Journal of the American Chemical Society
Page 4 of 5
1
2
3
4
5
6
7
8
9
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
Scheme 9. A proposed mechanism-the possible role of the cation.
(4) Caron, S.; Dugger, R. W.; Ruggeri, S. G.; Ragan, J. A.; Ripin,
D. H. B. Chem. Rev. 2006, 106, 2943.
5) Mahmood, A.; Robinson, G. E.; Powell, L.; Org. Process Res.
Dev. 1999, 3, 363.
6) Thottathil, J. K.; Moniot, J. L.; Mueller, R. H.; Wong, M. K. Y.;
Kissick, T. P. J. Org. Chem. 1986, 51, 3140.
7) (a) Stahl, S. S.; Ryland, B. L. Angew. Chem. Int. Ed. 2014, 53,
824. (b) Cao, Q.; Dornan, L. M.; Rogan, L.; Hughes, N. L.; Muldoon,
M. J. Chem. Commun. 2014, 50, 4524. (c) Piera, J.; Bäckvall, J. E.
Angew. Chem. Int. Ed. Engl. 2008, 47, 3506. (d) de Nooy, A. E. J.;
Besemer, A. C.; van Bekkum, H. Synthesis, 1996, 1153 and
references therein. (e) Sheldon, R. A.; Arends, I. W. C. E. Adv. Synth.
Catal. 2004, 1051.
(
(
(
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
8
(
8) (a) Dalmer, O., Heyns, K. U.S. Pat. 1940, 2, 190, 377. (b)
Heyns, K. Lieb. Ann. Chem. 1947, 558, 177.
(9) Han, L.; Xing, P.; Jiang, B. Org. Lett. 2014, 16, 3428.
(10) Zope, B. N.; Hibbitts, D. D.; Neurock, M.; Davis, R. J.
Science, 2010, 330, 74.
(11) Buffin, B. P.; Clarkson, J. P.; Belitz, N. L.; Kundu, A. J. Mol.
Catal. A. 2005, 225, 111.
In summary, we have developed a practical and efficient
environmentally benign catalytic protocol of Fe(NO ·9H
TEMPO/MCl to accomplish the oxidation of alcohols to
3
)
3
2
O
/
carboxylic acids using O2 or air as terminal oxidant at room
temperature while the oxidation of benzylic alcohols stopped in
the aldehyde stage. The reaction may be easily conducted on 9 to
55 gram-scale with pure O , air/pure O , or air flow conditions.
(12) Zhang, Z. H.; Zhen, J. D.; Liu, B.; Lv, K. L.; Deng, K. J.
Green Chem. 2015, 17, 1308.
(
13) Kerdi, F.; Rass, H. A.; Pinel, C.; Besson, M.; Peru, G.; Leger,
B.; Rio, S.; Monflier, E.; Ponchel, A. Appl. Catal. A. 2015, 506, 206.
14) Itoh, A.; Hashimoto, S.; Kuwabara, K.; Kodama, T.; Masaki,
2
2
First total synthesis of natural product phlomic acid was
accomplished using this aerobic oxidation protocol and EATA.
Further studies especially the mechanism are being actively
pursued in this laboratory.
(
Y. Green Chem. 2005, 7, 830.
(15) Iwahama, T.; Yoshino, Y.; Keitoku, T.; Sakaguchi, S.; Ishii, Y.
J. Org. Chem. 2000, 65, 6502.
(
16) Yamada, Y. M. A.; Arakawa, T.; Hocke, H.; Uozumi, Y.
Angew. Chem. Int. Ed. 2007, 46, 704.
17) Liu, M. X.; Wang, H. N.; Zeng, H. Y.; Li, C. J. Sci. Adv. 2015,
ASSOCIATED CONTENT
Supporting Information
Experimental procedure, spectroscopic data, and the H/ C NMR
spectra of all the products. This material is available free of
charge via the Internet at http://pubs.acs.org.
(
1, e1500020.
1
13
(18) (a) Martín, S. E.; Suárez, D. F. Tetrahedron Lett. 2002, 43,
4475. (b) Firouzabadi, H.; Iranpoor, N.; Amani, K. Synthesis, 2003,
408. (c) Namboodiri, V. V.; Polshettiwar, V.; Varma, R. S.
Tetrahedron Lett. 2007, 48, 8839. (d) Wang, N.; Liu, R.; Chen, J.;
Liang, X. Chem. Commun. 2005, 5322.
(19) Ma, S.; Liu, J. X.; Li, S. H.; Chen, B.; Cheng, J. J.; Kuang, J.
Q.; Liu, Y.; Wan, B. Q.; Wang, Y. L.; Ye, J. T.; Yu, Q.; Yuan, W. M.;
Yu, S. C. Adv. Synth. Catal. 2011, 353, 1005.
AUTHOR INFORMATION
Corresponding Author
(20) CAUTION: Oxygen in use in combination with organic
solvents; remove all ignition sources including sources of sparks,
static, or flames since oxygen increases intensity of any fire.
Inhalation of pure oxygen should be avoided as well. The flash point
Notes
The authors declare no competing financial interests.
o
of DCE is 13 C. Lower and upper explosive limit of DCE in air is
ACKNOWLEDGMENT
6.2% and 16.0%. For more information, see: Cheremisinoff, N. P.
Handbook
of
Hazardous
Chemical
Properties,
Financial support from National Natural Science Foundation of
China (21232006) and National Basic Research Program
Butterworth-Heinemann, Woburn, 1999. Yaws, C. L. Yaws’
Handbook of Thermodynamic and Physical Properties of Chemical
Compounds, Knovel, 2003.
(
2015CB856600) are greatly appreciated. We thank Mr. Lin
Weilong for supplying (S)-dimethyl prolinol.
(
21) Aitzetmüller, K.; Tsevegsüren, N.; Vosmann, K. Fett/Lipid.
997, 99, 74.
22) (a) Huang, X.; Cao, T.; Han, Y. L.; Jiang, X. G.; Lin, W. L.;
1
(
Zhang, J. S.; Ma, S. Chem. Commun. 2015, 51, 6956. (b) Tang, X. J.;
Huang, X.; Cao, T.; Han, Y. L.; Jiang X. G.; Lin, W. L.; Tang, Y.;
Zhang, J. S.; Ma, S. Org. Chem. Front. 2015, 2, 688.
REFERENCES
(
1) Metzler, D. E. Biochemistry: The Chemical Reactions of Living
Cells (Academic Press, New York, 2001), vol. 1.
2) (a) Nozaki, M. Oxygenases and Dioxygenases, Biochemistry,
Topics in Current Chemistry, p.147 (Springer, Berlin, 1979), vol. 78.
b) Blomberg, M. R. A. Biochemistry, 2016, 55, 489 (c) Thrower, J.
(23) Cartledge, G. H. J. Am. Chem. Soc. 1928, 50, 2863.
(24) (a) Wieland, H.; Richter, D. Justus Liebigs Annalen der
(
Chemie, 1931, 486, 226. (b) Giannandrea, R.; Mastrorilli, P.; Nobile,
C. F.; Suranna, G. P. J. Mol. Catal., 1994, 94, 27. (c) Lederer, P.;
Lunak, S.; Macova, E.; Veprek-Siska, J. Collection Czechosiovak
Chem. Commun. 1982, 47, 392. (d) Yamada, T.; Rhode, O.; Takai, T.;
Mukaiyama, T. Chem. Lett. 1991, 5.
(25) Scepaniak, J. J.; Wright, A. M.; Lewis, R. A., Wu, G. and
Hayton, T. W. J. Am. Chem. Soc. 2012, 134, 19350.
(26) Epstein, I. R.; Kustin, K.; Warshaw, L. J. J. Am. Chem. Soc.
1980, 102, 3751.
(
S.; Blalock III, R.; Klinman, J. P. Biochemistry, 2001, 40, 9717. (d)
Zhang, Z. H., Barlow, J. N.; Baldwin, J. E.; Schofield, C. J.
Biochemistry, 1997, 36, 15999.
(3) (a) Bolm, C.; Legros, J.; Paih, J. L.; Zani, L. Iron-catalyzed
reactions in organic synthesis. Chem. Rev. 2004, 104, 6217. (b)
Gorpalaiah, K. Chem. Rev. 2013, 113, 3248. c) Bauer, I.; Knölker, H.
J. Chem. Rev. 2015, 115, 3170.
ACS Paragon Plus Environment