244
A. Corma et al. / Journal of Catalysis 265 (2009) 238–244
[10] P. Landon, P.J. Collier, A.J. Papworth, C.J. Kiely, G.J. Hutchings, Chem. Commun.
18 (2002) 2058–2059.
[11] X. Zhang, A. Corma, Angew. Chem., Int. Ed. Engl. 120 (23) (2007) 4430.
[12] M. Boronat, P. Concepción, A. Corma, S. González, F. Illas, P. Serna, J. Am. Chem.
Soc. 129 (51) (2007) 16230.
[13] (a) S. Carrettin, J. Guzman, A. Corma, Angew. Chem., Int. Ed. 44 (15) (2005)
2242–2245;
(b) C. Gonzalez-Arellano, A. Corma, M. Iglesias, F. Sanchez, Chem. Commun.
(2005) 3451–3453.
[14] (a) J.K. Edwars, B. Solsona, P. Landon, A.F. Carley, A. Herzing, C.J. Kiely, G.J.
Hutchings, J. Catal. 236 (1) (2005) 69–79;
(b) D.I. Enache, J.K. Edwards, P. Landon, B. Solsona, A.F. Carley, A.A. Herzing, M.
Watanabe, C.J. Kiely, D.W. Knight, G.J. Hutchings, Science 311 (2006) 362–365.
[15] (a) A. Abad, P. Concepción, A. Corma, H. García, Angew. Chem., Int. Ed. 44 (26)
(2005) 4066–4069;
(b) A. Corma, M.E. Domine, Chem. Commun. 32 (2005) 4042–4044.
[16] (a) F. Gasparrini, M. Giovannoli, D. Misiti, G. Natile, G. Palmieri, Tetrahedron
39 (1983) 3181–3184;
epoxidations carried out in the presence of a radical scavenger
definitively prove the existence of a dual pathway for the oxygen
transfer with chiral Au(III) catalyst: (A) a radical allylic oxidation
pathway (responsible of the formation of a, b-unsaturated ketones
an alcohols), and (B) a non-radical process where the metal would
mediate in a concerted or a nearly concerted transfer of oxygen
from the oxidant to the olefin to form the epoxide.
Electrochemical and UV–Vis experiments confirm that during
epoxidation an Au(III)/Au(I) redox cycle occurs with the interven-
tion of molecular oxygen.
This work provides a starting point in the design for aerobic
enantioselective epoxidations of olefins without the need of a sac-
rificial reducing agent.
(b) F. Gasparrini, M. Giovannoli, D. Misiti, G. Natile, G. Palmieri, Tetrahedron
40 (1984) 165–170;
Acknowledgements
(c) F. Gasparrini, M. Giovannoli, D. Misiti, G. Natile, G. Palmieri, J. Org. Chem.
55 (1990) 1323–1328;
Financial support by the Dirección General de Investigación
Científica y Técnica of Spain (Project MAT2006-14274-C02-01)
and Generalidad Valenciana (Projects GV04B-270 and PROMETEO
2008/130) is gratefully acknowledged. I.D. and T.R. thank Consejo
Superior de Investigaciones Científicas for I3-P fellowships.
(d) X.-Q. Li, C. Li, F.-B. Song, C. Zhang, J. Chem. Res. 12 (2007) 722–724.
[17] H. Saltzmann, J.G. Sharefkin, Org. Syn. 43 (1963) 60.
[18] (a) J.P. Collman, L. Zeng, J.I. Brauman, Inorg. Chem. 43 (2004) 2672;
(b) A.B. Kazi, G.D. Jones, D.A. Vicic, Organometallics 24 (2005) 6051.
[18] A.B. Kazi, G.D. Jones, D.A. Vicic, Organometallics 24 (2005) 6051.
[19] W.C. Barrette, H.W. Johnson, D.T. Sawyer, Anal. Chem. 56 (1984) 1890–1898.
[20] B. Guan, D. Xing, G. Cai, X. Wan, N. Yu, Z. Fang, L. Yang, Z. Shi, J. Am. Chem. Soc.
127 (2005) 18004.
References
[21] V.P. Pushkarev, V.I. Kovalchuk, J.L. d’Ihi, J. Phys. Chem. B 108 (2004) 5341–
5348.
[1] (a) R.A. Sheldon, J.K. Kochi, Metal-Catalyzed Oxidations of Organic
Compounds, Academic Press, New York, 1981;
[22] The electrochemical response (on scanning the potential in the negative
direction the cyclic voltammogram) evidenced the existence of two well-
defined cathodic peaks at +125 and ꢁ5 mV followed by a wave at ꢁ480 mV. In
agreement with prior data concerning different Au(III) complexes, peaks at
+125 and ꢁ5 mV could be ascribed to the two-step reduction of Au(III) to
Au(I), subsequently reduced to Au(0) at potentials ca ꢁ500 mV.
[23] G.B. Shul‘pin, A.E. Shilov, G. Süss-Fink, Tetrahed. Lett. 42 (2001) 7253–7256.
[24] (a) J.T. Groves, R. Quinn, J. Am. Chem. Soc. 107 (1985) 5790–5792;
(b) C. Balley, R.S. Drago, J. Chem. Soc. Chem. Commun. (1987) 179–180;
(c) A.S. Goldstein, R.H. Beer, R.S. Drago, J. Am. Chem. Soc. 116 (1994) 2424–
2429.
(b) Oxygen complexes and oxygen activation by transition metals, in: A.E.
Martell, D.T. Sawyer (Eds.), Proceedings of the Fifth Annual IUCCP Symposium,
Plenum Press, New York, 1988.
[2] R.S. Drago, Coord. Chem. Rev. 117 (1992) 185.
[3] D.T. Sawyer, Oxygen Chemistry, Oxford University Press, Oxford, 1991.
[4] D. Enders, L. Kramps, J. Zhu, Tetrahedron: Asymmetry 9 (22) (1988) 3959–
3962.
[5] T-S. Lai, R. Zhang, K.-K. Cheung, C.-M. Che, H.-L. Kwong, Chem. Commun. 15
(1988) 1583–1584.
[6] M.S. Sigman, D.R. Jensen, S. Rajaram, Curr. Opin. Drug Discovery Develop. 5 (6)
(2002) 860–869.
[25] (a) E.N. Jacobsen, W. Zhang, A.R. Muci, J.R. Ecker, L. Deng, J. Am. Chem. Soc. 113
(1991) 7063–7064;
[7] M. Haruta, N. Yamada, T. Kobayashi, S. Ilima, J. Catal. 115 (1989) 301–309.
[8] (a) A.S.K. Hashmi, Chem. Rev. 107 (7) (2007) 3180;
(b) G.C. Bond, D.T. Thompson, Catal. Rev. Sci. Eng. 41 (1999) 319–388.
[9] (a) G.C. Bond, J. Mol. Catal. A: Chem. 156 (2000) 1;
(b) A. Corma, C. González-Arellano, M. Iglesias, F. Sánchez, Angew. Chem., Int.
Ed. Engl. 46 (41) (2007) 7820.
(b) T. Irie, K. Noda, N. Matsumoto, T. Katsuki, Tetrahedron Lett. 31 (50) (1990)
7345–7348.
[26] G.B. Shul‘pin, J. Mol. Catal. A: Chem. 189 (2002) 39–66.
[27] H. Yoon, T.R. Wagler, K.J. O’Connor, C.J. Burrows, J. Am. Chem. Soc. 112 (1990)
4568–4570.