic acid (5.0 mg,
0.03 mmol), and 1,2,4-triazole (13.8 mg, 0.2 mmol). The reaction
mixture was stirred at 15 ˚C for the time indicated in
Table
[²]
, and then
the solvent was removed under vacuum. The residue was purified by
silica gel chromatography to yield the desired addition product.
Crystal Structure
Determination of Compound 9k
C12H12BrN3O, M = 294.16;
a block crystal (0.410 × 0.337 × 0.251 mm), T = 293 (2), λ(MoKα) = 0.71073 Å, orthorhombic,
space group: P212121, a = 7.9498
(12) Å, b = 12.4724
(17) Å, c = 25.479
(4) Å, V = 2526.3
(6) ų, 15229 total reflections, 5718
unique, Rint = 0.0851, R1 = 0.0437
(I > 2σ), wR2 = 0.0827,
Flack parameter: 0.023 (11). Please see CCDC 782894.
Crystal Structure
Determination of Compound 10
C12H19N3S2, M = 269.42;
a block crystal (0.425 × 0.396 × 0.350 mm), T = 293 (2), λ(MoKα) = 0.71073 Å,
monoclinic, space group: P21, a = 6.8332
(12) Å, b = 10.5576
(18) Å, c = 10.0377
(17) Å, V = 689.2
(2) ų, 3825 total reflections, 2766
unique, Rint = 0.0380, R1 = 0.0497
(I > 2σ), wR2 = 0.1301,
Flack parameter: 0.06 (10). Please see CCDC 782895.