DOI: 10.1126/science.1128383. Chemoselective Hydrogenation of Nitro Compounds with Supported Gold Catalysts

Chemoselective Hydrogenation of Nitro Compounds with Supported Gold Catalysts

10.1126/science.1128383

Crossref journal-article

American Association for the Advancement of Science (AAAS)

Science (221)

Abstract

The selective reduction of a nitro group when other reducible functions are present is a difficult process that often requires stoichiometric amounts of reducing agents or, if H 2 is used, the addition of soluble metals. Gold nanoparticles supported on TiO 2 or Fe 2 O 3 catalyzed the chemoselective hydrogenation of functionalized nitroarenes with H 2 under mild reaction conditions that avoided the accumulation of hydroxylamines and their potential exothermic decomposition. These chemoselective hydrogenation gold catalysts also provide a previously unknown route for the synthesis of the industrially relevant cyclohexanone oxime from 1-nitro-1-cyclohexene.

Bibliography

Corma, A., & Serna, P. (2006). Chemoselective Hydrogenation of Nitro Compounds with Supported Gold Catalysts. Science, 313(5785), 332â334.

Authors 2

Avelino Corma (first)
Pedro Serna (additional)

References 27 Referenced 1,425

10.1016/S0920-5861(97)00005-9
M. Suchy P. Winternitz M. Zeller World (WO) Patent 91/00278 (1991).
F. Kovar F. E. Armond U.S. Patent 3 975 444 (1976).
J. Butera J. Bagli WO Patent 91/09023 (1991).
10.1016/0040-4020(59)80025-9
R. Braden H. Knupfer S. Hartung U.S. Patents 4 002 673 and 4 051 177 (1977).
M. A. Narendra O. P. Shivanand D. R. Madhukar WO Patent 2005.070.869 (2005).
W. Gerhar et al . U.S. Patent 6 395 934 (2002).
P. N. Rylander, Catalytic Hydrogenation in Organic Synthesis (Academic Press, New York, 1979), p. 122. / Catalytic Hydrogenation in Organic Synthesis (1979)
U. Siegrist P. Baumeister H.-U. Blaser Catalysis of Organic Reactions F. Herkes Ed. vol. 75 of Chemical Industries (Dekker New York 1998).
H.-U. Blaser, U. Siegrist, H. Steiner, in Aromatic Nitro Compounds: Fine Chemicals through Heterogeneous Catalysis, R. A. Sheldon, H. van Bekkum, Eds. (Wiley-VCH, Weinheim, Germany, 2001), p. 389. / Aromatic Nitro Compounds: Fine Chemicals through Heterogeneous Catalysis (2001)
E. Janin, J. Catal.215, 243 (2003). / J. Catal. (2003)
10.1021/ja031768x
10.1006/jcat.1998.2199
10.1002/anie.200500382
A. Corma, M. E. Domine, Chem. Commun.32, 4042 (2005). / Chem. Commun. (2005)
S. Naito, M. Tanimoto, J. Chem. Soc. Chem. Commun.12, 832 (1988). / J. Chem. Soc. Chem. Commun. (1988)
S. A. Blankenship A. Rokicki J. A. Perkins U.S. Patent 2003.232.719 (2003).
10.1016/j.jcat.2005.09.023
C. González-Arellano, A. Corma, M. Iglesias, Chem. Commun.15, 3451 (2005). / Chem. Commun. (2005)
10.1016/j.apcata.2004.12.048
J. E. Bailie, G. J. Hutchings, Chem. Commun.21, 2151 (1999). / Chem. Commun. (1999)
10.1021/cr030698
10.1021/jp9909053
Materials and methods are available as supporting material on Science Online.
Detailed product distributions with the different catalysts are given in tables S1 to S6.
We thank the World Gold Council for supplying the gold catalysts that were used as well as for the corresponding transmission electron microscopy images and F. Sánchez M. Iglesias and C. González-Arellano for useful comments. This work was supported by Ministerio de Educación y Ciencia (grant MAT2003-07945-C02-01).

Dates

Type	When
Created	19 years, 1 month ago (July 20, 2006, 5:12 p.m.)
Deposited	1 year, 7 months ago (Jan. 9, 2024, 11:15 p.m.)
Indexed	2 weeks, 1 day ago (Aug. 7, 2025, 4:56 p.m.)
Issued	19 years, 1 month ago (July 21, 2006)
Published	19 years, 1 month ago (July 21, 2006)
Published Print	19 years, 1 month ago (July 21, 2006)

Funders 0

None

BibTeX

@article{Corma_2006, title={Chemoselective Hydrogenation of Nitro Compounds with Supported Gold Catalysts}, volume={313}, ISSN={1095-9203}, url={http://dx.doi.org/10.1126/science.1128383}, DOI={10.1126/science.1128383}, number={5785}, journal={Science}, publisher={American Association for the Advancement of Science (AAAS)}, author={Corma, Avelino and Serna, Pedro}, year={2006}, month=jul, pages={332–334} }

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