PAPER
Aerobic Oxidative Hydroxylation of Arylboronic Acids
299
1
H NMR (400 MHz, CDCl ): δ = 7.65 (dd, J = 7.9, 1.5 Hz, 1 H),
.32–7.16 (m, 1 H), 6.99 (dd, J = 8.1, 1.4 Hz, 1 H), 6.67 (td, J = 7.8,
.4 Hz, 1 H), 5.29 (s, 1 H).
(3) For reviews, see: (a) Suzuki, A.; Yamamoto, Y. Chem. Lett.
2011, 40, 894. (b) Suzuki, A. Angew. Chem. Int. Ed. 2011,
50, 6722.
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7
1
1
3
(4) (a) Xu, J.; Wang, X.; Shao, C.; Su, D.; Cheng, G.; Hu, Y.
Org. Lett. 2010, 12, 1964. (b) Chowdhury, A. D.; Mobin, S.
M.; Mukherjee, S.; Bhaduri, S.; Lahiri, G. K. Eur. J. Inorg.
Chem. 2011, 3232. (c) Inamoto, K.; Nozawa, K.; Yonemoto,
M.; Kondo, Y. Chem. Commun. 2011, 47, 11775. (d) Yang,
H.; Li, Y.; Jiang, M.; Wang, J.; Fu, H. Chem. Eur. J. 2011,
17, 5652. (e) Kaboudin, B.; Abedi, Y.; Yokomatsu, T. Eur.
J. Org. Chem. 2011, 6656. (f) Zou, Y.-Q.; Chen, J.-R.; Liu,
X.-P.; Lu, L.-Q.; Davis, R. L.; Jørgensen, K. A.; Xiao, W.-J.
Angew. Chem. Int. Ed. 2012, 51, 784. (g) Pitre, S. P.;
McTiernan, C. D.; Ismaili, H.; Scaiano, J. C. J. Am. Chem.
Soc. 2013, 135, 13286.
C NMR (100 MHz, CDCl ): δ = 154.8, 1383, 130.2, 122.4, 115.2,
3
8
5.7.
4
-Hydroxybenzaldehyde (2p)4a
Yield: 115 mg (94%); yellowish solid; mp 113–115 °C (EtOAc–
PE).
1
H NMR (400 MHz, CDCl ): δ = 9.87 (s, 1 H), 7.82 (d, J = 8.7 Hz,
3
2
H), 6.98 (d, J = 8.6 Hz, 2 H), 6.34 (s, 1 H).
13
C NMR (100 MHz, CDCl ): δ = 191.3, 161.7, 132.5, 129.8, 116.0.
3
-Acetylphenol (2q)5i
4
Yield: 124 mg (91%); white solid; mp 107–108 °C (EtOAc–PE).
(5) (a) Webb, K. S.; Levy, D. Tetrahedron Lett. 1995, 36, 5117.
1
H NMR (400 MHz, CDCl ): δ = 8.09 (br, 1 H), 7.92 (d, J = 8.6 Hz,
3
(
b) Simon, J.; Salzbrunn, S.; Prakash, G. K. S.; Petasis, N.
2
H), 6.96 (d, J = 8.6 Hz, 2 H), 2.59 (s, 3 H).
A.; Olah, G. A. J. Org. Chem. 2001, 66, 633. (c) Prakash, G.
K. S.; Chacko, S.; Panja, C.; Thomas, T. E.; Gurung, L.;
Rasul, G.; Mathew, T.; Olah, G. A. Adv. Synth. Catal. 2009,
13
C NMR (100 MHz, CDCl ): δ = 198.7, 161.5, 131.2, 129.5, 115.6,
3
2
6.3.
3
51, 1567. (d) Gogoi, A.; Bora, U. Synlett 2012, 23, 1079.
Phenol (2r)4a
(
e) Mulakayala, N.; Ismail Kumar, K. M.; Rapolu, R. K.;
Yield: 79 mg (84%); white solid; mp 40–41 °C (EtOAc–PE).
Kandagatla, B.; Rao, P.; Oruganti, S.; Pal, M. Tetrahedron
Lett. 2012, 53, 6004. (f) Travis, B. R.; Ciaramitaro, B. P.;
Borhan, B. Eur. J. Org. Chem. 2002, 3429. (g) Maleczka, R.
E.; Shi, F.; Holmes, D.; Smith, M. R. J. Am. Chem. Soc.
1
H NMR (400 MHz, CDCl ): δ = 7.24 (t, J = 7.7 Hz, 2 H), 6.93 (t,
3
J = 7.4 Hz, 1 H), 6.86–6.80 (m, 2 H), 5.13 (br, 1 H).
13
C NMR (100 MHz, CDCl ): δ = 155.4, 129.7, 120.8, 115.3.
3
2
003, 125, 7792. (h) Kianmehr, E.; Yahyaee, M.; Tabatabai,
1
,3-Diphenyl-2,3-epoxypropan-1-one (5)12
K. Tetrahedron Lett. 2007, 48, 2713. (i) Zhu, C.; Wang, R.;
Falck, J. R. Org. Lett. 2012, 14, 3494.
A mixture of hydroquinone (110 mg, 1 mmol), the α,β-unsaturated
ketone 4 (208 mg, 1 mmol), and KOH (168 mg, 3.0 mmol) in 1:1
(6) (a) Hosoi, K.; Kuriyama, Y.; Inagi, S.; Fuchigami, T. Chem.
Commun. 2010, 46, 1284. (b) Jiang, H.; Lykke, L.; Pedersen,
S. U.; Xiao, W.-J.; Jørgensen, K. A. Chem. Commun. 2012,
H O–DMF (5 mL) was stirred at 60 °C under open air for 10 h. Af-
2
ter complete consumption of 4 (monitored by TLC, eluent: PE–
EtOAc, 20:1), the reaction was quenched carefully by the addition
of aq 2 M HCl (15 mL). The resulting mixture was extracted with
EtOAc (3 × 20 mL). The combined organic layers were washed
with H O (30 mL) and brine (10 mL) and dried (Na SO ). After the
4
8, 7203. (c) Qj, H.-L.; Chen, D.-S.; Ye, J.-S.; Huang, J.-M.
J. Org. Chem. 2013, 78, 7482.
(
7) (a) Cammidge, A. N.; Goddard, V. H. M.; Schubert, C. P. J.;
Gopee, H.; Hughes, D. L.; Gonzalez-Lucas, D. Org. Lett.
2
2
4
removal of the solvent, the resulting residue was purified by chro-
matography (silica gel, 5% EtOAc in PE) to give 5 as a colorless
solid; yield: 78 mg (35%); mp 84–85 °C (EtOAc–PE).
1
2
011, 13, 6034. (b) Kaewmati, P.; Somsook, E.; Dhital, R.
N.; Sakurai, H. Tetrahedron Lett. 2012, 53, 6104.
8) (a) Anderson, K. W.; Ikawa, T.; Tundel, R. E.; Buchwald, S.
L. J. Am. Chem. Soc. 2006, 128, 10694. (b) Chen, G.; Chan,
A. S. C.; Kwong, F. Y. Tetrahedron Lett. 2007, 48, 473.
(c) Willis, M. C. Angew. Chem. Int. Ed. 2007, 46, 3402.
(d) Gallon, B. J.; Kojima, R. W.; Kaner, R. B.; Diaconescu,
P. L. Angew. Chem. Int. Ed. 2007, 46, 7251. (e) Schulz, T.;
Torborg, C.; Schaeffner, B.; Huang, J.; Zapf, A.; Kadyrov,
R.; Boerner, A.; Beller, M. Angew. Chem. Int. Ed. 2009, 48,
918. (f) Sergeev, A. G.; Schulz, T.; Torborg, C.;
(
H NMR (400 MHz, CDCl ): δ = 8.02 (ddd, J = 5.3, 3.1, 1.2 Hz, 2
3
H), 7.65–7.60 (m, 1 H), 7.53–7.47 (m, 2 H), 7.44–7.36 (m, 5 H),
4.30 (d, J = 1.9 Hz, 1 H), 4.08 (d, J = 1.9 Hz, 1 H).
13
C NMR (100 MHz, CDCl ): δ = 193.1, 135.5, 134.0, 129.1, 129.0,
3
128.9, 128.8, 128.4, 125.8, 61.0, 59.4.
Acknowledgment
Spannenberg, A.; Neumann, H.; Beller, M. Angew. Chem.
Int. Ed. 2009, 48, 7595. (g) Yu, C.-W.; Chen, G. S.; Huang,
C.-W.; Chern, J.-W. Org. Lett. 2012, 14, 3688.
This work was supported by National Natural Science Foundation
of China (21202048), Program for Minjiang Scholar (10BS216),
Science Research Item of Science and Technology of Xiamen City
(
9) (a) Tlili, A.; Xia, N.; Monnier, F.; Taillefer, M. Angew.
Chem. Int. Ed. 2009, 48, 8725. (b) Zhao, D.; Wu, N.; Zhang,
S.; Xi, P.; Su, X.; Lan, J.; You, J. Angew. Chem. Int. Ed.
(3502z201014), the Natural Science Foundation of Fujian Province,
China (2013J01050), and Promotion Program for Young and Middle-
aged Teacher in Science and Technology Research of Huaqiao
University (ZQN-PY120).
2
009, 48, 8729. (c) Paul, R.; Ali, M. A.; Punniyamurthy, T.
Synthesis 2010, 4268. (d) Maurer, S.; Liu, W.; Zhang, X.;
Jiang, Y.; Ma, D. Synlett 2010, 976. (e) Jing, L.; Wei, J.;
Zhou, L.; Huang, Z.; Li, Z.; Zhou, X. Chem. Commun. 2010,
Supporting Information for this article is available online at
http://www.thieme-connect.com/ejournals/toc/synthesis. SnuIoipgfmr tooatrin guSIopi
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(
2
6, 4767. (f) Yang, D.; Fu, H. Chem. Eur. J. 2010, 16, 2366.
g) Chen, J.; Yuan, T.; Hao, W.; Cai, M. Catal. Commun.
011, 12, 1463. (h) Thakur, K. G.; Sekar, G. Chem.
nnfo itrmart
Commun. 2011, 47, 6692. (i) Chan, C.-C.; Chen, Y.-W.; Su,
C.-S.; Lin, H.-P.; Lee, C.-F. Eur. J. Org. Chem. 2011, 7288.
(j) Xu, H.-J.; Liang, Y.-F.; Cai, Z.-Y.; Qi, H.-X.; Yang, C.-
Y.; Feng, Y.-S. J. Org. Chem. 2011, 76, 2296. (k) Yang, K.;
Li, Z.; Wang, Z.; Yao, Z.; Jiang, S. Org. Lett. 2011, 13, 4340.
(l) Jia, J.; Jiang, C.; Zhang, X.; Jiang, Y.; Ma, D.
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