New Horizons of Process Chemistry pp 29-40 | Cite as
Heterogeneous Platinum Metal Catalyzed Deuterium Generation and Labeling Methods Using Hydrogen Gas and Deuterium Oxide as Key Reagents
Abstract
Deuterium (heavy hydrogen, D or 2H), a stable isotope of hydrogen (1H) consists of one proton, one neutron and one electron and used extensively in a wide range of fields including science, chemistry, medicine, etc. We have developed quite simple and post-synthetic D labeled methods using a combination of platinum metal on carbon and deuterium oxide (D2O) as the catalyst and a D source in the presence of organic substrates, and a highly pure D2 gas preparation method occurred at room temperature (rt) via the catalytic H2–D2 exchange reaction between the H atom of the H2 gas with the D atom of D2O without any substrates. This review illustrates and describes such straightforward and useful methodologies.
Keywords
Deuterium labeling H–D exchange C–H activation Platinum-group metal on carbon Deuterium gas preparation Deuterium oxide Hydrogen gasReferences
- 1.Foster, A. B., “Deuterium Isotope Effects in Studies of Drug Metabolism” Trends Pharmacol. Sci. (1984) 5, 524–527.Google Scholar
- 2.Davidova, I. A.; Gieg, L. M.; Nanny, M.; Kropp, K. G.; Suflita, J. M., “Stable Isotopic Studies of n-Alkane Metabolism by a Sulfate-Reducing Bacterial Enrichment Culture” Appl. Environ. Microbiol. (2005) 71, 8174–8182.Google Scholar
- 3.Lowry, T. H.; Richardson, K. S., “Mechanism and Theory in Organic Chemistry”, Harper & Row, New York (1987).Google Scholar
- 4.Perrin, C. L.; Dong, Y., “Secondary Deuterium Isotope Effects on Acidity of Carboxylic Acids and Phenols”, J. Am. Chem. Soc. (2007) 129, 4490–4497.Google Scholar
- 5.Kondo, A.; Ishigure, T.; Koike, Y., “Fabrication Process and Optical Properties of Perdeuterated Gradedindex Polymer Optical Fiber” J. Lightwave Technol. (2005) 23, 2443–2448.Google Scholar
- 6.Suzuki, Y.; Korenaga, T.; Chikaraishi, Y., “A Novel Method to Identify Illegal Diesel Fuel, II: the Use of [1-D] N-Alkane with Stable Hydrogen Isotope Analysis” Chem. Lett. (2006) 35, 532–533.Google Scholar
- 7.Sanderson, K., “Big Interest in Heavy Drugs” Nature (2009) 458, 269.Google Scholar
- 8.Harms, A. A.; Schoepf, K. F.; Miley, G. H.; Kingdon, D. R., “Principles of Fusion Energy: An Introduction to Fusion Energy for Students of Science and Engineering”, World Scientific, Singapore (2000).Google Scholar
- 9.Scrimgeour, C. M.; Rollo, M. M.; Mudambo, S. M. K. T.; Handley, L. L.; Prosser, S. J., ‘‘A Simplified Method for Deuterium/Hydrogen Isotope Ratio Measurements on Water Samples of Biological Origin’’, Biol. Mass Spectrom., (1993) 22, 383–387.Google Scholar
- 10.Benedict, M; Pigford, T. H., “Nuclear Chemical Engineering”, McGraw-Hill, New York, (1957).Google Scholar
- 11.Kikuchi, M.; Azumi, M., ‘‘Frontiers in Fusion Research II: Introduction to Modern Tokamak Physics’’, Tritium and Deuterium Chemistry, pp. 327–333, Springer, Heidelberg, (2015).Google Scholar
- 12.Sajiki, H.; Hattori, K.; Aoki, F.; Yasunaga, K.; Hirota, K., “Pd/C–H2–Catalyzed Deuterium Exchange Reaction of the Benzylic Site in D2O”, Synlett (2002) 1149–1151.Google Scholar
- 13.Maegawa, T.; Akashi, A.; Esaki, H.; Aoki, F.; Sajiki, H.; Hirota, K., “Efficient and Selective Deuteration of Phenylalanine Derivatives Catalyzed by Pd/C”, Synlett (2005) 845–847.Google Scholar
- 14.Kurita, T.; Hattori, K.; Seki, S.; Mizumoto, T.; Aoki, F.; Yamada, Y.; Ikawa, K.; Maegawa, T.; Monguchi, Y.; Sajiki, H., “Efficient and Convenient Heterogeneous Palladium-Catalyzed Regioselective Deuteration at the Benzylic Position”, Chem. Eur. J., (2008) 14, 664–673.Google Scholar
- 15.Sajiki, H.; Aoki, F.; Esaki, H.; Maegawa, T.; Hirota, K., “Efficient C–H/C–D Exchange Reaction on the Alkyl Side Chain of Aromatic Compounds Using Heterogeneous Pd/C in D2O”, Org. Lett. (2004) 6, 1485–1487.Google Scholar
- 16.Sajiki, H.; Esaki, H.; Aoki, F.; Maegawa, T.; Hirota, K., “Palladium-Catalyzed Base-Selective H–D Exchange Reaction of Nucleosides in Deuterium Oxide”, Synlett (2005) 1385–1388.Google Scholar
- 17.Esaki, H.; Aoki, F.; Maegawa, T.; Hirota, K.; Sajiki, H., “Synthesis of Base-Selectively Deuterium-Labeled Nucleosides by the Pd/C-Catalyzed H–D Exchange Reaction in Deuterium Oxide”, Heterocycles (2005) 66, 361–369.Google Scholar
- 18.Esaki, H.; Ito, N.; Sakai, S.; Maegawa, T.; Monguchi, Y.; Sajiki, H., “General Method of Obtaining Deuterium Labelling heterocyclic Compounds Using Neutral D2O with Heterogeneous Pd/C”, Tetrahedron (2006) 62, 10954–10961.Google Scholar
- 19.Esaki, H.; Aoki, F.; Umemura, M.; Kato, M.; Maegawa, T.; Monguchi, Y.; Sajiki, H., “Efficient H–D Exchange Reaction of Alkyl-substituted Benzene Derivatives Using Pd/C–H2–D2O System”, Chem. Eur. J. (2007) 13, 4052–4063.Google Scholar
- 20.Modutlwa, N.; Tada, H.; Sugahara, Y.; Shiraki, K.; Hara, N.; Deyashiki, Y.; Maegawa, T.; Monguchi, Y.; Sajiki, H., “Deuterium-Labelled Benzyladenine: Synthesis and Application as a Surrogate”, Heterocycles (2012) 84, 419–429.Google Scholar
- 21.Sajiki, H.; Ito, N.; Esaki, H.; Maesawa, T.; Maegawa, T.; Hirota, K., “Aromatic Ring Favorable and Efficient H–D Exchange Reaction Catalyzed by Pt/C”, Tetrahedron Lett. (2005) 46, 6995–6998.Google Scholar
- 22.Ito, N.; Esaki, H.; Maesawa, T.; Imamiya, E.; Maegawa, T.; Sajiki, H., “Pt/C-Catalyzed Efficient H–D Exchange Reaction of Aromatic Rings And its Scope and Limitations”, Bull. Chem. Soc. Jpn. (2008) 81, 278–286.Google Scholar
- 23.Ito, N.; Watahiki, T.; Maesawa, T.; Maegawa, T.; Sajiki, H., “Synergistic Effect of a Palladium-on-Carbon/Platinum-on-Carbon Mixed Catalyst in Hydrogen/Deuterium Exchange Reactions of Alkyl-Substituted Aromatic Compounds”, Adv. Synth. Catal. (2006) 348, 1025–1028.Google Scholar
- 24.Ito, N.; Watahiki, T.; Maesawa, T, Maegawa, T.; Sajiki, H., “H–D Exchange Reaction Taking Advantage of a Synergistic Effect of a Heterogeneous Pd and Pt Mixed Catalyst”, Synthesis (2008) 9, 1467–1478.Google Scholar
- 25.Maegawa, T.; Ito, N.; Ohno, K.; Monguchi, Y.; Sajiki, H., “Bimetallic Palladium-Platinum on Carbon Catalyzed H–D Exchange Reaction: Synergistic Effect on Multiple Deuterium Incorporation”, Synthesis (2009) 16, 2674–2678.Google Scholar
- 26.Maegawa, T.; Fujiwara, Y.; Inagaki, Y.; Esaki, H.; Monguchi, Y.; Sajiki, H., “Mild and Efficient H–D Exchange of Alkanes Based on C–H Activation Catalyzed by Heterogeneous Rhodium on Charcoal”, Angew. Chem. Int. Ed. (2008) 47, 5394–5397.Google Scholar
- 27.Maegawa, T.; Fujiwara, Y.; Inagaki, Y.; Monguchi, Y.; Sajiki, H., “A Convenient and Effective Method for the Regioselective Deuteration of Alcohols”, Adv. Synth. Catal. (2008) 350, 2215–2218.Google Scholar
- 28.Fujiwara, Y.; Iwata, H.; Sawama, Y.; Monguchi, Y.; Sajiki, H., “Regio-, Chemo- and Stereoselective Deuterium Labeling Method of Sugars Based on Ruthenium-Catalyzed C–H Bond Activation”, Chem. Commun. (2010) 46, 4977–4979.Google Scholar
- 29.Maegawa, T.; Hirota, K.; Tatematsu, K.; Mori, Y.; Sajiki, H., “Facile and Efficient Postsynthetic Tritium Labeling Method Catalyzed by Pd/C in HTO” J. Org. Chem. (2005) 70, 10581–10583.Google Scholar
- 30.Esaki, H.; Kurita, T.; Fujiwara, Y.; Maegawa, T.; Monguchi, Y.; Sajiki, H., “An Efficient Deuteration Method Catalyzed by Heterogeneous Platinum Group Metals”, J. Synth. Org. Chem., Jpn. (2007), 65, 1179–1190.Google Scholar
- 31.Sawama, Y.; Monguchi, Y.; Sajiki, H., ‘‘Efficient H–D Exchange Reactions Using Heterogeneous Platinum-Group Metal on Carbon–H2–D2O System’’, Synlett (Account), (2012) 23, 959–972.Google Scholar
- 32.Sajiki, H., “Development of Deuterium Labeling Method Based on the Heterogeneous Platinum Group Metal-Catalyzed C–H Activation”, J. Pharm. Soc. Jpn. (2013) 133, 1177–1193.Google Scholar
- 33.Mann, W. B.; Newell, W. C., “The Exchanges of Energy between a Platinum Surface and Hydrogen and Deuterium Molecules”, Proc. Roy. Soc., A (1937) 158, 397–403.Google Scholar
- 34.Coppock, J. B. M., “The Volume Coefficient of Expansion of Deuterium” Trans. Faraday Soc. (1935) 31, 913–914.Google Scholar
- 35.Knowlton, J. W.; Rossini, F. D., “Method and Apparatus for the Rapid Conversion of Deuterium Oxide into Deuterium”, J. Res. Nat. Bur. Stand. (1937) 19, 605–612.Google Scholar
- 36.Farkas, A.; Farkas, L.; Yudkin, J., “Decomposition of Sodium Formate by E. coli in the Presence of Heavy Water”, Proc. Roy. Soc. (1934) B115, 373–379.Google Scholar
- 37.von Hahn, H. E.; Peters, E., “Kinetics of Copper(II)- and Copper(I)-Catalyzed Deuterium Exchange in Sulfuric and Perchloric Acid Solutions” J. Phys. Chem. (1971) 75, 571–579.Google Scholar
- 38.Palibroda, N.; Grecu, E.; Mărginean, P., “Catalytic Activity of Ni—Cr2O3 in the II2–NH3 and H2–H2O Deuterium Exchange Reactions” Isotopenpraxis (1986) 22, 435–438.Google Scholar
- 39.El-Nour, F. A.; Belacy, N.; Abdel-Khalik, M.; Khalil, T.; Aly, H. F., “H/D Isotopic Exchange between Hydrogen and Water Vapour on Ni/Cr2O3/ThO2 Catalysts” Isotopenpraxis (1990) 26, 529–531.Google Scholar
- 40.Mochizuki, M.; Noda, S.; Morishima, T., “A Simple Method for Determination of Heavy Water by. Combined Use of Gas Chromatography and Platinum Catalyst”, Radioisotopes (1987) 36, 163–168.Google Scholar
- 41.Baba, A.; Nishikawa, M.; Eguchi, T., “Isotope Exchange Reaction on Li2ZrO3”, J. Nucl. Mater. (1997), 250, 29–35.Google Scholar
- 42.Yoshida, T.; Okano, T.; Saito, K.; Otsuka, S., “Activation of Water. 3. Oxidative Addition of Water to Rhodium(I) Hydrido Compounds and Application as Catalyst for Deuteration of Aromatic Hydrocarbons and Hydrogen with D2O”, Inorg. Chim. Acta. (1980) 44, L135–L136.Google Scholar
- 43.Collman, J. P.; Wagenknecht, P. S.; Hembre, R. T.; Lewis, N. S., “Dihydrogen Complexes of Metalloporphyrins: Characterization and Hydrogen-transfer Reactivity” J. Am. Chem. Soc. (1990) 112, 1294–1295.Google Scholar
- 44.Grundler, P. V.; Yazyev, O. V.; Aebischer, N.; Helm, L.; Laurenczy, G.; Merbach, A. E., “Kinetic Studies on the First Dihydrogen Aquacomplex, [Ru(H2)(H2O)5]2+: Formation under H2 Pressure and Catalytic H/D Isotope Exchange in Water”, Inorg. Chim. Acta. (2006) 359, 1795–1806.Google Scholar
- 45.Sajiki H., Kurita T., Esaki H., Aoki F., Maegawa T., Hirota K., ‘‘Complete Replacement of H2 by D2 via Pd/C-Catalyzed H/D Exchange Reaction’’, Org. Lett., (2004) 6, 3521–3523.Google Scholar
- 46.Kurita T., Aoki F., Mizumoto T., Maejima T., Esaki H., Maegawa T., Monguchi Y., Sajiki H., ‘‘Facile and Convenient Method of Deuterium Gas Generation Using a Pd/C Catalyzed H2–D2 Exchange Reaction and Its Application to Synthesis of Deuterium-Labeled Compounds’’, Chem. Eur. J., (2008) 14, 3371–3379.Google Scholar
- 47.Sajiki, H., “Selective Inhibition of Benzyl Ether Hydrogenolysis with Pd/C Due to the Presence of Ammonia, Pyridine and Ammonium Acetate”, Tetrahedron Lett., (1995) 36, 3465–3468.Google Scholar
- 48.Sajiki, H.; Hattori, K.; Hirota, K., “The Formation of a Novel Pd/C-Ethylenediamine Complex Catalyst: Chemoselective Hydrogenation without Deprotection of the O-Benzyl and N-Cbz Groups”, J. Org. Chem., (1998) 63, 7990–7992.Google Scholar
- 49.Sajiki, H.; Hirota, K., “A Novel Type of Pd/C-catalyzed Hydrogenation Using a Catalyst Poison: Chemoselective Inhibition of the Hydrogenolysis of O-Benzyl Protective Groups by the Addition of a Nitrogen-containing Base”, Tetrahedron (1998) 54, 13981–13996.Google Scholar
- 50.Sajiki, H.; Hirota, K., “Pd/C-catalyzed Chemoselective Hydrogenation in the Presence of a Phenolic MPM Protective Group Using Pyridine as a Catalyst Poison”, Chem. Pharm. Bull. (2003) 51, 320–324.Google Scholar
- 51.Mori, A.; Miyakawa, Y.; Ohashi, E.,; Haga, T.; Maegawa, T.; Monguchi, Y.; Sajiki, H., “Pd/C-Catalyzed Chemoselective Hydrogenation in the Presence of Diphenylsulfide”, Org. Lett. (2006) 8, 3279–3281.Google Scholar
- 52.Mori, A.; Mizusaki, T.; Miyakawa, Y.; Ohashi, E.,; Haga, T.; Maegawa, T.; Sajiki, H., “Chemoselective Hydrogenation Method Catalyzed by Pd/C Using Diphenylsulfide as a Reasonable Catalyst Poison”, Tetrahedron (2006) 62, 11925–11932.Google Scholar
- 53.Yabe, Y.; Yamada, T.; Nagata, S.; Sawama, Y.; Monguchi, Y.; Sajiki, H., “Development of Palladium on Boron Nitride Catalyst and Its Application to Semihydrogenation of Alkynes”, Adv. Synth. Catal. (2012) 354, 1264–1268.Google Scholar
- 54.Maegawa, T.; Akashi, A.; Esaki, H.; Aoki, F.; Sajiki, H.; Hirota K., “Efficient and Selective Deuteration of Phenylalanine Derivatives Catalyzed by Pd/C”, Synlett (2005) 845–847.Google Scholar
- 55.Maegawa, T.; Akashi, A.; Yaguchi, K.; Iwasaki, Y.; Shigetsura, M.; Monguchi, Y.; Sajiki, H., “Efficient and Practical Arene Hydrogenation by Heterogeneous Catalysts under Mild Conditions”, Chem. Eur. J. (2009) 6953–6963.Google Scholar
- 56.Hattori, T.; Ida, T.; Tsubone, A.; Sawama, Y.; Monguchi, Y.; Sajiki, H., “Facile Arene Hydrogenation under Flow Conditions Catalyzed by Rhodium or Ruthenium on Carbon”, Eur. J. Org. Chem.. (2015) 2492–2497.Google Scholar
- 57.Sawama, Y.; Mori, M.; Yamada, T.; Monguchi, Y.; Sajiki, H., “Hydrogen Self-Sufficient Arene Reduction to Cyclohexane Derivatives Using a Combination of Platinum on Carbon and 2-Propanol”, Adv. Synth. Catal. (2015) 3667–3670.Google Scholar