X. Chen et al. / Tetrahedron 66 (2010) 1990–1993
1993
KOH (0.17 g, 3.0 mmol) in methanol (40 mL) was stirred in an ice
Acknowledgements
bath for 12 h. Then, 1-(pyridylcaobonylmethyl)pyridium iodide (3)
(2.45 g, 7.5 mmol) and ammonium acetate (3.85 g, 50 mmol) were
added and the resulting mixture was heated at refluxed for 48 h.
After evaporation, the residue was purified by column chroma-
tography on silica gel eluted with petroleum ether/ethyl acetate
(6:1) to afford the product (R)-4 in 65% yield (1.93 g) as a light
Partial supports of this work from the National Science Foun-
dation of China (Nos. 20725206 and 20732004), the Specialized
Research Fund for the Doctoral Program of Higher Education in
China, the US National Science Foundation (CHE-0717995), and the
donors of the Petroleum Research Fund-administered by the
American Chemical Society are gratefully acknowledged.
yellow solid. 1H NMR (CDCl3, 400 Hz)
d 8.85 (s, 2H), 8.72 (d, 2H,
J¼4.0 Hz), 8.68 (d, 2H, J¼4.0 Hz), 8.19 (s, 1H), 7.97 (d, 1H, J¼3.6 Hz),
7.86–7.80 (ddd, 5H, J¼6.4, 6.0, 2.8 Hz), 7.59 (d, 2H, J¼8.8 Hz), 7.21–
7.45 (m, 8H), 5.21 (t, 2H), 4.45 (t, 2H), 3.30 (s, 3H), 2.37 (s, 3H). 13C
Supplementary data
NMR (CDCl3,100 MHz) d 156.3,155.5,152.8,151.1,149.2,136.8, 134.1,
The characterization data of the catalytic asymmetric reaction
products and the NMR and IR spectra are provided. Supplementary
data associated with this article can be found in online version, at
134.0, 133.5, 130.9, 130.6, 129.7, 129.6, 128.3, 127.8, 126.7, 126.5,
125.9, 125.8, 124.1, 123.7, 122.0, 121.3, 120.7, 116.3, 99.0, 94.7, 77.3,
76.3, 56.1. HRMS (ESþ) calcd for C39H31N3O4 (MþH): 606.2393,
found: 606.1713.
3.1.2. Preparation and characterization of (R)-3-(40-2,20:60200-terpyr-
idine)-1,10-bi-2-naphthol, (R)-5. To
a solution of (R)-4 (1.93 g,
References and notes
3 mmol) in CH2Cl2, CF3COOH (3.2 mL, 30 mmol) was added, and
the solution was stirred for 12 h. A saturated NaHCO3 solution
(30 mL) was added to quench the reaction. CH2Cl2 (50 mL) was
used for extraction and the combined organic layer was dried over
Na2SO4. After removal of the organic solvent under reduced
pressure, the residue was purified by column chromatography on
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silica gel eluted with petroleum ether/ethyl acetate (3:1) to afford
20
the product (R)-5 in 85% yield (1.40 g) as a light yellow solid. [a]
D
þ111.4 (c 0.72, CH2Cl2). 1H NMR (CDCl3, 400 MHz)
d 8.76 (s, 2H),
8.62 (d, 2H, J¼8.0 Hz), 8.52 (d, 2H, J¼4.8 Hz), 8.26 (s, 1H), 7.93 (d,
1H, J¼8.0 Hz), 7.84 (ddd, 4H, J¼7.6, 8.4, 7.6 Hz), 7.21–7.45 (m, 10H).
13C NMR (CDCl3, 100 MHz)
d 155.9, 154.6, 153.1, 151.4, 149.6, 148.5,
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3.2. General procedure for the catalytic asymmetric process
Under nitrogen, to a flask containing (R)-5 (25.9 mg, 0.05 mmol,
20 mol %) in dry CH2Cl2 was sequentially added methyl propiolate
(85
m
L, 1.0 mmol), ZnEt2 (0.67 mL, 1.5 M in toluene, 1.0 mmol), and
Ti(OiPr)4 (125
mL, 1.0 M in toluene, 0.125 mmol). The reaction mix-
ture was stirred at room temperature for 24 h. An aldehyde
(0.25 mmol) was then added at 0 ꢀC and the reaction was allowed
to proceed at 0 ꢀC for 48 h. Saturated aqueous ammonium chloride
was added to quench the reaction, and CH2Cl2 was used for ex-
traction. After the organic solution was dried over Na2SO4 and fil-
tered, the solvent was removed under reduced pressure. The
residue was purified by column chromatography on silica gel eluted
with petroleum ether/ethyl acetate (9:1) to afford the product. The
ee’s were determined by HPLC analysis (OD-H column. Eluent:
n-Hexane/i-PrOH).
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(b) KrOhnke, F. Synthesis 1976, 1–24.