Highly Efficient Gold (I) Complex Catalyst for Hydration of Alkynes

Gold 2003
Eiichiro Mizushima, Masato Tanaka,
Abstract Hydration of carbon-carbon unsaturated bonds is one of the environmentally benign routes to carbon-oxygen compounds. In this category, hydration of alkynes to give carbonyl compounds is well known reaction and has been extensively studied. Acid-catalysis is the most conventional method, while it is applicable only to electron rich acetylenes to give corresponding methylketones in satisfactory yields.[1,2] For the hydration of simple alkynes, another catalysts such as mercury(II) salts were required,[3] which is inconsistent with the guiding principle of Green Chemistry.[4] In this context, various kinds of transition metal complex catalysts such as ruthenium (II), ruthenium (III), rhodium, platinum, gold (III), and others have been attempted.[5] However, catalyst efficiency of these catalyst systems is still insufficient. For example, in the hydration of 3-pentyn-1-ol catalyzed by cis-PtCl2(TPPTS)2 [TPPTS = P(m-C6H4SO3Na)3], initial turnover frequency (TOF) up to 550 /h has been claimed, while the overall TOF remains about 100 /h.[6] Recently, it was reported that gold (I) species effectively catalyzes addition of methanol to simple acetylenes.[7] In a patent application by the same authors, propargyl alcohol was claimed to be hydrated by the same catalyst system.[8] We have found out that gold (I)-acid systems efficiently catalyze the hydration of simple acetylenes in methanol as a solvent. The efficiency was two orders of magnitude higher than reported transition metal catalyst systems.
1-Octyne (1 mmol), (Ph3P)AuCH3 (0.01 mmol, 1 mol %) and concentrated sulfuric acid (0.5 mmol, 50 mol %) were mixed in aqueous methanol (1.5 ml, methanol : H2O = 2 : 1 v/v) and the mixture was heated for 1 h at 70 °C to afford the Markovnikov hydration product, 2-octanone, in 95% yield without anti-Markovnikov hydration and possible methanol addition.[7] In the absence of either the Au catalyst or sulfuric acid, the reaction did not proceed at all.
The reaction was significantly affected by the reaction media. Without using any solvent (otherwise the same conditions as above), the reaction did not furnish 2-octanone. The use of 2-propanol (71%), dioxane (56%), acetonitrile (53%) or THF (11%) gave lower yields as shown in parentheses, and the use of dichloromethane, DMF or toluene as solvent resulted in even lower yields. As a consequence, the use of methanol was the best choice for this reaction.
The addition of appropriate ligands significantly enhanced the catalytic performance, which enabled to minimize the quantity of the precious catalyst. When the reaction was carried out with 0.01 mol% catalyst (reaction conditions: (Ph3P)AuCH3 0.002 mmol, sulfuric acid 0.5 mmol, 1-octyne 20 mmol, water 1 ml, methanol 10 ml, 70 °C, 1 h), the yield of 2-octanone was 35% (TOF = 3500 /h). The yield was dramatically increased to 99% (TOF = 9900 /h) under atmospheric CO or to 90 % (TOF = 9000 /h) with the addition of P(OPh)3. The ligand effect is ambiguous at this time. It seemed to be associated with the stability of the catalyst. The reactions without ligand addition occasionally resulted in the catalyst deterioration, as visualized by metallic particle precipitation. However, in the presence of CO or phosphites, the particle formation was not evident any more by sight.
The other acid co-catalysts including CF3SO3H, CH3SO3H and H3PW12O40 also resulted in extremely high performance even in the absence of the coordinative additives. A reaction of 1-octyne using only 0.005 mol% of the gold catalyst, under otherwise identical conditions as before, formed 2-octanone in 70% yield (TOF = 14000 /h) under N2, and in 78% yield (TOF = 15600 /h) under CO.
This catalytic procedure could be applied to various alkynes. Both aliphatic and aromatic terminal alkynes including those bearing functionalities such as alkoxy, cyano, chloro, and olefinic groups were all hydrated under similar reaction to give corresponding methyl ketones. Ethynylcyclohexene and hexynonitrile reacted at the acetylenic groups remaining olefinic and cyano groups intact. Propargylic alcohols gave the mixture of methyl ketones and alpha,beta-unsaturated aldehydes which means anti-Markovnikov addition somewhat taking place. In the reactions of substituted phenylacetylenes, electronegative groups decreased the reactivity suggesting that the reaction mechanism is electrophilic.


References
[1] For example, R. C. Larock, W. W. Leong in Comprehensive Organic Synthesis, Vol. 4 (Eds.: B. M. Trost, I. Fleming, M. F. Semmelhack), Pergamon Press, Oxford, 1991, p. 269.
[2] A. D. Allen, Y. Chiang, A. J. Kresge, T. T. Tidwell, J. Org. Chem. 1982, 47, 775 and references cited there in.
[3] V. Jäger, H. G. Viehe in Houben-Weyl, Methoden der Organiche Chemie, Vol. 5/2a (Ed.: E. Müller), Thieme Verlag, Stuttgart, 1977, p.726.
[4] P. T. Anastas and J. C. Warner, “Green Chemistry: Theory and Practice,” Oxford University Press, Oxford, 1998.
[5] a) M. Tokunaga, T. Suzuki, N. Koga, T. Fukushima, A. Horiuchi, Y. Wakatsuki, J. Am. Chem. Soc. 2001, 123, 11917; b) D. B. Grotjahn, C. D. Incarvito, A. L. Rheingold, Angew. Chem. Int. Ed. 2001, 40, 3884; c) Y. Fukuda, K. Utimoto, J. Org. Chem., 1991, 56, 3729 and references cited there in.
[6] L. W. Francisco, D. A. Moreno, J. D. Atwood, Organometallics 2001, 20, 4237.
[7] J. H. Teles, S. Brode, M. Chabanas, Angew. Chem. Int. Ed. 1998, 37, 1415.
[8] J. H. Teles, M. Schulz (BASF AG), WO-A1 9721648, 1997 [Chem. Abstr. 1997, 127, 121499].


Keywords: catalyst, Water, Ketone, Carbonyl Compounds, Alkynes, Addition, Gold Complex, Hydration
Full Access to Technical Paper
PDF version for $20.00
Other papers from Gold 2003
Search
Sort By:  Relevance
Showing results 1 - 50 of 101
Text
Summary: -
Proceedings: Gold 2003
Author(s): Elma van der Lingen, Madeleine du Toit, Cristian Cretu, Lizelle Glaner
Keywords: hard, gold alloys, Strengthening, age hardening
Year: 2003
Text
Summary: -
Proceedings: Gold 2003
Author(s): Inga Tuzovskaya, Alexey Pestryakov, Valery Gurin, Andrey Simakov, Miguel Avalos, Mario Farias
Year: 2003
Text
Summary: -
Proceedings: Gold 2003
Year: 2003
Text
Proceedings: Gold 2003
Keywords: gold-platinum alloys, ethylene glycol, Heat treatment, Electro-oxidation, Kirkendall effect, Cyclic Voltammetry
Year: 2003
Text
Proceedings: Gold 2003
Author(s): Nina Bogdanchikova, Bernard E. Nieuwenhuys
Keywords: Oxidation, Methane, oxide, additive, Alkali, Hydrocarbons, propene
Year: 2003
Text
Summary: -
Proceedings: Gold 2003
Author(s): Michael Cortie, Herman Schwarzer, Stephen Roberts, Gary Pattrick
Keywords: Gold Catalysis, Intermetallic compounds, AuAl2, CO oxidation
Year: 2003
Text
Proceedings: Gold 2003
Author(s): Andreas Zielonka, Renate Freudenberger
Keywords: electroforming, electrodeposition/electroplating, implant, Gold, medical application
Year: 2003
Text
Summary: -
Proceedings: Gold 2003
Author(s): Neil E Izatt, Steven R Izatt, Ronald L Bruening
Year: 2003
Text
Proceedings: Gold 2003
Author(s): Jeanette Hohls, Cristian Cretu, Lesley Cornish, Daven Compton
Keywords: Fecraloy, oxidation resistance, Gold
Year: 2003
Text
Summary: -
Proceedings: Gold 2003
Author(s): Elma van der Lingen, Stella Valenzuela, Don Martin
Keywords: mesoporous, nanoporous, ultracapacitor
Year: 2003
Text
Proceedings: Gold 2003
Year: 2003
Text
Summary: -
Proceedings: Gold 2003
Year: 2003
Text
Summary: -
Proceedings: Gold 2003
Author(s): Tim W Ellis
Year: 2003
Text
Summary: -
Proceedings: Gold 2003
Author(s): Stephan Roberts, Elma van der Lingen, Herman Schwarzer
Keywords: spongy gold, selective catalytic reduction, NOx
Year: 2003
Text
Summary: -
Proceedings: Gold 2003
Year: 2003
Text
Summary: -
Proceedings: Gold 2003
Year: 2003
Text
Proceedings: Gold 2003
Author(s): Shawn D. Lin, Bernard E. Nieuwenhuys
Keywords: nitrous oxide, Oxidation, Alkali, Ammonia, nitric oxide, Reduction, oxide, selectivity
Year: 2003
Text
Proceedings: Gold 2003
Author(s): Ko-ichi Sugawara
Keywords: electron microscopy, nanoparticle, Morphology, Computer simulation, Image analysis, cluster science, Statistics
Year: 2003
Text
Proceedings: Gold 2003
Author(s): Bob Stewart, Carel Wreesmann, Geoff Smith
Keywords: Plants, Induced hyperaccumulation, Gold, Phytomining, nanoparticles
Year: 2003
Text
Summary: -
Proceedings: Gold 2003
Year: 2003
Text
Proceedings: Gold 2003
Author(s): Prati Laura, Rossi Michele
Keywords: gold on carbon, liquid phase oxidation
Year: 2003
Text
Proceedings: Gold 2003
Author(s): Uzi Landman
Keywords: gold nanoclusters, oxidation reactions, relativistic effects, nanocatalysis
Year: 2003
Text
Proceedings: Gold 2003
Author(s): Masayuki Kanehara, Etsushi Kodzuka, Yasunori Oumi, Tsuneji Sano
Keywords: gold nanoparticle, self-assembly
Year: 2003
Text
Summary: -
Proceedings: Gold 2003
Year: 2003
Text
Summary: -
Proceedings: Gold 2003
Author(s): Suresh Bharagva, Martin Bennett
Keywords: Ab Initio Calculations, Gold Complexes, Cyclometallated, Heterovalent complexes, Carbon-carbon coupling, Binuclear
Year: 2003
Text
Proceedings: Gold 2003
Author(s): Yutaka Okinaka
Year: 2003
Text
Summary: -
Proceedings: Gold 2003
Author(s): Sandrine Arrii, Albert Renouprez
Keywords: supported catalysts, CO oxidation, support effects, Gold, laser vaporization
Year: 2003
Text
Summary: -
Proceedings: Gold 2003
Author(s): Elena Cerrada, Ana Ade, Maria Contel
Keywords: Dipolar cycloaddition, Gold, nitrones, organometallics
Year: 2003
Text
Summary: -
Proceedings: Gold 2003
Author(s): Aalbert Zwijnenburg, Wim G Sloofs, Jacob A Moulijn
Year: 2003
Text
Summary: -
Proceedings: Gold 2003
Author(s): Cris Kostmann, Gunter Stephani
Year: 2003
Text
Summary: -
Proceedings: Gold 2003
Year: 2003
Text
Summary: -
Proceedings: Gold 2003
Author(s): Elma Van der Lingen, Michael Cortie
Keywords: Gold Catalysis, zinc oxide, CO oxidation
Year: 2003
Text
Summary: -
Proceedings: Gold 2003
Keywords: Cyclic Voltammetry, Surface Active Sites, Electrochemistry, Surface, Metastability, RHE, Electrocatalysis, Gold, Premonolayer Oxidation, Cyclic redox mediators, Active state electrochemistry, Protruding surface atoms, Metastable Surface States
Year: 2003
Text
Proceedings: Gold 2003
Author(s): Peter CLAUS, Herbert HOFMEISTER, Christian MOHR
Keywords: nanoparticles, hydrogenation, indentification of active sites, catalysis by gold, real structure
Year: 2003
Text
Summary: -
Proceedings: Gold 2003
Author(s): Uwe Manz
Keywords: Electroless, Plating, Barrel, Electronics
Year: 2003
Text
Summary: -
Proceedings: Gold 2003
Author(s): P Centomo, D Ferrari, W Meyer-Zaika, G Schmid
Year: 2003
Text
Summary: The preparation of a vapour compound sensor is reported. It is based on a vapochromic organometallic gold compound and optical fiber. The results are comapred with other reported VO«S sensor
Proceedings: Gold 2003
Author(s): Candido Bariain, Elena Cerrada, Julian Garrido, Ignacio R Matias, Mariano Laguna
Keywords: vapochromic, Gold, organometallic, environmental sensor
Year: 2003
Text
Proceedings: Gold 2003
Author(s): Gilbert P. van Berkel, Bernard E. Nieuwenhuys
Keywords: chemisorption, Au(100), nitric oxide, phase transition
Year: 2003
Text
Proceedings: Gold 2003
Author(s): V. La Parola, B. Pawelec, J. L. G. Fierro
Year: 2003
Text
Summary: -
Proceedings: Gold 2003
Author(s): Andrea Beck, Gabor Peto, Csaba Daroczi, Krisztina Frey
Keywords: Au/SiO2/Si(100), Size dependence, UPS, support effect, TEM, AFM, CO oxidation
Year: 2003
Text
Summary: -
Proceedings: Gold 2003
Author(s): Fernando Canales, Silvia Canales, Olga Crespo, Antonio Laguna, Carmen Larraz
Keywords: aurophilic interactions, polynuclear, chalcogenide, Gold
Year: 2003
Text
Summary: -
Proceedings: Gold 2003
Keywords: plasmon resonance, colour, crystal structure, melting point, band gap, nanotechnology
Year: 2003
Text
Summary: -
Proceedings: Gold 2003
Author(s): Christopher Corti
Year: 2003
Text
Summary: -
Proceedings: Gold 2003
Author(s): David James, Lucy Millard, Jane Greaves, Jorge Soares
Year: 2003
Text
Summary: -
Proceedings: Gold 2003
Year: 2003
Text
Summary: -
Proceedings: Gold 2003
Author(s): Mihaly Hegedus
Year: 2003
Text
Proceedings: Gold 2003
Author(s): Kageeporn Wongpreedee, Alan M Russell
Keywords: Gold, interconnection wire, transformation, Kinetics, Composite, Dislocation
Year: 2003
Text
Proceedings: Gold 2003
Author(s): Chih-Huey Lin, Hsin-Yen Tsai, Chih-Huey Lin, Hsin-Yen Tsai
Keywords: Au, Al2O3, Au, Al2O3, impregnation, NH4OH treatment, NH4OH treatment, impregnation
Year: 2003
Text
Summary: -
Proceedings: Gold 2003
Author(s): Aya Kawamoto, Masakazu Date, Susumu Tsubota, Mitsutaka Okumura, Masatake Haruta
Year: 2003
Text
Summary: -
Proceedings: Gold 2003
Author(s): Matthew Hall, Albert F Carley, Graham John Hutchings,
Keywords: XPS, Au - Fe catalysts, Low temperature CO oxidation
Year: 2003