Angewandte Chemie International Edition

Cover image for Vol. 43 Issue 34

August 27, 2004

Volume 43, Issue 34

Pages 4379–4535

    1. Cover Picture: Ab Initio NMR Spectra for Molecular Systems with a Thousand and More Atoms: A Linear-Scaling Method (Angew. Chem. Int. Ed. 34/2004) (page 4379)

      Christian Ochsenfeld, Jörg Kussmann and Felix Koziol

      Version of Record online: 25 AUG 2004 | DOI: 10.1002/anie.200490114

      A missing link between theory and experiment for the difficult puzzle of assigning NMR spectra for molecules with more than a thousand atoms is provided by the calculation of ab initio NMR spectra, as symbolized in the cover picture. In their Communication on page 4485 ff., C. Ochsenfeld et al. describe how an approximate solution of the Schrödinger equation becomes possible by reducing the computational effort from cubic to linear.

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      Capillary Electrophoresis Analysis of DNA Adducts as Biomarkers for Carcinogenesis (page 4389)

      Oliver Johannes Schmitz, Christian Christoph Theophil Wörth, Dirk Stach and Manfred Wießler

      Version of Record online: 25 AUG 2004 | DOI: 10.1002/anie.200490116

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      Stereoselective Synthesis of β-D-Mannopyranosides with Reactive Mannopyranosyl Donors Possessing a Neighboring Electron-Withdrawing Group (page 4389)

      Adel A.-H. Abdel-Rahman, Simon Jonke, El Sayed H. El Ashry and Richard R. Schmidt

      Version of Record online: 25 AUG 2004 | DOI: 10.1002/anie.200490119

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      Probing the Mechanism of the Heck Reaction with Arene Diazonium Salts by Electrospray Mass and Tandem Mass Spectrometry (page 4389)

      Adão A. Sabino, Angelo H. L. Machado, Carlos Roque D. Correia and Marcos N. Eberlin

      Version of Record online: 25 AUG 2004 | DOI: 10.1002/anie.200490120

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      Enzyme Microarrays: On-Chip Determination of Inhibition Constants Based on Affinity-Label Detection of Enzymatic Activity (page 4389)

      Jörg Eppinger, Daniel P. Funeriu, Masato Miyake, Lucile Denizot and Jun Miyake

      Version of Record online: 25 AUG 2004 | DOI: 10.1002/anie.200490121

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    7. Microsystem Engineering for Lab-on-a-Chip Devices. By Oliver Geschke, Henning Klank and Pieter Tellemann. (page 4393)

      Jaisree Moorthy, David T. Eddington and David J. Beebe

      Version of Record online: 25 AUG 2004 | DOI: 10.1002/anie.200385159

    8. Metal–Ligand Bonding. By Bob Janes and Elaine Moore. (pages 4394–4395)

      Siegfried Schindler

      Version of Record online: 25 AUG 2004 | DOI: 10.1002/anie.200385190

    9. Möbius Aromatic Hydrocarbons: Challenges for Theory and Synthesis (pages 4396–4398)

      Takeshi Kawase and Masaji Oda

      Version of Record online: 15 JUL 2004 | DOI: 10.1002/anie.200460050

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      Twisting a belt-shaped loop of p orbitals results in a Möbius structure (see scheme). Only recently have synthetic chemists realized this idea first proposed by Heilbronner 40 years ago. The interaction of theory and synthesis, which has distinguished the concept of aromaticity since its inception, has opened a new chapter in this field.

    10. Borromean Rings: A One-Pot Synthesis (pages 4399–4401)

      Christoph A. Schalley

      Version of Record online: 7 JUL 2004 | DOI: 10.1002/anie.200460583

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      Elegance and precision are shown in the self-assembly strategy developed by Stoddart, Atwood, and co-workers for the synthesis of molecular Borromean rings. Metal-ion template effects direct the dynamic formation of covalent bonds, which result in the energetically favorable product having the highly symbolic ring motif (see picture).

    11. Cubic Liquid-Crystalline Nanoparticles (pages 4402–4409)

      Da Yang, Bruce Armitage and Seth R. Marder

      Version of Record online: 15 JUL 2004 | DOI: 10.1002/anie.200301683

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      Cubosomes, cubic liquid-crystalline nanoparticles (see cryo-TEM image), can be prepared from aqueous dispersions of cubic lipid–water phases and are stabilized in the presence of dispersing agents and through polymerization of reactive lipids in cubic lipid assemblies. These nanoparticles can incorporate and release lipophilic, amphiphilic, and water-soluble molecules in a controlled manner.

    12. Theoretical Chemistry of Gold (pages 4412–4456)

      Pekka Pyykkö

      Version of Record online: 25 AUG 2004 | DOI: 10.1002/anie.200300624

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      A golden age for theoretical chemistry: From studies of small molecules to molecular dynamics simulations, including the aurophilic attraction and predictions for new species such as the those for the [WAu12] cluster depicted, theoretical chemistry of gold has come of age. Certain aspects of the softness and the electronic plasmon oscillations may provide further challenges.

    13. Reversible Mechanochemistry of a PdII Coordination Polymer (pages 4460–4462)

      Jos M. J. Paulusse and Rint P. Sijbesma

      Version of Record online: 28 JUL 2004 | DOI: 10.1002/anie.200460040

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      Breaking up and making up: The ultrasonic cleavage of high-molecular-weight linear coordination polymers of phosphane telechelic polytetrahydrofuran and palladium dichloride in dilute solution is a reversible process (see picture). Sonication for 1 h led to a decrease in the weight-averaged molecular weight of the polymer from 1.7×105 to 1.0×105 g mol−1. Upon leaving the sample to stand for 24 h, the original molecular weight was completely restored.

    14. Efficient Photocatalytic Decomposition of Organic Contaminants over CaBi2O4 under Visible-Light Irradiation (pages 4463–4466)

      Junwang Tang, Zhigang Zou and Jinhua Ye

      Version of Record online: 25 AUG 2004 | DOI: 10.1002/anie.200353594

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      Green degradation: Organic contaminants such as volatile organic compounds and dyes (e.g. acetaldehyde and methylene blue (MB)) can be photocatalytically degraded over a novel CaBi2O4 catalyst. The reaction is environmentally friendly (O2 oxidant) and proceeds at room temperature under visible-light irradiation of wide-ranging wavelength (see picture: x=conversion of CH3CHO into CO2, A=absorbance).

    15. Artificial Cells: Temperature-Dependent, Reversible Li+-Ion Uptake/Release Equilibrium at Metal Oxide Nanocontainer Pores (pages 4466–4470)

      Achim Müller, Dieter Rehder, Erhard T. K. Haupt, Alice Merca, Hartmut Bögge, Marc Schmidtmann and Gabriele Heinze-Brückner

      Version of Record online: 25 AUG 2004 | DOI: 10.1002/anie.200453762

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      Lithium ion trafficking: Surprisingly stable and soluble spherical molybdenum oxide based porous nanocontainers/artificial cells (see graphic) interact specifically with their environment, for example, with cations abundant in solution, to incorporate them at well-defined internal cell positions. In the present case, the traffic of Li+ ions between the “outside and inside” is in equilibrium (homeostasis) as measured by NMR spectroscopy. (Li purple, Mo blue, O red)

    16. Synthesis of Diode Molecules and Their Sequential Assembly to Control Electron Transport (pages 4471–4475)

      Ping Jiang, Gustavo M. Morales, Wei You and Luping Yu

      Version of Record online: 25 AUG 2004 | DOI: 10.1002/anie.200460110

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      A sequential deprotection and immobilization procedure was enabled by the synthesis of two thiophene–thiazole diblock oligomers with two different thiol protection groups. Investigation of the I/V behaviors of these diblock molecules between two gold electrodes (see picture) showed that the rectifying direction was controlled by their orientation between the electrodes.

    17. Direct Organocatalytic Enantioselective Mannich Reactions of Ketimines: An Approach to Optically Active Quaternary α-Amino Acid Derivatives (pages 4476–4478)

      Wei Zhuang, Steen Saaby and Karl Anker Jørgensen

      Version of Record online: 25 AUG 2004 | DOI: 10.1002/anie.200460158

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      You're in control of which diastereomer of a quaternary α-amino acid derivative is formed in a direct organocatalytic diastereoselective and enantioselective Mannich reaction of ketimines with aldehydes (see scheme). The reactions are high yielding and can be controlled through the choice of the catalyst to give either diastereomer of the product with diastereomeric ratios as high as >20:1 and with 83–98 % ee. Pg=protecting group.

    18. A C3-Symmetrical Chiral Trisoxazoline Zinc Complex as a Functional Model for Zinc Hydrolases: Kinetic Resolution of Racemic Chiral Esters by Transesterification (pages 4479–4482)

      Clémence Dro, Stéphane Bellemin-Laponnaz, Richard Welter and Lutz H. Gade

      Version of Record online: 25 AUG 2004 | DOI: 10.1002/anie.200460187

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      Mimicking the activity of tris(histidine)zinc-based enzymes, chiral dinuclear trisoxazolinezinc complexes such as the triflato cation (see picture) are the first non-enzymatic catalysts for the asymmetric transesterification of activated esters. First results of the kinetic resolution of amino acid phenolates establish the stereoselectivity for this reaction. (F pink, N blue, O red, S yellow, Zn cyan)

    19. Stereoselective Synthesis of a Topologically Chiral Molecule: The Trefoil Knot (pages 4482–4485)

      Laure-Emmanuelle Perret-Aebi, Alexander von Zelewsky, Christiane Dietrich-Buchecker and Jean-Pierre Sauvage

      Version of Record online: 25 AUG 2004 | DOI: 10.1002/anie.200460250

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      Tying nice neat knots is demonstrated on a molecular level with the stereoselective synthesis of a trefoil knot. The key reaction was the completely stereoselective formation of a double-stranded helical precursor from two pinene–bipyridine threads around two CuI centers (the pinene moieties contain stereogenic centers). The helix was then transformed through several steps into 1; demetallation of the complex 1 yielded the configurationally predetermined free trefoil knot.

    20. Ab Initio NMR Spectra for Molecular Systems with a Thousand and More Atoms: A Linear-Scaling Method (pages 4485–4489)

      Christian Ochsenfeld, Jörg Kussmann and Felix Koziol

      Version of Record online: 11 AUG 2004 | DOI: 10.1002/anie.200460336

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      A method for the calculation of NMR shieldings is presented, which allows for the first time the study of molecular systems with one thousand and more atoms at the ab initio level (see picture), by reducing the computational scaling from cubic to linear. This opens new possibilities for the often difficult assignment of experimental NMR spectra.

    21. Asymmetric Synthesis Utilizing Circularly Polarized Light Mediated by the Photoequilibrium of Chiral Olefins in Conjunction with Asymmetric Autocatalysis (pages 4490–4492)

      Itaru Sato, Rie Sugie, Yohei Matsueda, Yuri Furumura and Kenso Soai

      Version of Record online: 25 AUG 2004 | DOI: 10.1002/anie.200454162

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      The light touch: Asymmetric photoequilibrium and autocatalysis act as sources of homochirality in a highly enantioselective preparation of chiral alcohols (see scheme). This process is initiated by left- and right-circularly polarized light (CPL) and exploits the resulting photoequilibrium between chiral olefin substrates to yield 2-alkynyl-5-pyrimidyl alkanols.

    22. Mechanistic Studies of a Reaction Promoted by the [YLi3{tris(binaphthoxide)}] Complex: Are Three 1,1′-Bi-2-naphthol Units in a Rare-Earth–Alkali-Metal Heterobimetallic Complex Necessary? (pages 4493–4497)

      Noriyuki Yamagiwa, Shigeki Matsunaga and Masakatsu Shibasaki

      Version of Record online: 25 AUG 2004 | DOI: 10.1002/anie.200454202

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      The power of three: Mechanistic studies based on the kinetic profiles of the catalytic asymmetric 1,4-addition of an amine to chalcone revealed that all three binol ligands of the [YLi3{tris(binaphthoxide)}] complex 1 are involved in the active species of the Y–Li heterobimetallic catalyst.

    23. Synthesis and Structure of a Dimetallated Buckybowl: Coordination of One {Cp*Ru}+ Unit to Each Side of Corannulene (pages 4497–4500)

      Paul A. Vecchi, Celedonio M. Alvarez, Arkady Ellern, Robert J. Angelici, Andrzej Sygula, Renata Sygula and Peter W. Rabideau

      Version of Record online: 25 AUG 2004 | DOI: 10.1002/anie.200454225

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      A significantly flattened corannulene, which is η6-coordinated on each side by a {Cp*Ru}+ moiety, is revealed in the X-ray structure analysis of [(Cp*Ru)2266-C20H10)][PF6]2. The reaction of [{Cp*Ru(μ3-Cl)}4] with Ag+ ions and the curved-surface buckybowl corannulene (C20H10) in CD3NO2 solvent affords this dimetallated corannulene complex (see picture).

    24. A 1,3-Diaza-2,4-distannacyclobutanediide: Synthesis, Structure, and Bonding (pages 4500–4504)

      Hazel Cox, Peter B. Hitchcock, Michael F. Lappert and Luc J.-M. Pierssens

      Version of Record online: 25 AUG 2004 | DOI: 10.1002/anie.200460039

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      A combined experimental and computational study throws light on the structure and bonding of the diamagnetic {(SnN)2} compound [{Sn{N(SiMe3)}Cl}2] (see picture), obtained from the reaction of [Sn{N(SiMe3)2}(μ-Cl)]2 with AgOCN.

    25. Biomimetic Oxidation of Chromium(III): Does the Antidiabetic Activity of Chromium(III) Involve Carcinogenic Chromium(VI)? (pages 4504–4507)

      Irma Mulyani, Aviva Levina and Peter A. Lay

      Version of Record online: 25 AUG 2004 | DOI: 10.1002/anie.200460113

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      The insulin-enhancing activities of some CrIII complexes, such as [Cr3O(OCOEt)6(OH2)3]+ (1), previously attributed to specific interactions of CrIII ions with cellular insulin receptors, are more likely to be caused by the formation of [CrO4]2− (2). Oxidation of 1 to 2 by biologically relevant oxidants, including enzymes (see scheme), and inhibition of an isolated protein tyrosine phosphatase by a CrVI complex are reported.

    26. Rhodizonate Metal Complexes with a 2D Chairlike M6 Metal–Organic Framework: [M(C6O6)(bpym)(H2O)]⋅n H2O (pages 4507–4510)

      Chih-Chieh Wang, Chen-Tsung Kuo, Pi-Tai Chou and Gene-Hsiang Lee

      Version of Record online: 25 AUG 2004 | DOI: 10.1002/anie.200460278

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      Two transition-metal rhodizonate complexes, [M(C6O6)(bpym)(H2O)]⋅n H2O (M=Cd, n=1; M=Mn, n=2; bpym=2,2′-bipyrimidine), are reported. Both the rhodizonate and bpym ligands are bis-bidentate ligands (see the Cd example depicted) which chelate the metal ions, thus forming a novel 2D chairlike M6 metal–organic framework.

    27. The Singlet Excited State of a Stable Dialkylsilylene Is Responsible for Its Photoreactions (pages 4510–4512)

      Mitsuo Kira, Shintaro Ishida, Takeaki Iwamoto, Armin de Meijere, Mamoru Fujitsuka and Osamu Ito

      Version of Record online: 25 AUG 2004 | DOI: 10.1002/anie.200460317

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      The singlet 1,1-diradical (1B1) state of a silylene plays a key role in its photoreactions with benzenes and alkenes, even though similar 1B1 states are rarely encountered in carbene chemistry. The photochemical addition to alkenes should be stepwise and the ring closure of the intermediate singlet 1,3-diradicals was very facile with rates (kc) of more than 109 s−1 (see scheme).

    28. The Isolation and Crystal Structure of a Cyclic Selenenate Ester Derived from Bis(2,6-diformyl-4-tert-butylphenyl)diselenide and its Glutathione Peroxidase-Like Activity (pages 4513–4515)

      Sanjio S. Zade, Harkesh B. Singh and Ray J. Butcher

      Version of Record online: 25 AUG 2004 | DOI: 10.1002/anie.200460380

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      Enzyme mimicry: Halogenation of diselenide 1 affords the cyclic selenenate ester 2 (see scheme) through a highly unstable selenenic acid intermediate. Compound 2 exhibits a strong intramolecular nonbonding Se⋅⋅⋅O interaction. Both 1 and 2 show excellent glutathione peroxidase-like catalytic activity.

    29. Allosteric and Electrostatic Reprogramming of a Ditopic Ligand (pages 4515–4518)

      Christian J. Baylies, Lindsay P. Harding, John C. Jeffery, T. Riis-Johannessen and Craig R. Rice

      Version of Record online: 25 AUG 2004 | DOI: 10.1002/anie.200460424

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      A potentially tetradentate pyridyl–thiazole ligand chain and an additional “external” crown ether binding site connect the two halves of a new ditopic ligand. The pyridyl-thiazole binding sites can be changed or “reprogrammed” by the addition of Ba2+: In the presence of Hg2+ and Na+ the ligand L1 forms a dinuclear double helicate ([Hg2(L1)2Na2]6+), whereas in the presence of Hg2+ and Ba2+ a mononuclear species is formed ([Hg(L1)Ba]4+).

    30. Catalytic Growth of Au Nanoparticles by NAD(P)H Cofactors: Optical Sensors for NAD(P)+-Dependent Biocatalyzed Transformations (pages 4519–4522)

      Yi Xiao, Valeri Pavlov, Semion Levine, Tamara Niazov, Gil Markovitch and Itamar Willner

      Version of Record online: 25 AUG 2004 | DOI: 10.1002/anie.200460608

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      Gold-plated gold: NAD(P)H cofactors mediate the catalytic growth of Au nanoparticles in the presence of AuCl4 and CTAB (cetyltrimethylammonium bromide; see picture). The process allows for the optical detection of the cofactors and the analysis of NAD(P)+-dependent biocatalyzed transformations in solutions and on surfaces.

    31. Total Synthesis of Xerulinic Acid (pages 4523–4526)

      Achim Sorg and Reinhard Brückner

      Version of Record online: 25 AUG 2004 | DOI: 10.1002/anie.200453729

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      An inhibitor of the biosynthesis of cholesterol, xerulinic acid, has been synthesized for the first time. The convergent approach applied involves the palladium-catalyzed coupling of an enediynoic ester building block, a conjunctive C6 bisstannane, and a bromine-containing methylenebutenolide (see scheme; R=Me3SiCH2CH2).

    32. A Flexible, Palladium-Catalyzed Indole and Azaindole Synthesis by Direct Annulation of Chloroanilines and Chloroaminopyridines with Ketones (pages 4526–4528)

      Marc Nazaré, Claudia Schneider, Andreas Lindenschmidt and David William Will

      Version of Record online: 25 AUG 2004 | DOI: 10.1002/anie.200460122

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      The “ringmaster” [Pd(tBu3P)2] serves as the catalyst in the direct synthesis of indoles by annulation of ortho-chloroanilines with ketones (see picture). This versatile method can be used to synthesize a variety of functionalized indoles and azaindoles. DMA=dimethylacetamide.

    33. Efficient Whole-Cell Biotransformation in a Biphasic Ionic Liquid/Water System (pages 4529–4531)

      Holger Pfruender, Maya Amidjojo, Udo Kragl and Dirk Weuster-Botz

      Version of Record online: 25 AUG 2004 | DOI: 10.1002/anie.200460241

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      Biocompatible ionic liquids act as a substrate reservoir and an in situ extracting agent in biotransformations with whole cells (see scheme). In the reduction of 4-chloroacetophenone to (R)-1-(4-chlorophenyl)ethanol, high product concentration (82 g L−1) and purity (99.6 % ee) were achieved without the addition of cofactors and without damaging the biocatalyst.

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      Preview: Angew. Chem. Int. Ed. 34/2004 (page 4535)

      Version of Record online: 25 AUG 2004 | DOI: 10.1002/anie.200490118

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