Finally, by using 1a and 2a as model substrates, the recovery
and reuse of TBAF/H2O was investigated. Upon completion
of the reaction, the resulting mixture was extracted with diethyl
ether. To the remaining aqueous phase containing TBAF were
added 1a and 2a. The mixture was then submitted to similar
procedures. The reuse study was repeated for 3 times, from which
3a was obtained in a yield of 75%, 70% or 56%, respectively.
Notes and references
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Experimental
Flash chromatographic purification of products was performed
on silica gel (200–300 mesh). Thin-layer chromatography was
visualized with UV light (254 and 365 nm). H and 13C NMR
1
spectra were determined on a Bruker AC 400 spectrometer as
CDCl3 solutions. Chemical shifts were expressed in parts per
million (d) downfield from the internal standard tetramethyl-
silane and were reported as s (singlet), d (doublet), t (triplet),
m (multiplet) and coupling constants J were given in Hz. Mass
spectra were obtained in API mode using a Waters Acquity SQ
HPLC-mass spectrometer. The HRMS (High-Resolution Mass
Spectra) were performed on a JEOL HX 110A spectrometer.
A typical procedure for the synthesis of 3a through tandem
reaction in water
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To a flask containing 1-phenylbuta-2,3-dien-1-one (1a, 1 mmol)
and bromoacetophenone (2a, 1 mmol) were added TBAF·3H2O
(2 mmol) and water (4 mL). The mixture was stirred at 80 ◦C for 2
h. It was then cooled to room temperature and extracted with di-
ethyl ether (5 mL ¥ 3). The combined organic phases were dried,
filtered and concentrated under vacuum. The residue was puri-
fied by column chromatography on silica gel eluted with ethyl
acetate/hexane (5–10%) to give 2-aceto-1,4-diphenylbutane-1,4-
dione (3a):15a 1H NMR (400 MHz, CDCl3) d: 2.23 (s, 3H), 3.60
(dd, J1 = 18.0 Hz, J2 = 6.4 Hz, 1H), 3.78 (dd, J1 = 18.0 Hz, J2 =
6.4 Hz, 1H), 5.29 (t, J = 6.4 Hz, 1H), 7.42–7.63 (m, 6H), 7.96 (d,
J = 7.6 Hz, 2H), 8.07 (d, J = 7.6 Hz, 2H). 13C NMR (100 MHz,
CDCl3) d: 29.53, 38.02, 56.81, 128.18, 128.65, 128.86, 128.98,
133.53, 133.84, 136.00, 136.09, 196.23, 196.87, 202.29. MS: m/z
281 (MH)+. 3b–3x were obtained in a similar manner.
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In summary, we have developed an efficient and sustain-
able synthetic pathway toward 1,3,4¢-tricarbonyl compounds
through tandem reaction of 1,2-allenic ketones with a-halo
carbonyl compounds under the promotion of TBAF·3H2O in
water. Notable features of this process include: 1) effective
generation and transformation of the proposed allenyl anions
in water; 2) the unprecedented tandem reaction of 1,2-allenic
ketones resulting in the otherwise difficult to obtain 1,3,4¢-
tricarbonyl compounds; 3) remarkably enhanced reactivity and
chemoselectivity by using water as the reaction medium; 4) easy
recovery and effective reuse of TBAF/H2O.
Acknowledgements
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Chankeshwara, Green Chem., 2007, 9, 1335; (b) N. Parikh, D. Kumar,
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This work was supported by the Natural Science Foundation of
China (Nos. 20972042 and 20911140238), Innovation Scientists
and Technicians Troop Construction Projects of Henan Province
(No. 104100510019) and PCSIRT (IRT1061).
This journal is
The Royal Society of Chemistry 2011
Green Chem., 2011, 13, 3218–3223 | 3223
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