The Journal of Organic Chemistry
Note
Scheme 3. Gram Scale Experiments
ACKNOWLEDGMENTS
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This project was supported by the Natural Science Foundation
of China (NSFC 20972163 and 21025208), the Ministry of
Science and Technology (2011CB808600), and the Chinese
Academy of Sciences.
REFERENCES
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27.1, 26.2, 14.8; HRMS(EI) Calcd for C16H18O3 258.1256, found
258.1260.
General Procedure for the Synthesis of Wieland−Miescher
and Hajos−Parrish Ketones. To 2-alkylcyclohexane-1,3-dione (0.1
mmol) were added chiral amine catalyst (3.2 mg, 0.01 mmol) and m-
NO2C6H4CO2H (0.8 mg, 0.005 mmol) under solvent-free conditions
at ambient temperature. The reaction was monitored by 1H NMR and
stopped in the given time. The reaction mixture was directly isolated
by flash chromatography to give the pure product. Products 7a−7f, 7i,
and 7j are known compounds.10,12
(S)-8a-Phenyl-3,4,8,8a-tetrahydronaphthalene-1,6(2H,7H)-
dione (7g). The reaction was carried out with slight modification of
standard conditions. Dicholormethane (0.5 mL) was added to first
dissolve the catalyst and 6g, and the resulting homogeneous solution
was concentrated under a vacuum to remove DCM. The obtained
residue was kept at room temperature. After 4 h, when the reaction
was completed as monitored by TLC, the reaction mixture was directly
purified by flash chromatography to give 7g as a colorless syrup: 92%
20
1
yield, 79% ee; [α]D = 16 (c = 0.5, CHCl3); H NMR (300 MHz,
CDCl3) δ 7.44−7.29 (m, 3H), 7.17 (dd, J = 5.3, 3.2 Hz, 2H), 6.23 (s,
1H), 2.79−2.55 (m, 2H), 2.55−2.38 (m, 3H), 2.38−2.17 (m, 2H),
2.11−1.95 (m, 2H), 1.89−1.66 (m, 1H); 13C NMR (75 MHz,
CDCl3): δ 205.5, 195.9, 159.9, 135.0, 126.8, 126.7, 125.2, 124.1, 57.8,
36.3, 30.7, 30.2, 30.1, 20.8; HRMS(EI) Calcd for C16H16O2 240.1150,
found 240.1153. The ee value was determined by chiral HPLC [Daicel
Chiralpak OD-H column, λ = 254 nm, 2-propanol/n-hexane = 3:97,
flow rate = 0.8 mL min−1]: tR = 21.97 min (minor), tR = 24.11 min
(major).
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(S)-Ethyl 2-(4,7-Dioxo-1,2,3,4,4a,5,6,7-octahydronaphtha-
len-4a-yl)acetate (7h). The reaction was conducted following the
procedure of 7g. Colorless syrup: 82% yield, 86% ee, [α]D20 = −11 (c =
0.5, CHCl3); 1H NMR (300 MHz, CDCl3) δ 5.91 (d, J = 1.5 Hz, 1H),
4.11 (q, J = 7.1 Hz, 2H), 3.05−2.68 (m, 4H), 2.68−2.32 (m, 4H),
2.27−2.05 (m, 3H), 1.72 (ddd, J = 17.9, 13.4, 9.0 Hz, 2H), 1.24 (d, J =
7.1 Hz, 4H); 13C NMR (75 MHz, CDCl3) δ 208.2, 197.7, 169.1, 163.4,
127.2, 61.3, 52.8, 40.4, 38.0, 33.4, 31.7, 26.9, 23.6, 14.0; HRMS(EI)
Calcd for C14H18O4 250.1205, found 250.1208. The ee value was
determined by chiral HPLC [Daicel Chiralpak AD-H column, λ = 254
nm, 2-propanol/n-hexane = 1:9, flow rate = 1.0 mL min−1]: tR = 13.09
min (major), tR = 15.21 min (minor).
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ASSOCIATED CONTENT
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■
S
* Supporting Information
́ ́
Viozquez, S. F.; Guillena, G.; Najera, C. Org. Synth. 2011, 88, 330.
NMR and HPLC spectra for all the final products. This
material is available free of charge via the Internet at http://
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AUTHOR INFORMATION
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Corresponding Author
Notes
The authors declare no competing financial interest.
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dx.doi.org/10.1021/jo202433v | J. Org. Chem. 2012, 77, 2526−2530