ChemCatChem

Cover image for Vol. 5 Issue 5

Special Issue: Homogeneous Catalysis

May 2013

Volume 5, Issue 5

Pages 1037–1210

  1. Cover Pictures

    1. Top of page
    2. Cover Pictures
    3. Editorial
    4. Graphical Abstract
    5. News
    6. Minireview
    7. Highlights
    8. Communications
    9. Full Papers
    1. You have free access to this content
      Cover Picture: Gold(I)-Catalyzed Domino Reaction of Allyl 2-en-4-ynyl Ethers to 1,3,6-Trien-4-yl Ketones (ChemCatChem 5/2013) (page 1037)

      Prof. Dr. A. Stephen K. Hashmi, Dipl.-Chem. Katharina Graf, Dr. Martin Ackermann and Dr. Frank Rominger

      Article first published online: 26 APR 2013 | DOI: 10.1002/cctc.201390018

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      Golden metamorphose! The cover picture shows a linear unsaturated molecule, which in the presence of a gold catalyst rearranges to a complicated branched product, an isomerization involving an oxygen atom transfer. This resembles the fascinating metamorphose of a caterpillar to a butterfly. In their Full Paper on p. 1200 ff., A. S. K. Hashmi, K. Graf et al. report that this conversion proceeds in a highly diastereoselective manner. A complex cascade involving activation by π coordination of gold, a [3,3]-sigmatropic rearrangement, and an electrocyclic ring opening is suggested as the mechanism of this conversion.

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      Inside Cover: Ring Expansions Within the Gold-Catalyzed Cycloisomerization of O-Tethered 1,6-Enynes. Application to the Synthesis of Natural-Product-like Macrocycles (ChemCatChem 5/2013) (page 1038)

      Dr. Antoine Simonneau, Dr. Youssef Harrak, Louis Jeanne-Julien, Dr. Gilles Lemière, Dr. Virginie Mouriès-Mansuy, Dr. Jean-Philippe Goddard, Prof. Dr. Max Malacria and Prof. Dr. Louis Fensterbank

      Article first published online: 26 APR 2013 | DOI: 10.1002/cctc.201390019

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      Nature's first green is gold The cover picture shows the gold(I)-catalyzed cycloisomerization of O-tethered 1,6-enynes, which proceeds via fused tricyclic compounds with a dihydropyran moiety. As described in their Communication on p. 1096 ff., L. Fensterbank et al. continue this ring-expansion with a two-step sequence for the transformation of the cyclized compounds into valuable ketomacrolactones, with a motif that echoes natural products. And all this in the golden surroundings of Paris!

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      Inside Back Cover: Palladium(II) Complexes with Small N-Heterocyclic Carbene Ligands as Highly Active Catalysts for the Suzuki–Miyaura Cross-Coupling Reaction (ChemCatChem 5/2013) (page 1211)

      Dr. Michał S. Szulmanowicz, Dr. Andrzej Gniewek, Dr. Wojciech Gil and Prof. Dr. Anna M. Trzeciak

      Article first published online: 26 APR 2013 | DOI: 10.1002/cctc.201390022

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      Palladium double act he cover picture shows different forms of palladium catalyst present in the Suzuki–Miyaura reaction mixture. In their Full Paper on p. 1152 ff., A. M. Trzeciak et al. describe the use of palladium complexes of the formula [Pd(NHC)2X2] (NHC[DOUBLE BOND]N-heterocyclic carbene) as catalyst precursors to form Pd0NHC complexes and Pd0 nanoparticles. All of these species are involved in the catalytic cycle leading to 2-methylbiphenyl as a reaction product.

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      Back Cover: Synthesis of Poly(silyl ether)s by Rhodium(I)–NHC Catalyzed Hydrosilylation: Homogeneous versus Heterogeneous Catalysis (ChemCatChem 5/2013) (page 1212)

      Guillermo Lázaro, Dr. Manuel Iglesias, Dr. Francisco J. Fernández-Alvarez, Dr. Pablo J. Sanz Miguel, Prof. Jesús J. Pérez-Torrente and Prof. Luis A. Oro

      Article first published online: 26 APR 2013 | DOI: 10.1002/cctc.201390023

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      Rhodium-catalyzed polymerization goes heavyweightThe cover picture shows a neutral rhodium(I) N-heterocyclic carbene hydrosilylation catalyst immobilized on the surface of MCM-41. In their Full Paper on p. 1133 ff., F. J. Fernández-Alvarez, L. A. Oro et al. describe how these rhodium-containing materials catalyze the preparation of poly(silyl ether)s by hydrosilylation. These results show that the immobilized catalysts provide polymers with higher average molecular weight than those obtained by using the corresponding homogenous systems, which could be attributed to a confinement effect exerted by the channels of MCM-41.

  2. Editorial

    1. Top of page
    2. Cover Pictures
    3. Editorial
    4. Graphical Abstract
    5. News
    6. Minireview
    7. Highlights
    8. Communications
    9. Full Papers
    1. You have free access to this content
      The International Symposium on Homogeneous Catalysis (pages 1039–1040)

      Prof. Phillipe Kalck and Prof. Rinaldo Poli

      Article first published online: 26 APR 2013 | DOI: 10.1002/cctc.201300236

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      Catalysis à la carte: Based on the International Symposium on Homogeneous Catalysis (ISHC), this Special Issue has a particular focus on homogeneous catalysis. Organometallic, supramolecular, bioinspired, coordination, and organocatalysis can all be found in this great collection of articles.

  3. Graphical Abstract

    1. Top of page
    2. Cover Pictures
    3. Editorial
    4. Graphical Abstract
    5. News
    6. Minireview
    7. Highlights
    8. Communications
    9. Full Papers
    1. Graphical Abstract: ChemCatChem 5/2013 (pages 1043–1049)

      Article first published online: 26 APR 2013 | DOI: 10.1002/cctc.201390020

  4. News

    1. Top of page
    2. Cover Pictures
    3. Editorial
    4. Graphical Abstract
    5. News
    6. Minireview
    7. Highlights
    8. Communications
    9. Full Papers
  5. Minireview

    1. Top of page
    2. Cover Pictures
    3. Editorial
    4. Graphical Abstract
    5. News
    6. Minireview
    7. Highlights
    8. Communications
    9. Full Papers
    1. Phosphine Organocatalysis in the Synthesis of Natural Products and Bioactive Compounds (pages 1055–1065)

      Dr. Catherine Gomez, Dr. Jean-François Betzer, Dr. Arnaud Voituriez and Dr. Angela Marinetti

      Article first published online: 12 OCT 2012 | DOI: 10.1002/cctc.201200442

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      From all natural to bioactive: This review shows that organocatalytic methods based on the use of nucleophilic phosphorus catalysts have been successfully applied as key steps in the formal or total synthesis of complex natural products. These methods also afford suitable tools for the constitution of either focused or diversity-oriented-synthesis inspired libraries of small molecules for biological screening.

  6. Highlights

    1. Top of page
    2. Cover Pictures
    3. Editorial
    4. Graphical Abstract
    5. News
    6. Minireview
    7. Highlights
    8. Communications
    9. Full Papers
    1. Chiral Cyclopentadienyl-type Ligands: a New Breakthrough for Asymmetric C[BOND]H Functionalisation (pages 1067–1068)

      Dr. Jean-Baptiste Sortais and Prof. Dr. Christophe Darcel

      Article first published online: 7 MAR 2013 | DOI: 10.1002/cctc.201200874

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      Ligand breakthrough: Using a well-designed chiral cyclopentadienyl rhodium complex as the catalyst, an efficient asymmetric C[BOND]H bond functionalization/cyclization was performed at RT in the presence of a catalytic amount of dibenzoylperoxide (DBPO) leading to tetrahydroiso-quinolinone derivatives with moderate to good yields and very good enantiomeric ratios.

    2. Asymmetric Copper-catalyzed 1,4-Additions and Allylic Substitutions with Nucleophiles Formed by the Hydrometalation of Alkenes (pages 1069–1071)

      Dr. Radovan Šebesta

      Article first published online: 25 MAR 2013 | DOI: 10.1002/cctc.201200926

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      From pots and pans to hydrometalation: Hydrometalation reactions using boron and zirconium hydrides transform alkenes into useful alkylmetal nucleophiles. These nucleophiles can be employed in the copper-catalyzed 1,4-additions to α,β-unsaturated carbonyl compounds or allylic substitutions. Important advances have been achieved recently, which enabled also enantioselective versions of these transformations.

    3. Improving the Efficiency of the Hydrogenation of Carbonates and Carbon Dioxide to Methanol (pages 1072–1074)

      Dr. Yuehui Li, Dr. Kathrin Junge and Prof. Dr. Matthias Beller

      Article first published online: 12 MAR 2013 | DOI: 10.1002/cctc.201300013

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      On the way to a green carbon cycle: Ding and co-workers developed the highly efficient catalyst 1 for the hydrogenation of cyclic carbonates to diols and methanol (TON up to 87 000) by modification of the industrially applied omega process.

  7. Communications

    1. Top of page
    2. Cover Pictures
    3. Editorial
    4. Graphical Abstract
    5. News
    6. Minireview
    7. Highlights
    8. Communications
    9. Full Papers
    1. A Tertiary Phosphonium Salt as a Promoter for the Hydrogenation of CO (pages 1075–1078)

      Dr. Jan H. Blank, Dr. Robert Hembre, Dr. James Ponasik and Prof. David J. Cole-Hamilton

      Article first published online: 14 SEP 2012 | DOI: 10.1002/cctc.201200176

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      A big promotion: One reason for the irreproducibility that is sometimes found in hydrogenation reactions of CO catalysed by [Ru3(CO)12] in molten [PBu4]Br is the possible presence of [HPBu3]Br, which acts as a promoter by providing a source of HBr.

    2. Direct Amidation of Aldehydes with Primary Amines under Mild Conditions Catalyzed by Diolefin-Amine–RhI Complexes (pages 1079–1083)

      Rafael E. Rodríguez-Lugo, Dr. Mónica Trincado and Prof. Dr. Hansjörg Grützmacher

      Article first published online: 12 OCT 2012 | DOI: 10.1002/cctc.201200495

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      Rhodium teaches toleration: The diolefin-amine–RhI complex [Rh(OTf)(trop2NH)(PPh3)] (see scheme) is an effective pre-catalyst for the amidation of a wide range of aldehydes with primary amines. The corresponding amides are obtained in good-to-excellent yields under very mild reactions conditions and a variety of functional groups are tolerated.

    3. Supramolecular Ligands in Gold(I) Catalysis (pages 1084–1087)

      Dr. Rafael Gramage-Doria, Rosalba Bellini, Jeroen Rintjema and Prof. Dr. Joost N. H. Reek

      Article first published online: 25 OCT 2012 | DOI: 10.1002/cctc.201200541

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      Golden (I): A supramolecular ligand–template strategy is applied to gold(I) catalysis. The supramolecular ligands, formed from a phosphoramidite backbone and two templates, display different regioselectivity in the hydroalkoxylation of allenes compared to non-supramolecular analogues. Based on these findings, the catalytic activity of gold(I) complexes could be tunable at a supramolecular level.

    4. Switching the Lactide Polymerization Activity of a Cerium Complex by Redox Reactions (pages 1088–1091)

      Andreas Sauer, Jean-Charles Buffet, Thomas P. Spaniol, Haruki Nagae, Prof. Kazushi Mashima and Prof. Jun Okuda

      Article first published online: 20 DEC 2012 | DOI: 10.1002/cctc.201200705

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      The old switcheroo! The ring-opening polymerization activity towards meso-lactide significantly differs when cerium complexes with two bis(phenolate) ligands (OSSO type) change their oxidation state from +4 to +3. This switch can be performed in situ by chemical reduction or oxidation of the catalyst. The redox switching is possible up to three times in a row. PLA=polylactide.

    5. Fe-Catalyzed Olefin Epoxidation with Tridentate Non-Heme Ligands and Hydrogen Peroxide as the Oxidant (pages 1092–1095)

      Dr. Bernabé F. Perandones, Dr. Enrique del Río Nieto, Dr. Cyril Godard, Prof. Sergio Castillón, Dr. Pilar De Frutos and Prof. Carmen Claver

      Article first published online: 25 FEB 2013 | DOI: 10.1002/cctc.201200764

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      Do it with a tridentate ligand: The use of readily available tridentate nitrogen donor ligands gives highly active and selective Fe catalysts in the epoxidation of a series of alkenes.

    6. Ring Expansions Within the Gold-Catalyzed Cycloisomerization of O-Tethered 1,6-Enynes. Application to the Synthesis of Natural-Product-like Macrocycles (pages 1096–1099)

      Dr. Antoine Simonneau, Dr. Youssef Harrak, Louis Jeanne-Julien, Dr. Gilles Lemière, Dr. Virginie Mouriès-Mansuy, Dr. Jean-Philippe Goddard, Prof. Dr. Max Malacria and Prof. Dr. Louis Fensterbank

      Article first published online: 9 NOV 2012 | DOI: 10.1002/cctc.201200484

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      Goldenyne: O-tethered 1,6-enynes that contain a strained ring at the 3 position can cycloisomerize upon cationic gold(I) catalysis through a ring-expansion process. A two-step sequence allows the transformation of the cyclized compounds into ketomacrolactones, which are reminiscent of natural products.

  8. Full Papers

    1. Top of page
    2. Cover Pictures
    3. Editorial
    4. Graphical Abstract
    5. News
    6. Minireview
    7. Highlights
    8. Communications
    9. Full Papers
    1. Stoichiometric C[BOND]H Bond Cleavage Reaction in a Bis(carboxylato)ruthenium(II) Complex and Its Application to the Catalytic H–D Exchange Reaction of Carboxylic Acids (pages 1101–1115)

      Prof. Masafumi Hirano, Ryo Fujimoto, Kohei Hatagami, Nobuyuki Komine and Prof. Sanshiro Komiya

      Article first published online: 6 MAR 2013 | DOI: 10.1002/cctc.201200686

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      No carboxylato ligand, no activation: A series of bis(carboxylato)ruthenium(II) complexes are prepared. An internal stereospecific C[BOND]H bond cleavage reaction occurs to give a ruthenalactone through prior dissociation of a PMe3 ligand. Here, a coordinated carboxylato ligand acts as an internal base, and a typical proton acceptor such as a proton sponge does not assist the reaction.

    2. Resorcinarene-Functionalised Imidazolium Salts as Ligand Precursors for Palladium-Catalysed Suzuki–Miyaura Cross-Couplings (pages 1116–1125)

      Dr. Neslihan Şahin, Dr. David Sémeril, Dr. Eric Brenner, Dr. Dominique Matt, Prof. İsmail Özdemir, Prof. Cemal Kaya and Loïc Toupet

      Article first published online: 6 MAR 2013 | DOI: 10.1002/cctc.201200716

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      Resourceful resorcinarene: Imidazolium salts based on a rigid resorcinarene platform are used as catalyst precursors in Suzuki–Miyaura cross-coupling reactions, fostering higher catalytic activity than precursor salts devoid of a cavity. The Pd centres of the catalysts obtained from the precursors are found to locate preferentially outside the cavity and the presence of a bulky resorcinarenyl substituent seems to favor the reductive elimination step.

    3. Ruthenium(II)-Catalyzed Hydrogen Generation from Formic Acid using Cationic, Ammoniomethyl-Substituted Triarylphosphine Ligands (pages 1126–1132)

      Weijia Gan, Dr. Dennis J. M. Snelders, Prof. Paul J. Dyson and Prof. Gábor Laurenczy

      Article first published online: 13 MAR 2013 | DOI: 10.1002/cctc.201200782

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      Proceed with cation: New RuII catalysts for aqueous-phase HCOOH decomposition into H2 and CO2 that use a series of oligocationic, ammoniomethyl-substituted triarylphosphine ligands are developed. Excellent activities are achieved, that is, TOFs of 1950 h−1 and TONs of over 10 000.

    4. Synthesis of Poly(silyl ether)s by Rhodium(I)–NHC Catalyzed Hydrosilylation: Homogeneous versus Heterogeneous Catalysis (pages 1133–1141)

      Guillermo Lázaro, Dr. Manuel Iglesias, Dr. Francisco J. Fernández-Alvarez, Dr. Pablo J. Sanz Miguel, Prof. Jesús J. Pérez-Torrente and Prof. Luis A. Oro

      Article first published online: 11 SEP 2012 | DOI: 10.1002/cctc.201200309

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      Getting stuck to rhodium: A new family of rhodium N-heterocyclic carbene (NHC) species is described. The chlorido derivative was immobilized on the inorganic support MCM-41. Both the homo- and heterogeneous catalysts are effective for the copolymerization of terephthalaldehyde and 1,1,3,3,5,5-hexamethyltrisiloxane, which affords the corresponding poly(silyl ether).

    5. Intramolecular Hydroamination Reactions Catalyzed by Neutral and Cationic Group IV Pyridylamido Complexes (pages 1142–1151)

      Dr. Lapo Luconi, Dr. Andrea Rossin, Dr. Giulia Tuci, Stéphane Germain, Dr. Emmanuelle Schulz, Dr. Jérôme Hannedouche and Dr. Giuliano Giambastiani

      Article first published online: 28 SEP 2012 | DOI: 10.1002/cctc.201200389

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      Back to the future! State-of-the-art group IV metal polymerization catalysts are applied to intramolecular C[BOND]N bond-forming reactions. Cationic species show remarkable catalytic activities for the production of N-containing heterocycles from secondary amino alkenes. Additional studies on the amido precursors highlight the role of metal coordination environment on the final catalytic performance.

    6. Palladium(II) Complexes with Small N-Heterocyclic Carbene Ligands as Highly Active Catalysts for the Suzuki–Miyaura Cross-Coupling Reaction (pages 1152–1160)

      Dr. Michał S. Szulmanowicz, Dr. Andrzej Gniewek, Dr. Wojciech Gil and Prof. Dr. Anna M. Trzeciak

      Article first published online: 26 OCT 2012 | DOI: 10.1002/cctc.201200428

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      A robust cross-coupling system: [Pd(NHC)2X2] complexes are synthesized and evaluated in aryl–aryl cross-coupling catalysis. All the obtained complexes demonstrate very high activity in the Suzuki–Miyaura reaction performed in ethylene glycol under mild conditions. Mechanistic investigations reveal an operationally homogeneous reaction pathway, as evidenced by using ESI-MS, TEM, and mercury poisoning experiments.

    7. Preparation of Polymer Supported Phosphine Ligands by Metal Catalyzed Living Radical Copolymerization and Their Application to Hydroformylation Catalysis (pages 1161–1169)

      Dr. Andrés F. Cardozo, Dr. Eric Manoury, Dr. Carine Julcour, Dr. Jean-François Blanco, Prof. Henri Delmas, Dr. Florence Gayet and Prof. Rinaldo Poli

      Article first published online: 30 JAN 2013 | DOI: 10.1002/cctc.201200446

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      Controlled length polystyrene-supported PPh3 ligands are made by atom transfer radical polymerization, involving direct copolymerization of styrene and 4-diphenylphosphinostyrene (SDPP). Controlled Mn and low dispersity are obtained with low SDPP content (≤25 %). The performance of these polymeric ligands in rhodium-catalyzed hydroformylation of 1-octene is evaluated as a function of polymer length, degree of P incorporation, and P/Rh ratio.

    8. Palladium-Catalyzed Ethylene/Methyl Acrylate Cooligomerization: Effect of a New Nonsymmetric α-Diimine (pages 1170–1183)

      Angelo Meduri, Dr. Tiziano Montini, Prof. Dr. Fabio Ragaini, Prof. Dr. Paolo Fornasiero, Prof. Ennio Zangrando and Dr. Barbara Milani

      Article first published online: 5 NOV 2012 | DOI: 10.1002/cctc.201200520

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      Di(e)imine another day: Pd–dmso complexes with α-diimines are synthesized, characterized, and applied to ethylene/methyl acrylate cooligomerization. The complex with a new nonsymmetric α-diimine and dmso was found to be highly productive and showed a long catalyst lifetime. In the graphic, cat=[Pd(CH3)(L)(Ar-BIAN)][PF6].

    9. Artificial Copper Enzymes for Asymmetric Diels–Alder Reactions (pages 1184–1191)

      Dr. Peter J. Deuss, Dr. Gina Popa, Prof. Dr. Alexandra M. Z. Slawin, Dr. Wouter Laan and Prof. Dr. Paul C. J. Kamer

      Article first published online: 1 MAR 2013 | DOI: 10.1002/cctc.201200671

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      Finding the ligand: The covalent modification of sterol carrier protein type 2 like domain with nitrogen ligands affords artificial metalloenzymes for the copper-catalyzed Diels–Alder reaction (see picture). A distinct influence of the location of the ligand within the host on the catalytic performance was observed. An ee of 25 % was found for one ligand–protein construct. The results provide a suitable framework for the development of more selective systems.

    10. Practical and Efficient Organocatalytic Enantioselective α-Hydroxyamination Reactions of β-Ketoamides (pages 1192–1199)

      Dr. Damien Mailhol, Dr. Juan-Carlos Castillo, Dr. Kishor Mohanan, Dr. Rodrigo Abonia, Dr. Yoann Coquerel and Prof. Dr. Jean Rodriguez

      Article first published online: 18 FEB 2013 | DOI: 10.1002/cctc.201200723

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      Constrained chiral center: The first general, efficient and highly enantioselective α-hydroxyamination reactions of carbonyl compounds are described, securing a practical synthetic access to conformationally constrained α-amino acid derivatives exhibiting a quaternary chiral center at the α-position.

    11. Gold(I)-Catalyzed Domino Reaction of Allyl 2-en-4-ynyl Ethers to 1,3,6-Trien-4-yl Ketones (pages 1200–1204)

      Prof. Dr. A. Stephen K. Hashmi, Dipl.-Chem. Katharina Graf, Dr. Martin Ackermann and Dr. Frank Rominger

      Article first published online: 7 MAR 2013 | DOI: 10.1002/cctc.201200787

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      Old is gold! The gold(I)-catalyzed reaction of allyl 2-en-4-ynyl ethers represents a new mechanistic pathway leading to 1,3,6-trien-4-yl ketones under mild reaction conditions (see scheme). Remarkable diastereoselectivity combined with perfect regioselectivity is the key feature of the reaction cascade.

    12. Development of a Stepwise Reductive Deoxygenation Process by Ru-Catalysed Homogeneous Ketone Reduction and Pd-Catalysed Hydrogenolysis in the Presence of Cu Salts (pages 1205–1210)

      Dr. Damian M. Grainger, Dr. Antonio Zanotti-Gerosa, Dr. Kevin P. Cole, Dr. David Mitchell, Dr. Scott A. May, Patrick M. Pollock and Joel R. Calvin

      Article first published online: 1 FEB 2013 | DOI: 10.1002/cctc.201200526

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      Homo and hetero—genius! A stepwise catalytic reduction of ketone 1 to alcohol 2 and subsequently to aryl(imidazo[1,2-b]pyridazinyl)methane 3 is described, which provides synthetically useful chemoselectivity at acceptably low catalyst loadings.

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