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Z. Li et al.
Letter
Synlett
F–
H
F–
H
(3) (a) Adam, W.; Smerz, A. K. Tetrahedron 1996, 52, 5799.
(b) Smith, A. M. R.; Rzepa, H. S.; White, A. J. P.; Billen, D.; Hii, K.
K. J. Org. Chem. 2010, 75, 3085.
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A.; Liu, H.; Chen, B. C.; Zhou, P. Tetrahedron 1998, 54, 10481.
(5) Odagi, M.; Furukori, K.; Yamamoto, Y.; Sato, M.; Iida, K.;
Yamanaka, M.; Nagasawa, K. J. Am. Chem. Soc. 2015, 137, 1909.
(6) Lu, M.; Zhu, D.; Lu, Y.; Zeng, X.; Tan, B.; Xu, Z.; Zhong, G. J. Am.
Chem. Soc. 2009, 131, 4562.
F–
H
O
O
O
O
O
O
O
O
air
F–
OH–
R1
–O
R2
R2
R1
R2
R2
R1
R1
O
OH
A
1
B
C
F–, OH-
(7) Labat, G.; Meunier, B. J. Chem. Soc., Chem. Commun. 1990, 1414.
(8) Takikawa, H.; Takada, A.; Hikita, K.; Suzuki, K. Angew. Chem. Int.
Ed. 2008, 47, 7446.
O
O
(9) Christoffers, J. J. Org. Chem. 1999, 64, 7668.
R1
R2
(10) Rössle, M.; Christoffers, J. Tetrahedron 2009, 65, 10941.
(11) Chuang, G. J.; Wang, W. K.; Lee, E.; Ritter, T. J. Am. Chem. Soc.
2011, 133, 1760.
OH
2
(12) Miao, C.-B.; Wang, Y.-H.; Xing, M.-L.; Lu, X.-W.; Sun, X.-Q.; Yang,
H.-T. J. Org. Chem. 2013, 78, 11584.
Scheme 2 A plausible mechanism for the hydroxylation reaction
(13) 2-Hydroxy-1,3-diketones 2; General Procedure
A mixture of 1,3-diketone 1 (1.0 mmol), KF (0.1 mmol), and
NaOH (0.2 mmol) in DMF (4.8 mL) and H2O (0.2 mL) was stirred
at 120 °C under air for 12 h. When the reaction was complete
(TLC), the mixture was cooled to r.t., diluted with EtOAc, and
washed with sat. aq Na2CO3. The resulting organic phase was
dried (MgSO4) and concentrated under reduced pressure. The
residue was purified by column chromatography [silica gel, PE–
EtOAc (20:1)]. Analytical data for representative products are
given below.
Acknowledgment
The authors thank the National Natural Science Foundation of China
(21462038, 21362034, 21162024) and the Key Laboratory of Eco-
Environment-Related Polymer Materials for Ministry of Education for
their financial support of this work.
Supporting Information
2-Hydroxy-1,3-diphenylpropane-1,3-dione (2a)
White solid; yield: 95%; mp 92–94 °C. 1H NMR (600 MHz,
CDCl3): δ = 7.99 (d, J = 7.8 Hz, 4 H, ArH), 7.47–7.55 (m, 6 H, ArH),
6.86 (s, 1 H, CH). 13C NMR (150 MHz, CDCl3): δ = 185.7, 135.5,
132.4, 126.7, 127.1, 93.1. Anal. Calcd for C15H12O3: C, 74.99; H,
5.03. Found: C, 74.86; H, 5.05.
Supporting information for this article is available online at
S
u
p
p
ortiInfogrmoaitn
S
u
p
p
ortioInfgrmoaitn
References and Notes
1-(2-Furyl)-2-hydroxy-3-phenylpropane-1,3-dione (2n)
White solid; yield: 80%; mp 76–78 °C. 1H NMR (600 MHz,
CDCl3) δ = 7.96 (d, J = 7.2 Hz, 2 H, ArH), 7.47–7.62 (m, 4 H, ArH
(1) (a) Christoffers, J.; Baro, A.; Werner, T. Adv. Synth. Catal. 2004,
346, 143. (b) Pritchard, D. R.; Wilden, J. D. Tetrahedron Lett.
2010, 51, 1819. (c) Siliphaivanh, P.; Harrington, P.; Witter, D. J.;
Otte, K.; Tempest, P.; Kattar, S.; Kral, A. M.; Fleming, J. C.;
Deshmukh, S. V.; Harsch, A.; Secrist, P. J.; Miller, T. A. Bioorg.
Med. Chem. Lett. 2007, 17, 4619.
and FuH), 7.23–7.27 (m, 2 H, ArH and FuH), 6.77 (s, 1 H, CH). 13
C
NMR (150 MHz, CDCl3): δ = 182.5, 177.7, 151.0, 146.1, 134.7,
132.4, 128.7, 127.0, 115.8, 112.7, 92.7. Anal. Calcd for C13H10O4:
C, 67.82; H, 4.38. Found: C, 67.74; H, 4.39.
(2) (a) Asahara, H.; Nishiwaki, N. J. Org. Chem. 2014, 79, 11735.
(b) Andriamialisoa, R.; Langlois, N.; Langlois, Y. Tetrahedron Lett.
1985, 26, 3563.
© Georg Thieme Verlag Stuttgart · New York — Synlett 2015, 26, 2863–2865