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DOI: 10.1055/s-0030-1259318
Chiral Brønsted Acids and Their Calcium Salts in Catalytic Asymmetric Mannich Reactions of Cyclic 1,3-Diketones
Publication History
Publication Date:
13 January 2011 (online)
Abstract
Asymmetric calcium-catalyzed direct Mannich reactions of 1,3-dicarbonyl compounds with imines have been developed. The reactions proceed under mild conditions and provide the corresponding products with high enantiomeric excess.
Key words
Mannich reaction - organocatalysis - calcium - BINOL phosphoric acid - amino acid
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References and Notes
The absolute configuration of the products was obtained from X-ray crystal structure analysis of compound 6c. On the basis of this structure the absolute configuration was assigned to be the S configuration.
15
General Procedure
for Direct Mannich Reaction: In a typical experiment pyrone 2 or 1,3-cyclohexadione (5;
1.0 equiv), aldimine 3 (1.5 equiv), and
the calcium catalyst (5 mol%) were suspended in Bu2O
in a screw-capped vial and the resulting mixture was allowed to
stir at -40 ˚C for 60-72 h. Purification
of the crude product by column chromatography on silica gel afforded
the corresponding product 4 or 6.
(
R
)-
tert
-Butyl(4-hydroxy-6-methyl-2-oxo-2
H
-pyran-3-yl)(
p
-tolyl)methylcarbamate (4a): Isolated by column chromatography
(CH2Cl2-acetone, 10:1) as a white
solid in 49% yield and 88% ee. The ee was determined
by HPLC using Chiralpak AD-H column [(n-hexane-i-PrOH, 90:10), flow rate: 0.6 mL/min;
major enantiomer: t
R = 29.59
min; minor enantiomer: t
R = 22.07
min]; [α]D -6.1
(c = 1.84, CH2Cl2);
mp 173-175 ˚C. ¹H NMR (400
MHz, CDCl3): δ = 7.22 (d, J = 8.0 Hz, 2 H), 7.02 (d, J = 8.0 Hz, 2 H), 6.79 (d, J = 12.0 Hz, 1 H), 6.05 (d, J = 12.0 Hz, 1 H), 5.88 (s,
1 H), 3.41 (s, 1 H), 2.23 (s, 3 H), 2.07 (s, 3 H), 1.39 (s, 9 H).
¹³C
NMR (100 MHz, CDCl3): δ = 166.10, 164.94,
161.74, 157.40, 137.67, 136.82, 129.09, 126.12, 102.60, 100.84, 81.11,
28.48, 21.05, 19.85. IR (KBr): 3359, 2980, 1700, 1651, 1530, 1161,
884, 783 cm-¹. MS (EI): m/z (%) = 345
(2) [M+], 339 (30), 251 (41),
230 (58), 200(100), 145 (64), 77 (92).
(
R
)-
tert
-Butyl(2-hydroxy-6-oxocyclohex-1-enyl)(
p
-tolyl)-methylcarbamate (6a): Isolated by column chromatography
(CH2Cl2-acetone, 10:1) as a white
solid in 47% yield and 73% ee. The ee was determined
by HPLC using Chiralpak AD-H column [(n-hexane-i-PrOH, 92:8), flow rate: 0.6 mL/min;
major enantiomer: t
R = 20.23
min; minor enantiomer: t
R = 17.98
min]; [α]D +4.43
(c = 0.75, CH2Cl2);
mp 132-134 ˚C. ¹H NMR (400
MHz, CDCl3): δ = 10.60 (br s, 1 H),
7.19 (d, J = 8.0 Hz, 2 H), 7.00
(d, J = 8.0 Hz, 2 H), 6.82 (d, J = 9.9 Hz, 1 H), 5.99 (d, J = 9.9 Hz, 1 H), 2.45 (t, J = 6.0 Hz, 2 H), 2.22 (s, 5
H), 1.79-1.89 (m, 2 H), 1.35 (s, 9 H). ¹³C
NMR (100 MHz, CDCl3): δ = 173.73, 157.32,
136.00, 128.80, 125.92, 116.22, 80.60, 48.78, 37.02, 29.64, 28.54,
21.15, 20.62. IR (KBr): 3455, 2922, 1710, 1490, 1165, 1025, 779
cm-¹. MS (EI): m/z (%) = 331 (56) [M+],
266 (58), 239 (92), 194 (100), 116 (58), 78 (52), 70 (98).