The Chemical Record

Cover image for Vol. 16 Issue 6

Special Issue: 15th Anniversary of Nobel Prize to Ryoji Noyori

December 2016

Volume 16, Issue 6

Pages 2427–2815

  1. Cover Picture

    1. Top of page
    2. Cover Picture
    3. Guest Editorial
    4. Personal Account
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      Cover Picture (page 2427)

      Version of Record online: 7 DEC 2016 | DOI: 10.1002/tcr.201690005

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  2. Guest Editorial

    1. Top of page
    2. Cover Picture
    3. Guest Editorial
    4. Personal Account
    1. You have free access to this content
  3. Personal Account

    1. Top of page
    2. Cover Picture
    3. Guest Editorial
    4. Personal Account
    1. Binap and Phosphoramidites as Privileged Chiral Ligands for the Metal-Catalyzed Enantioselective 1,3-Dipolar Cycloaddition of Azomethine Ylides (pages 2430–2448)

      Carmen Nájera and José M. Sansano

      Version of Record online: 5 APR 2016 | DOI: 10.1002/tcr.201500283

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      Taking control: 2,2′-Bis(diphenylphosphino)-1,1′-binaphthyl (binap) and phosphoramidites are privileged chiral ligands that have been tested in the coinage-metal-catalyzed 1,3-dipolar cycloadditions of metalloazomethine ylides and electrophilic alkenes. Tuning of the ligands and cations allow control of the enantioselectivity of the reaction.

    2. What are the Limitations of Enzymes in Synthetic Organic Chemistry? (pages 2449–2459)

      Manfred T. Reetz

      Version of Record online: 15 JUN 2016 | DOI: 10.1002/tcr.201600040

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      Problem solver in biocatalysis: when applying enzymes in organic chemistry, metabolic-pathway engineering, mutasynthesis, or synthetic cascade reaction design, directed evolution can solve many, but not all, the problems.

    3. Adaptable P–X Biaryl Phosphite/Phosphoroamidite-Containing Ligands for Asymmetric Hydrogenation and C–X Bond-Forming Reactions: Ligand Libraries with Exceptionally Wide Substrate Scope (pages 2460–2481)

      Oscar Pàmies and Montserrat Diéguez

      Version of Record online: 21 JUN 2016 | DOI: 10.1002/tcr.201600062

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      Predicting catalysis: The design of ligand libraries for the discovery of suitable metal catalysts for asymmetric hydrogenation and C–X bond-forming reactions are reviewed.

    4. Calcium, Strontium and Barium Homogeneous Catalysts for Fine Chemicals Synthesis (pages 2482–2505)

      Yann Sarazin and Jean-François Carpentier

      Version of Record online: 29 JUN 2016 | DOI: 10.1002/tcr.201600067

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      The design of discrete, stable complexes of the large alkaline earths calcium, strontium, and barium by our research group, together with their implementation as potent molecular precatalysts in hydroamination, hydrophosphination, hydrophosphonylation, cross-dehydrogenative reactions, is retraced.

    5. A Decennary Journey towards the Efficient Asymmetric Hydrogenation of Highly Functionalized Ketones (pages 2506–2520)

      Wanfang Li, Bin Lu and Zhaoguo Zhang

      Version of Record online: 7 JUL 2016 | DOI: 10.1002/tcr.201600064

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      Opening up the scope: Using the Ru–SunPhos complex as a catalyst, the chemo- and enantioselective hydrogenation of a range of highly functionalized ketones, including γ-heteroatom-substituted β-keto esters, δ-ketal-β-keto esters, γ-halo-γ,δ-unsaturated-β-keto esters, 3-oxo glutaric acid derivatives, β,δ-diketo carboxamides, and γ-heteroatom-substituted β-diketones, has been realized. These substrates are very challenging, but useful for organic synthesis.

    6. The Hiyama Cross-Coupling Reaction: New Discoveries (pages 2521–2533)

      Francisco Foubelo, Carmen Nájera and Miguel Yus

      Version of Record online: 14 JUL 2016 | DOI: 10.1002/tcr.201600063

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      In this account recent developments in the Hiyama cross-coupling reaction from 2010 up today are presented. The most important methodology involves formation of biaryl systems by using aryl bromides or iodides and aryl trialkoxy silanes: other variants are far less studied.

    7. Mass Spectrometric Back Reaction Screening of Quasi-Enantiomeric Products as a Mechanistic Tool (pages 2534–2543)

      Patrick G. Isenegger and Andreas Pfaltz

      Version of Record online: 15 JUL 2016 | DOI: 10.1002/tcr.201600072

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      Observing back and forth: Mass spectrometric back reaction screening of quasi-enantiomeric products may serve as a valuable tool for examining the mechanism of an enantioselective catalytic process. By comparing the results from the forward and back reaction, direct evidence for the involvement of a catalytic intermediate in the enantioselective step can be obtained. The potential of this method is demonstrated for various organocatalytic asymmetric reactions.

    8. Riding the Wave of Monodentate Ligand Revival: From the A/B Concept to Noncovalent Interactions (pages 2544–2560)

      Luca Pignataro and Cesare Gennari

      Version of Record online: 18 JUL 2016 | DOI: 10.1002/tcr.201600087

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      Catch the wave: The rediscovery of chiral monodentate ligands, which was made around 2000, triggered new trends in enantioselective transition-metal-catalysis, such as the use of ligand mixtures and an increasing interest in supramolecular ligands. This account summarizes the most important contributions provided by our group within this area between 2004 and 2015.

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      The Quest for Palladium-Catalysed Alkyl–Nitrogen Bond Formation (pages 2561–2572)

      Kilian Muñiz, Claudio Martínez and Álvaro Iglesias

      Version of Record online: 18 JUL 2016 | DOI: 10.1002/tcr.201600073

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      Pd(IV) for Csp3–N bond formation: The formation of alkyl–nitrogen bonds under homogeneous palladium catalysis can be conducted in a convenient manner, when a high-oxidation-state palladium(IV) complex is generated. C–N bond formation proceeds from such an intermediate with a transition state reminiscent of nucleophilic substitution. Processes of this type are involved in the diamination of alkenes and in the C–H amination of benzylic positions.

    10. Renovation of Optically Active Phenanthrolines as Powerful Chiral Ligands for Versatile Asymmetric Metal Catalysis (pages 2573–2584)

      Yuki Naganawa and Hisao Nishiyama

      Version of Record online: 8 AUG 2016 | DOI: 10.1002/tcr.201600078

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      The novel chiral ligands (S)-1, which adopt a N,N,O-tridentate coordination provided by the phenanthroline (phen) and the phenolic hydroxyl group, were recently designed by our group. As phen possesses greater coordination ability with various ions, (S)-1 can be applied to a broad range of metal catalysts and new reactions. This account summarizes our results on the application of (S)-1 in various kinds of metal catalysis.

    11. Triply Halide-Bridged Dinuclear Iridium(III) Complexes with Chiral Diphosphine Ligands as New Easy-to-Handle Iridium Catalysts for Asymmetric Hydrogenation of Imines and N-Heteroaromatics (pages 2585–2594)

      Kazushi Mashima, Kosuke Higashida, Atsuhiro Iimuro, Haruki Nagae and Yusuke Kita

      Version of Record online: 10 AUG 2016 | DOI: 10.1002/tcr.201600079

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      Triply halide-bridged dinuclear iridium complexes bearing chiral diphosphine ligands have advantages such as easy preparation as well as air and moisture stability, leading to easy handling in asymmetric synthesis. The dinuclear iridium complexes exhibited high catalytic activity toward asymmetric hydrogenation of imines and N-heteroaromatics.

    12. Features and Application in Asymmetric Catalysis of Chiral Phosphine–Phosphite Ligands (pages 2595–2618)

      Antonio Pizzano

      Version of Record online: 10 AUG 2016 | DOI: 10.1002/tcr.201600076

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      Take a P-OP! Phosphine–phosphite ligands (P-OP) are highly modular ligands, with two distinct coordination functions, that are useful for a wide variety of transformations in asymmetric catalysis.

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      The Development of Phosphine-Free "Tethered" Ruthenium(II) Catalysts for the Asymmetric Reduction of Ketones and Imines (pages 2619–2639)

      Hans G. Nedden, Antonio Zanotti-Gerosa and Martin Wills

      Version of Record online: 15 AUG 2016 | DOI: 10.1002/tcr.201600084

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      Caught in a bind: This review contains an account of the design and synthetic approaches to the tethered catalyst derivatives of the Noyori Ru/arene series of catalysts for asymmetric hydrogenation and transfer hydrogenation, together with details of their application to reductions of ketones and imines. Examples of industrial applications of the tethered catalysts, and their broader synthetic utility, are described

    14. Iron Group Hydrides in Noyori Bifunctional Catalysis (pages 2640–2654)

      Robert H. Morris

      Version of Record online: 15 AUG 2016 | DOI: 10.1002/tcr.201600080

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      An overview is presented of hydride-containing catalysts prepared in the Morris group for the efficient hydrogenation of simple ketones, imines, nitriles and esters and the asymmetric hydrogenation and transfer hydrogenation of prochiral ketones and imines. The work was inspired by and makes use of the Noyori metal-ligand bifunctional concepts involving the hydride-ruthenium amine-hydrogen HRuNH design.

    15. Searching for Practically Useful P-Chirogenic Phosphine Ligands (pages 2655–2669)

      Tsuneo Imamoto

      Version of Record online: 15 AUG 2016 | DOI: 10.1002/tcr.201600098

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      Ligands on a large scale: Enantiopure P-chirogenic phosphine ligands are efficiently prepared via phosphine boranes. Conformationally rigid and electron-rich P-chirogenic phosphine ligands, with a bulky alkyl group and a small group at the phosphorus atoms, exhibit excellent enantioselectivities in various metal-catalyzed asymmetric reactions. These ligands are also used in the mechanistic study of Rh-catalyzed asymmetric hydrogenation.

    16. Chiral Ligands for Rhodium-Catalyzed Asymmetric Hydroformylation: A Personal Account (pages 2670–2682)

      Caiyou Chen, Xiu-Qin Dong and Xumu Zhang

      Version of Record online: 15 AUG 2016 | DOI: 10.1002/tcr.201600055

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      A variety of chiral ligands for asymmetric hydroformylation have been developed over the past few decades. However, only a few ligands exhibit good performance in terms of the substrate tolerance and regio- and enantioselectivities and no examples have led to the application of the AHF reaction on a commercial scale. This account provides a brief introduction of the current efficient chiral ligands for asymmetric hydroformylation and the ongoing efforts we have made in this field.

    17. Allylic Alkylations with Enamine Nucleophiles (pages 2683–2692)

      Nicholas Butt, Guoqiang Yang and Wanbin Zhang

      Version of Record online: 25 AUG 2016 | DOI: 10.1002/tcr.201600071

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      The Pd-catalyzed allylic alkylation of carbonyl substrates via the generation of a nucleophilic enamine intermediate is a convenient and efficient methodology for carbon-carbon bond construction. In combination with chiral metallocene-based ligands, carbonyl substrates can be alkylated with a diverse array of allylic species including allylic amines, allylic alcohols and allylic ethers, affording the corresponding products with excellent enantioselectivities.

    18. Asymmetric Hydrogenation of Quinoline Derivatives Catalyzed by Cationic Transition Metal Complexes of Chiral Diamine Ligands: Scope, Mechanism and Catalyst Recycling (pages 2693–2707)

      Yi-Er Luo, Yan-Mei He and Qing-Hua Fan

      Version of Record online: 24 AUG 2016 | DOI: 10.1002/tcr.201600095

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      Asymmetric hydrogenation of various quinolines and their analogues have been achieved by using chiral cationic η-arene-N-monosulfonylated diamine/Ru(II) or Ir(III) catalysts in organic solvents, water, ionic liquids, oligo(ethylene glycol)s or even under solvent-free conditions in high yields with excellent enantioselectivities. The Ru-catalysts are stable and recyclable, and quinoline is reduced via a stepwise H+/H- transfer process outside the coordination sphere rather than a concerted mechanism.

    19. Progress of Chiral Schiff Bases with C1 Symmetry in Metal-Catalyzed Asymmetric Reactions (pages 2708–2735)

      Masahiko Hayashi

      Version of Record online: 22 SEP 2016 | DOI: 10.1002/tcr.201600091

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      In this personal account, various chiral Schiff base–metal-catalyzed enantioselective organic reactions were reported; the Schiff bases used were O,N,O- as well as N,N,P-tridentate ligands and N,N-bidentate ligands having C1 symmetry. Particularly, the enantioselective addition of trimethylsilyl cyanide, dialkylzinc, and organozinc halides to aldehydes; enantioselective 1,4-addition of dialkylzinc to enones; and asymmetric allylic oxidation were reported. Notably, remarkable ligand acceleration was observed for all reactions. The obtained products are used as key intermediates for optically active natural products and pharmaceuticals.

    20. Chiral Bidentate NHC Ligands Based on the 1,1′-Binaphthyl Scaffold: Synthesis and Application in Transition-Metal-Catalyzed Asymmetric Reactions (pages 2736–2749)

      Qin Xu, Peng Gu, Hanchun Jiang, Yin Wei and Min Shi

      Version of Record online: 26 SEP 2016 | DOI: 10.1002/tcr.201600103

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      This account summarizes the recent work of our group on the design and synthesis of chiral bidentate NHC ligands based on the 1,1′-binaphthyl scaffold, as well as the application of these NHC–metal complexes in transition-metal-catalyzed asymmetric redox reactions, cyclization reactions, and C–C bond formations.

    21. Transition-Metal-Catalyzed Asymmetric Hydrogenation and Transfer Hydrogenation: Sustainable Chemistry to Access Bioactive Molecules (pages 2750–2767)

      Tahar Ayad, Phannarath Phansavath and Virginie Ratovelomanana-Vidal

      Version of Record online: 4 OCT 2016 | DOI: 10.1002/tcr.201600100

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      Creating chirality: Over the last few decades, the development of new and highly efficient synthetic methods to obtain chiral compounds has become an increasingly important and challenging research area in modern synthetic organic chemistry. Recent work toward the synthesis of valuable chiral building blocks through transition-metal-catalyzed asymmetric hydrogenation and transfer hydrogenation of C=O, C=N, and C=C bonds is reported. Application of the methods to the synthesis of biologically relevant targets is also described.

    22. Transfer Hydrogenation in Water (pages 2768–2782)

      Xiaofeng Wu, Chao Wang and Jianliang Xiao

      Version of Record online: 17 OCT 2016 | DOI: 10.1002/tcr.201600089

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      Green conditions: Using water as solvent, transfer hydrogenation of various carbonyl and N-heterocyclic compounds with the Noyori–Ikariya catalyst and iridacycles has been shown to be feasible and practical. This article provides a summary of recent advances in this area.

    23. Catalytic Conversion of Renewable Resources into Bulk and Fine Chemicals (pages 2783–2796)

      Johannes G. de Vries

      Version of Record online: 20 OCT 2016 | DOI: 10.1002/tcr.201600102

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      Catalysis is the key technology for the conversion of biomass-derived platform chemicals into existing bulk chemicals. Highly selective low-temperature conversions make these multistep routes more attractive than single-step fermentation or high-temperature gasification or pyrolysis routes. Development of high yielding conversion of lignin into chemicals is still needed to complete the biorefinery concept.

    24. Advancement in Catalytic Asymmetric Hydrogenation of Ketones and Imines, and Development of Asymmetric Isomerization of Allylic Alcohols (pages 2797–2815)

      Takeshi Ohkuma and Noriyoshi Arai

      Version of Record online: 24 AUG 2016 | DOI: 10.1002/tcr.201600101

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      Optically active diphosphine/diamine/Ru(II) and the related complexes successfully catalyze asymmetric hydrogenation of ketones and imines with a base co-catalyst. The structural diversity of this type of complex achieves extremely high catalyst efficiency (TOF = 580 sec−1) and enantioselectivity of >99% in the best cases as well as a wide scope of substrates. Asymmetric isomerization (1,3-hydrogen shift) of γ,γ-disubstituted primary allylic alcohols is also catalyzed, affording the β-substituted aldehydes in almost enantiomerically pure form.