PAPER
Aerobic Oxidation of Benzylic Alcohols in Water
3391
1
H NMR (400 MHz, CDCl ): δ = 10.37 (s, 1 H), 7.93–7.91 (m, 1 H), Acknowledgment
3
7
.65 (d, J = 6.8 Hz, 1 H), 7.46–7.44 (m, 2 H).
The work was supported by National Natural Science Foundation of
China (21072170).
1
3
C NMR (100 MHz, CDCl ): δ = 192.1, 135.5, 134.0, 133.5, 130.0,
3
1
28.0, 127.3.
2
-Bromo-4-fluorobenzaldehyde (2m)23
Supporting Information for this article is available online at
White solid; yield: 150 mg (74%).
http://www.thieme-connect.com/ejournals/toc/synthesis.SnoIufproi
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1
H NMR (400 MHz, CDCl ): δ = 10.28 (s, 1 H), 7.98–7.94 (m, 1 H),
3
7.39 (d, J = 8.0 Hz, 1 H), 7.16–7.15 (m, 1 H).
13
References
C NMR (100 MHz, CDCl ): δ = 190.3, 165.9 (d, JC-F = 258.4 Hz),
3
1
32.1 (d, JC-F = 10.9 Hz), 130.4 (d, JC-F = 2.8 Hz), 128.2 (d, JC-F
=
(
1) Aqueous-Phase Organometallic Catalysis: Concepts and
Applications; Cornils, B.; Herrmann, W. A., Eds.; Wiley-
VCH: Weinheim, 2004.
11.2 Hz), 121.3 (d, JC-F = 23.9 Hz), 115.8 (d, JC-F = 21.3 Hz).
,4-Dichlorobenzaldehyde (2n)22
3
(
(
2) Butler, R. N.; Coyne, A. G. Chem. Rev. 2010, 110, 6302.
3) ten Brink, G.-J.; Arends, I. W. C. E.; Sheldon, R. A. Science
White solid; yield: 108 mg (62%).
1
H NMR (400 MHz, CDCl ): δ = 9.95 (s, 1 H), 7.96 (s, 1 H), 7.72
3
(Washington, D.C.) 2000, 287, 1636.
(d, J = 8.4 Hz, 1 H), 7.63 (d, J = 7.6 Hz, 1 H).
(4) Punniyamurthy, T.; Laxmidhar, R. Coord. Chem. Rev. 2008,
13
C NMR (100 MHz, CDCl ): δ = 189.6, 139.0, 135.8, 133.9, 131.3,
252, 134.
3
1
31.1, 128.4.
(5) Maclennan, A.; Banerjee, A.; Scott, R. W. J. Catal. Today
013, 207, 170.
6) Komiya, N.; Nakae, T.; Sato, H.; Naota, T. Chem. Commun.
006, 46, 4829.
(7) Verho, O.; Dilenstam, M. D. V.; Kärkäs, M. D.; Johnston, E.
V.; Åkermark, T.; Bäckvall, J. E.; Åkermark, B. Chem. Eur.
J. 2012, 18, 16947.
2
4
-(Trifluoromethyl)benzaldehyde (2o)24
(
Light yellow liquid; yield: 113 mg (65%).
2
1
H NMR (400 MHz, CDCl ): δ = 10.13 (s, 1 H), 8.05–8.02 (m, 2 H),
3
7.85–7.82 (m, 2 H).
13
C NMR (100 MHz, CDCl ): δ = 190.9, 138.4, 135.6, 135.2, 129.7,
3
(
(
8) Herrmann, W. A. Angew. Chem. Int. Ed. 2002, 41, 1290.
9) de Fremont, P.; Marion, N.; Nolan, S. P. Coord. Chem. Rev.
2009, 253, 862.
125.9 (q, JC-F = 3.8 Hz), 124.6, 121.8.
2
-(Trifluoromethyl)benzaldehyde (2p)25
Light yellow liquid; yield: 63 mg (36%).
(10) (a) Velazquez, H. D.; Verpoort, F. Chem. Soc. Rev. 2012, 41,
7032. (b) Schaper, L. A.; Hock, S. J.; Herrmann, W. A.;
Kuhn, F. E. Angew. Chem. Int. Ed. 2013, 52, 270.
11) Allen, S. E.; Walvoord, R. R.; Salinas, R. P.; Kozlowski, M.
C. Chem. Rev. 2013, 113, 6234.
12) (a) Liu, B.; Xia, Q. Q.; Chen, W. Angew. Chem. Int. Ed.
2009, 48, 5513. (b) Liu, B.; Liu, B.; Zhou, Y. B.; Chen, W.
Organometallics 2010, 29, 1457. (c) Liu, B.; Xu, D. C.;
Chen, W. Z. Chem. Commun. 2011, 47, 2883. (d) Liu, X.;
Xia, Q.; Zhang, Y.; Chen, C.; Chen, W. J. Org. Chem. 2013,
1
H NMR (400 MHz, CDCl ): δ = 10.44 (s, 1 H), 8.18–8.16 (m, 1 H),
3
7.84–7.82 (m, 1 H), 7.76–7.74 (m, 2 H).
(
13
C NMR (100 MHz, CDCl ): δ = 184.7, 129.7, 129.5, 128.4, 126.8
3
(q, JC-F = 32 Hz), 125.0, 122.1, 119.5 (q, JC-F = 272 Hz).
(
-Nitrobenzaldehyde (2q)17
4
Yellow solid; yield: 144 mg (95%).
1
H NMR (400 MHz, CDCl ): δ = 10.15 (s, 1 H), 8.38 (d, J = 8.8 Hz,
3
2
H), 8.07 (d, J = 8.0 Hz, 2 H).
7
8, 8531.
13
C NMR (100 MHz, CDCl ): δ = 190.4, 151.3, 140.2, 130.6, 124.4.
(13) (a) Liu, A.; Zhang, X.; Chen, W. Organometallics 2009, 28,
3
4
7
2
868. (b) Zhang, X.; Xia, Q.; Chen, W. Dalton Trans. 2009,
045. (c) Xi, Z.; Liu, B.; Lu, C.; Chen, W. Dalton Trans.
009, 7008. (d) Zhang, X.; Gu, S.; Xia, Q.; Chen, W.
2
-Nitrobenzaldehyde (2r)20
Yellow solid; yield: 131 mg (87%).
1
H NMR (400 MHz, CDCl ): δ = 10.42 (s, 1 H), 8.12 (d, J = 7.6 Hz,
J. Organomet. Chem. 2009, 694, 2359.
3
1
H), 7.97–7.95 (m, 1 H), 7.82–7.75 (m, 2 H).
(14) (a) Papini, G.; Pellei, M.; Lobbia, G. G.; Burini, A.; Santini,
C. Dalton Trans. 2009, 6985. (b) Godoy, F.; Segarra, C.;
Peris, E. Organometallics 2011, 30, 684.
15) (a) Gamez, P.; Arends, I. W. C. E.; Reedijk, J.; Sheldon, R.
A. Chem. Commun. 2003, 2414. (b) Gamez, P.; Arends, I.
W. C. E.; Sheldon, R. A.; Reedijk, J. Adv. Synth. Catal.
2004, 346, 805.
16) Zhu, Y.; Zhao, B.; Shi, Y. Org. Lett. 2013, 15, 992.
17) Ragagnin, G.; Betzemeier, B.; Quici, S.; Knochel, P.
Tetrahedron 2002, 58, 3985.
13
C NMR (100 MHz, CDCl ): δ = 188.3, 149.5, 134.2, 133.8, 131.3,
3
129.7, 124.6.
(
Thiophene-2-carbaldehyde (2s)19
Light yellow oil; yield: 85 mg (76%).
1
H NMR (400 MHz, CDCl ): δ = 9.90 (s, 1 H), 7.76–7.72 (m, 2 H),
3
(
(
7.18 (t, J = 4.4 Hz, 1 H).
13
C NMR (100 MHz, CDCl ): δ = 183.1, 143.9, 136.5, 135.2, 128.4.
3
Cinnamaldehyde (2u)17
(18) Jiang, N.; Ragauskas, A. J. Org. Lett. 2005, 7, 3689.
(
19) Hoover, J. M.; Stahl, S. S. J. Am. Chem. Soc. 2011, 133,
6901.
Colorless oil; yield: 117 mg (89%).
1
1
H NMR (400 MHz, CDCl ): δ = 9.68 (d, J = 7.6 Hz, 1 H), 7.55–
3
(20) Miao, C. X.; Wang, J. Q.; He, L. N.; Zhang, S. J. Chem.
Commun. 2011, 47, 2697.
7.53 (m, 2 H), 7.47–7.41 (m, 4 H), 6.72–6.66 (m, 1 H).
13
C NMR (100 MHz, CDCl ): δ = 193.8, 152.9, 133.9, 131.3, 129.1,
(21) Nath, P.; Punniyamurthy, T. Adv. Synth. Catal. 2007, 349,
3
128.5.
846.
(22) Pérez, L. J. M.; Cano, R.; Yus, M.; Ramón, D. J. Eur. J. Org.
Chem. 2012, 4548.
(23) Rauniyar, V.; Hall, D. G. J. Org. Chem. 2009, 74, 4236.
(24) Sun, H.-y.; Huang, W.-x. Adv. Synth. Catal. 2012, 354, 569.
(25) Gregg, B. T.; Quinn, J. F. J. Org. Chem. 2007, 72, 5890.
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Georg Thieme Verlag Stuttgart · New York
Synthesis 2013, 45, 3387–3391