ChemCatChem

Cover image for Vol. 3 Issue 9

September 19, 2011

Volume 3, Issue 9

Pages 1369–1511

  1. Cover Picture

    1. Top of page
    2. Cover Picture
    3. Graphical Abstract
    4. News
    5. Review
    6. Highlights
    7. Concept
    8. Communications
    9. Full Papers
    10. Preview
    1. Cover Picture: Acid-Catalyzed Furfuryl Alcohol Polymerization: Characterizations of Molecular Structure and Thermodynamic Properties (ChemCatChem 9/2011) (page 1369)

      Dr. Taejin Kim, Dr. Rajeev S. Assary, Dr. Christopher L. Marshall, Dr. David J. Gosztola, Dr. Larry A. Curtiss and Prof. Peter C. Stair

      Article first published online: 14 SEP 2011 | DOI: 10.1002/cctc.201190037

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      The cover picture shows furfuryl alcohol polymerization, an important reaction during the mineral acid treatment in aqueous solution. The identities of molecular intermediates and reaction mechanisms during the polymerization were investigated by Raman spectroscopy and density functional theory calculations. Detailed thermochemistry of protonation of furfuryl alcohol, initiation of polymerization, and formation of conjugated dienes and diketonic species were predicted using computational methods. In the Full Paper on p. 1451 ff., Taejin Kim, Rajeev S. Assary et al. report that a strong aliphatic C[DOUBLE BOND]C band in the measured and calculated Raman spectra support the formation of conjugated diene structure, as a result of acid catalyzed furfuryl alcohol polymerization, compared to diketone structure. This combined experimental and theoretical investigation provides a detailed molecular understanding of polymerization during the conversion of biomass to platform chemicals for alternative fuels and industrial chemicals. The initials IACT stand for the Institute for Atom-efficient Chemical Transformations, an Energy Frontier Research Center funded by the U.S. Department of Energy.

  2. Graphical Abstract

    1. Top of page
    2. Cover Picture
    3. Graphical Abstract
    4. News
    5. Review
    6. Highlights
    7. Concept
    8. Communications
    9. Full Papers
    10. Preview
    1. Graphical Abstract: ChemCatChem 9/2011 (pages 1371–1377)

      Article first published online: 14 SEP 2011 | DOI: 10.1002/cctc.201190038

  3. News

    1. Top of page
    2. Cover Picture
    3. Graphical Abstract
    4. News
    5. Review
    6. Highlights
    7. Concept
    8. Communications
    9. Full Papers
    10. Preview
  4. Review

    1. Top of page
    2. Cover Picture
    3. Graphical Abstract
    4. News
    5. Review
    6. Highlights
    7. Concept
    8. Communications
    9. Full Papers
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    1. Catalytic Applications of Terpyridines and their Transition Metal Complexes (pages 1384–1406)

      Dr. Andreas Winter, Prof. Dr. George R. Newkome and Prof. Dr. Ulrich S. Schubert

      Article first published online: 19 JUL 2011 | DOI: 10.1002/cctc.201100118

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      More to this than meets the eye: The concept of terpyridine complexes and catalysis is reviewed critically with respect to applications in conventional organometallic catalysis, as well as in electro- and photcatalytic processes.

  5. Highlights

    1. Top of page
    2. Cover Picture
    3. Graphical Abstract
    4. News
    5. Review
    6. Highlights
    7. Concept
    8. Communications
    9. Full Papers
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    1. Highly Efficient and Selective Catalytic N-Alkylation of Amines with Alcohols in Water (pages 1407–1409)

      Dr. Jakob Norinder and Prof. Dr. Armin Börner

      Article first published online: 11 JUL 2011 | DOI: 10.1002/cctc.201100197

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      Getting fresh with iridium: Water is the solvent of choice in the N-alkylation of amines with iridium catalysts. Numerous secondary and tertiary amines can be assembled with excellent yields and chemoselectivity.

    2. Catalytic Hydrogenolysis of C[BOND]O Bonds in Aryl Ethers (pages 1410–1411)

      Dr. Mamoru Tobisu and Prof. Dr. Naoto Chatani

      Article first published online: 8 JUL 2011 | DOI: 10.1002/cctc.201100181

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      The first cut is the deepest: Hydrogenolysis is now applicable to the inert C(aryl)[BOND]O bonds in aryl ethers by using a soluble nickel complex ligated by N-heterocyclic carbenes. The protocol is potentially useful in the depolymerization of aryl ether-based biopolymers, such as lignin and coal. COD: 1,5-cyclooctadiene.

  6. Concept

    1. Top of page
    2. Cover Picture
    3. Graphical Abstract
    4. News
    5. Review
    6. Highlights
    7. Concept
    8. Communications
    9. Full Papers
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    1. Turnover Numbers and Soluble Metal Nanoparticles (pages 1413–1418)

      Prof. Dr. Alexandre P. Umpierre, Prof. Dr. Ernesto de Jesús and Prof. Dr. Jairton Dupont

      Article first published online: 24 JUN 2011 | DOI: 10.1002/cctc.201100159

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      Defects beat faces: It is proposed that, for soluble metal nanoparticles, ideally the turnover number (TON) is determined by using the titrated number of active catalytic sites. However, in the absence of reliable titration methods, the TON figures should be reported as the number of moles of reactants consumed per mol of soluble metal nanoparticle and the figures should also be corrected by the number of exposed surface atoms by using the metal atom's magic number approach.

  7. Communications

    1. Top of page
    2. Cover Picture
    3. Graphical Abstract
    4. News
    5. Review
    6. Highlights
    7. Concept
    8. Communications
    9. Full Papers
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    1. “Ligand-Consuming” Formation of Rhodium-Hydride Species from [Rh(OH)(cod)]2 Without any Additional Hydride Sources for Catalytic Olefin Isomerizations and Cyclobutene Synthesis (pages 1419–1421)

      Dr. Ken Motokura, Kohei Nakayama, Dr. Akimitsu Miyaji and Prof. Toshihide Baba

      Article first published online: 15 JUL 2011 | DOI: 10.1002/cctc.201100185

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      Multiple talents: A coordinatively unsaturated rhodium-hydride (Rh[BOND]H) species is formed from [Rh(OH)(cod)]2 without any additional hydride sources. The formation of the Rh[BOND]H species is confirmed by using 1H NMR analysis and hydride transfer reactions using deuterated olefins. This Rh[BOND]H species displays excellent catalytic performances in the isomerization of olefins.

    2. Generation of Reactive Oxygen Species on Au/TiO2 after Treatment with Hydrogen: Testing the Link to Ethanol Low-Temperature Oxidation (pages 1422–1425)

      Dr. Vladimir I. Sobolev, Olga A. Simakova and Prof. Konstantin Y. Koltunov

      Article first published online: 2 AUG 2011 | DOI: 10.1002/cctc.201100133

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      Reduction for oxidation: After preliminary treatment with molecular hydrogen, Au/TiO2 and Au/Al2O3 catalysts were able to induce O2 isotope exchange at mild conditions (−15 °C), which is believed to proceed through highly reactive surface oxygen species. However, the relative intensity of such an exchange is markedly different (see picture) and is in accordance with the diverse profiles of ethanol oxidation over gold nanoparticles supported on TiO2, Al2O3, and SiO2 matrixes.

    3. Supported Copper Catalysts Prepared from Colloidal Copper for the Water-Gas Shift Reaction (pages 1426–1430)

      Jiann-Horng Lin and Prof. Vadim V. Guliants

      Article first published online: 5 JUL 2011 | DOI: 10.1002/cctc.201100092

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      Al2O3-supported copper nanoparticles prepared from cetyltrimethylammonium bromide (CTAB) capped copper nanoparticles are effective water-gas shift catalysts. High activity can be explained by the presence of well-dispersed Cu nanoparticles on the alumina support due to strong interaction between CTAB and the Cu nanoparticles.

    4. Aromatic Amination of Aryl Chlorides Catalyzed by Ni Nanoparticles in Aliphatic Phosphonium-Based Ionic Liquids (pages 1431–1434)

      Inge Geukens, Dr. Jan Fransaer and Dr. Dirk E. De Vos

      Article first published online: 1 JUL 2011 | DOI: 10.1002/cctc.201100073

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      It doesn′t cost a dime: A nickel-based system that catalyzes the aromatic amination of aryl chlorides is presented. Starting from a simple Ni(II) salt, aliphatic phosphonium-based ionic liquids (ILs) were found to stabilize the nickel nanoparticles formed in situ during the reaction. The IL also enables successful recycling of the system after the reaction.

    5. Mesoporous Polymeric Support Retaining High Catalytic Activity of Polyoxotungstate for Liquid-Phase Olefin Epoxidation using H2O2 (pages 1435–1438)

      Dr. Sanjeev P. Maradur, Changbum Jo, Dr. Dae-Heung Choi, Kyeongyeon Kim and Prof. Ryong Ryoo

      Article first published online: 1 JUL 2011 | DOI: 10.1002/cctc.201100045

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      Tungstate turnpike: Mesoporous polymer-supported polyoxotungstate acts as an effective heterogeneous catalyst in the liquid-phase olefin epoxidation using H2O2. The effectiveness is attributed to the optimized hydrophobic/hydrophilic balance within the uniform mesoporous environment. Furthermore, the catalyst can be recycled without significant loss of activity.

    6. Palladium-Catalyzed Synthesis of Arylpropargyl Ethers (pages 1439–1441)

      Dr. Saravanan Gowrisankar, Dr. Helfried Neumann and Prof. Dr. Matthias Beller

      Article first published online: 10 JUN 2011 | DOI: 10.1002/cctc.201100075

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      Adamant about this: A variety of aryl and heteroaryl propargyl ethers are obtained in good to excellent yields from activated and non-activated aryl bromides and chlorides in the presence of a sterically hindered, air-stable ligand by using a general palladium-catalyzed synthesis. Our protocol complements the known syntheses for alkynyl aryl ethers and 2H-1-benzopyrans and should find further applications in organic synthesis.

    7. Interlayer-Expanded Microporous Titanosilicate Catalysts with Functionalized Hydroxyl Groups (pages 1442–1446)

      Prof. Feng-Shou Xiao, Dr. Bin Xie, Haiyan Zhang, Liang Wang, Dr. Xiangju Meng, Prof. Weiping Zhang, Prof. Xinhe Bao, Dr. Bilge Yilmaz, Dr. Ulrich Müller, Prof. Hermann Gies, Dr. Hiroyuki Imai, Prof. Takashi Tatsumi and Prof. Dirk De Vos

      Article first published online: 11 JUL 2011 | DOI: 10.1002/cctc.201100144

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      Simple as that: A novel crystalline microporous titanosilicate (Ti-COE-4) with functionalized hydroxyl groups and medium micropore size (0.55 nm) is successfully synthesized through dimethylsilylation and calcination. The synergism of hydroxyl groups with active Ti sites in Ti-COE-4 significantly improves its catalytic activities in oxidation reactions.

    8. Allylic and Benzylic Oxidation over CrIII-Incorporated Mesoporous Zirconium Phosphate with 100 % Selectivity (pages 1447–1450)

      Apurba Sinhamahapatra, Narottam Sutradhar, Sandip K. Pahari, Provas Pal, Dr. Hari C. Bajaj, Dr. Muthirulandi Jayachandran and Dr. Asit Baran Panda

      Article first published online: 26 JUL 2011 | DOI: 10.1002/cctc.201100148

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      Elite selection: The selective oxidation of allylic and benzylic compounds to the corresponding carbonyl compounds (enones), using H2O2 as oxidant and methanol as solvent over chromiumincorporated mesoporous zirconium phosphate, is evaluated.

  8. Full Papers

    1. Top of page
    2. Cover Picture
    3. Graphical Abstract
    4. News
    5. Review
    6. Highlights
    7. Concept
    8. Communications
    9. Full Papers
    10. Preview
    1. Acid-Catalyzed Furfuryl Alcohol Polymerization: Characterizations of Molecular Structure and Thermodynamic Properties (pages 1451–1458)

      Dr. Taejin Kim, Dr. Rajeev S. Assary, Dr. Christopher L. Marshall, Dr. David J. Gosztola, Dr. Larry A. Curtiss and Prof. Peter C. Stair

      Article first published online: 22 JUL 2011 | DOI: 10.1002/cctc.201100098

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      I′m with the band: The strong aliphatic C[DOUBLE BOND]C band (1654 cm−1) observed in the measured Raman spectra is crucial evidence to understand the polymerization reaction mechanism (see figure). The formation of a conjugated diene structure instead of a diketone structure is involved in the furfuryl alcohol polymerization reaction. The B3LYP level of theory also indicates that the formation of diene is preferred over the formation of diketone.

    2. Elucidating the Directing Effect of Lewis Acids on the Reaction Pathway in Formal [3+3] Cyclocondensation Reactions: A Comprehensive In Situ Spectroscopic Study (pages 1459–1468)

      Leif R. Knöpke, Sebastian Reimann, Dr. Anke Spannenberg, Prof. Dr. Peter Langer, Prof. Dr. Angelika Brückner and Dr. Ursula Bentrup

      Article first published online: 22 JUL 2011 | DOI: 10.1002/cctc.201100150

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      The Lewis acid makes the difference! Different spectroscopic methods (UV/vis, ATR-IR, and Raman) were applied in situ as well as ex situ to elucidate the mode of action of different Lewis acids in the [3+3] cyclization reaction of a 1,3-bis(silyloxy)-1,3-butadiene with a ketenacetale. The different interaction of two different Lewis acids with the ketenacetale was spectroscopically characterized and identified as the crucial step, which influences the subsequent reaction pathways.

    3. Stereoselective Oxidation of 1-Phenyl-1,2-propanediol Mediated by Microorganisms (pages 1469–1473)

      Rodrigo S. Martins, Dr. Dávila S. Zampieri, Prof. J. Augusto R. Rodrigues, Prof. Patrícia O. Carvalho and Prof. Paulo J. S. Moran

      Article first published online: 29 JUL 2011 | DOI: 10.1002/cctc.201100145

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      Rest, then have a go: The oxidation of (1R,2S)-1-phenyl-1,2-propanediol [(1S,2R)-1] using Baker's yeast gives (S)-1-phenyl-2-hydroxy-1-propanone (2) in 64 % yield and 93 % ee. Cells resting time and acetone (5 vol %) are used to improve the bio-oxidation. The oxidation is probably realized by an oxidase, which depends on molecular oxygen. A kinetic resolution experiment gave (1S,2R)-1 in>99 % ee from (±)-anti-1.

    4. Hydrocracking of Anthracene to Ethyl Biphenyl Promoted by Coupling Supercritical Water and Cracking Catalysts (pages 1474–1479)

      Dr. Honglei Fan, Prof. Buxing Han, Prof. Tao Jiang, Jin Guo, Dr. Qian Wang, Dr. Yan Cheng and Dr. Suxiang Wu

      Article first published online: 26 JUL 2011 | DOI: 10.1002/cctc.201100142

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      A catalyst to keep you from cracking up: The hydrocracking of anthracene was catalyzed by NiFe/HZSM-5 to produce ethyl biphenyl in yields as high as 34 % in the presence of water. Water in the reaction system could enhance C[BOND]C bond breakage and promote the isomerization and hydrogen transfer reactions. The liquid product yields in the hydrocracking of the Daqing residue oil could also increase in the presence of water, which is consistent with the hydrocracking of anthracene.

    5. Influence of Potassium on the Synthesis of Methanethiol from Carbonyl Sulfide on Sulfided Mo/Al2O3 Catalyst (pages 1480–1490)

      Dr. Oliver Y. Gutiérrez, Christoph Kaufmann and Dr. Johannes A. Lercher

      Article first published online: 26 JUL 2011 | DOI: 10.1002/cctc.201100124

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      Potassium is the answer: Adding potassium to the MoS2 catalyst is necessary to achieve a high activity and selectivity from CH3SH from H2S-containing syngas. Acting as adsorption centers, the surface potassium cations promote the disproportionation of carbonyl sulfide to CO2 and CS2, but hinder the O[BOND]C and C[BOND]S bond cleavage, which is the preferred reaction on the sulfur vacancies of MoS2.

    6. Intramolecular CH Oxidative N-Allylation of C-Homoallylhydrazones to 5-Vinyl-2-pyrazolines Catalyzed by the [Pd(OAc)2]/BIMINAP System (pages 1491–1495)

      Dr. Thanh-Tung Dang, Dr. Ibrahim Abdellah, Dr. Yves Canac and Prof. Remi Chauvin

      Article first published online: 28 JUL 2011 | DOI: 10.1002/cctc.201100108

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      The BIMINAP ligand makes it possible! 5-vinyl-2-pyrazolines were obtained from C-homoallylhydrazones through Pd catalyzed intramolecular C[BOND]H oxidative allylic amination by using the atropochiral electron-poor BIMINAP ligand. BIMINAP=formal contraction of the acronyms BIMIP=2,2′-bis(diphenylphosphino)-1,1′-bibenzimidazole and BINAP=2,2′-bis(diphenylphosphino)-1,1′-binaphthyl.

    7. A Palladium-Catalyzed Multicascade Reaction: Facile Low-Temperature Hydrogenolysis of Activated Nitriles and Related Functional Groups (pages 1496–1502)

      Aaron J. Yap, Dr. Bun Chan, Dr. Alexander K. L. Yuen, Dr. Antony J. Ward, Prof. Anthony F. Masters and Prof. Thomas Maschmeyer

      Article first published online: 8 JUL 2011 | DOI: 10.1002/cctc.201100076

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      Control your children without being harsh: Herein we present a simple system for the otherwise difficult hydrogenolysis of nitriles, imines, and amines. This system can achieve high yields without using harsh conditions. Investigations into the mechanics of this system aid our understanding of what has been thought to be a simple process.

    8. High Ethylene Production through Oxidative Dehydrogenation of Ethane Membrane Reactors Based on Fast Oxygen-Ion Conductors (pages 1503–1508)

      Dr.  M. Pilar Lobera, Sonia Escolástico and Dr. José M. Serra

      Article first published online: 15 JUL 2011 | DOI: 10.1002/cctc.201100055

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      Straight on through to the other side: Catalytic membrane reactors based on solid-state oxygen conductors enabled us to achieve high ethylene productivity through the oxidative dehydrogenation of ethane. The selectivity is maximized by preventing the direct contact of molecular oxygen and hydrocarbons, by properly selecting the temperature and inlet gas flow rates, and by using methane as a diluting agent.

  9. Preview

    1. Top of page
    2. Cover Picture
    3. Graphical Abstract
    4. News
    5. Review
    6. Highlights
    7. Concept
    8. Communications
    9. Full Papers
    10. Preview
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      Preview: ChemCatChem 10/2011 (page 1511)

      Article first published online: 14 SEP 2011 | DOI: 10.1002/cctc.201190040

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