Angewandte Chemie International Edition in English

Cover image for Vol. 33 Issue 5

March 17, 1994

Volume 33, Issue 5

Pages 489–588

Currently known as: Angewandte Chemie International Edition

    1. Cover Picture (Angew. Chem. Int. Ed. Engl. 5/1994)

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199404881

      Thumbnail image of graphical abstract

      The cover picture shows the ultimate chiral object–a hand–holding a model of a complex containing a chelate bonding through nitrogen to symbolize the successful use of such complexes in asymmetric catalysis. Metal complexes with optically active ligands binding through N have gained in importance immensely in recent years. Togni and Venanzi compare the main classes of ligands and discuss catalytic aspects in their review on p. 497 ff. and thus help to bridge the gap which still exists between the theory of coordination chemistry and homogeneous catalysis. The picture was generated from a drawing by A. T. of his own hand and elaborated by U. Burckhardt at ETH with the program Adobe Illustrator 3.0.

  1. Reviews

    1. Top of page
    2. Reviews
    3. Highlights
    4. Communications
    5. Book Reviews
    1. Nitrogen Donors in Organometallic Chemistry and Homogeneous Catalysis (pages 497–526)

      Prof. Dr. Antonio Togni and Prof. Dr. Luigi M. Venanzi

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199404971

      Asymmetric catalysis–a very important field in synthetic organic chemistry–generally employs organometallic compounds with chiral ligands. Whereas at first primarily phosphanes were used, in recent years attention has turned to nitrogen ligands that are accessible in enantiomerically pure from, for example, from the naturally occurring amino acids. The properties of nitrogen compounds as ligands is one topic of this review; the second is the type of metals and ligands that are suitable as catalysts for specific reactions. One of the most prominent catalyzed reactions is the Sharpless dihydroxylation of olefins.

    2. Nitrile Imines: From Matrix Characterization to Stable Compounds (pages 527–545)

      Dr. Guy Bertrand and Prof. Dr. Curt Wentrup

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199405271

      By taking advantage of electronic and steric effects, nitrile imines have been stabilized to the extent that compounds such as 1 and 2 could be characterized even by X-ray crystallography. This intriguing class of compounds was postulated as reactive intermediates more than thirty years ago and detected in matrix and gas-phase studies at the beginning of the 1980s. Substituents with main group elements have played a significant role in the latest investigations, as nitrile imine 1 and other examples indicate. Yet purely organic nitrile imines like 2 are also stable.

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  2. Highlights

    1. Top of page
    2. Reviews
    3. Highlights
    4. Communications
    5. Book Reviews
    1. Novel Carbon Compounds with “Naked” Cn Units (pages 547–550)

      Priv.-Doz. Dr. Heinrich Lang

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199405471

      1,3-Dimetallaallenes 1 or carbyne complexes 2 are the simplest examples of compounds in which different transition metal complex fragments or units of main group elements are terminally bound to Cn bridges. Polymers such as 3 with C4 bridges which link d8 ML2 building blocks are of particular interest as materials with novel properties.

      • equation image
    2. Enzyme Mimics (pages 551–553)

      Dr. Anthony J. Kirby

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199405511

      The enzyme, the reaction mechanism, or substrate binding can be the basis for enzyme mimics. Together with a short overview of the approaches employed for enzyme imitation, in particular the results of two recent important papers on this topic are discussed: the “pepzymes” of Atassi and Manshouri and the “micelle procedure” of Menger and Fei (see also Angew. Chem. Int. Ed.1994, 106, 346).

  3. Communications

    1. Top of page
    2. Reviews
    3. Highlights
    4. Communications
    5. Book Reviews
    1. Molecular Solids as Ligands in Organometallic Chemistry: [Cpmath imageTi6Na7F19·2.5thf] (Cp* [DOUBLE BOND] C5Me5) and [Cpmath imageTi4Mg2F12·7thf], Links Between Ionic Solids and Organometallic Compounds (pages 555–556)

      Dr. Feng-Quan Liu, Annja Kuhn, Dr. Regine Herbst-Irmer, Priv.-Doz. Dr. Dietmar Stalke and Prof. Dr. Herbert W. Roesky

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199405551

      Central NaF and MgF2 frameworks are present in the title compounds obtained from the reaction of [Cp*TiF3] (Cp [DOUBLE BOND] C5Me5) with elemental sodium and magnesium, respectively. In these reactions TiIV is reduced to TiIII. The Cp*Ti units function as organometallics shields around the cagelike core and are responsible for the high solubility of the compounds.

    2. Kinetic Resolution of the Acrolein Dimer by Asymmetric Horner-Wadsworth-Emmons Reactions (pages 556–558)

      Tobias Rein, Dipl.-Chem. Nina Kann, Dr. Reinhard Kreuder, Benoit Gangloff and Dr. Oliver Reiser

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199405561

      Thumbnail image of graphical abstract

      Diastereoselectivities up to 98% de have been reached in kinetic resolutions of the racemic acrolein dimer 1 by reaction with the chiral phosphonates 2. Depending on the choice of substituents on the phosphoryl group (R [DOUBLE BOND] CF3CH2, C2H5), either (E)-3 or (Z)-3, both of which are versatile synthetic building blocks, can be obtained as the major product. The dominant isomer for (Z)-3 is the (S) isomer and for (E)-3 the (R) isomer.

    3. Ring Opening of Cyclopropane at 10 K (pages 558–559)

      Prof. Günther Maier and Stefan Senger

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199405581

      Thumbnail image of graphical abstract

      “Thermal” reactions at 10 K? How is it posible to achieve a thermal ring-opening of cyclopropane [Eq. (a)] and cyclopropene (both reactions have substantial energy barriers) at such extremely low temperatures? The answer is to be found in this communications.

    4. Buckminsterfullerene Adducts from Ortho-Quinodimethanes (pages 559–561)

      Dipl.-Chem. Andreas Gügel, Dipl.-Chem. Alexander Kraus, Dipl.-Chem. Jochen Spickermann, Dipl.-Chem. Pavel Belik and Prof. Dr. Klaus Müllen

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199405591

      Thumbnail image of graphical abstract

      Buckminsterfullerene derivatives with chromophoric, electrophoric, or ionophoric units are accessible from the key compound 1 in very good yields on reaction with aliphatic or aromatic amines. Compound 1 can be obtained from the fullerene and the precursor of the appropriate substituted o-quinodimethane.

    5. Regioselective Synthesis and Antiviral Activity of Purine Nucleoside Analogues with Acyclic Substituents at N7 (pages 562–563)

      Dr. Gerhard Jähne, Herbert Kroha, Armin Müller, Dr. Matthias Helsberg, Dr. Irvin Winkler, Dr. Gerhard Gross and Dr. Thomas Scholl

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199405621

      Thumbnail image of graphical abstract

      A new class of antiviral compounds is heralded by purine derivative 1, which in vitro tests showed to have good antiherpes action. This compound proves that, like the natural purine nucleosides with a cyclic residue at N9, derivatives with an acyclic substituent at N7 can also be active.

    6. The Influence of Charge Distribution on Bond Lengths in the P4O6 Framework in Compounds of the Type P4O6X (pages 563–565)

      Dipl.-Chem. Max Mühlhäuser, Priv.-Doz. Dr. Bernd Engels, Priv.-Doz. Dr. Christel M. Marian, Prof. Dr. Sigrid D. Peyerimhoff, Dr. Pablo J. Bruna and Prof. Dr. Martin Jansen

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199405631

      Thumbnail image of graphical abstract

      The amount of charge transferred on substitution can be used to explain the experimentally determined difference in P[BOND]O bond lengths between phosphorus oxides or oxide sulfides of the type P4O6X (X [DOUBLE BOND] O and S, respectively; structure shown on the right) and the parent compound P4O6. With the strongly electron-repelling substituent X [DOUBLE BOND] N, the observed effects should be reversed.

    7. The First Water-Dependent Liquid Clathrate: X-Ray Evidence in the Solid for a C[BOND]H ⃛π(Heteroarene) ⃛ H[BOND]C Interaction (pages 566–568)

      Prof. Dr. Roger Hunter, Dipl.-Chem. Renate H. Haueisen and Dr. Anne Irving

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199405661

      Thumbnail image of graphical abstract

      The air- and water-stable cyanoborate host compound 1 forms a liquid or solid clathrate with furan, depending on the water content. The X-ray structure analysis of the solid clathrate that crystallizes out of the liquid clathrate layer indicates the presence of novel C[BOND]H ⃛π(heteroarene) ⃛H[BOND]C interactions, as well as CN ⃛H[BOND]C(P) anion–cation hydrogen bonding.

    8. Reactions at Both Ends of a Dimetalated Olefin: CS2 Insertion into and Atom Transfer Reactions of [Re(CO)4-{trans-μ-HC[DOUBLE BOND]C(CO2Me)}Re(CO)4(NCMe)] (pages 568–569)

      Prof. Richard D. Adams, Linfeng Chen and Wengan Wu

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199405681

      Thumbnail image of graphical abstract

      First a functionalized C[BOND]C bond, then a C[BOND]E bond (E [DOUBLE BOND] O, S) are formed at the methyl propenate ligands in the title compound to afford 1. This takes place when the starting material is treated with CS2 and subsequently with pyridine-N-oxide or ethylenesulfide. In this reaction the CS2 molecule is inserted exclusively into the Re[BOND]Cα bond of the starting material, the O or S atom into the Re[BOND]Cβ bond of the intermediate.

    9. [SbN(SbCl)3(NSbCl2)(NSiMe3)2·SbCl3], an Unusual Nitridoantimony Complex with a Heterocubane Structure (pages 569–570)

      Dipl.-Chem. Markus Rhiel, Dr. Frank Weller, Prof. Dr. Jürgen Pebler and Prof. Dr. Kurt Dehnicke

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199405691

      Thumbnail image of graphical abstract

      A white, sparingly soluble, and moisture-sensitive precipitate, formed almost quantitatively from SbCl3 and N(SiMe3)3, proved to be the title complex pictured here. In its heterocubane framework, only the N atom bearing the SbCl3 group displays nitride character; the others bearing the SiMe3 and SbCl2 substituents have imide character.

    10. Continuous Enzymatic Synthesis of 2′-Deoxythymidine-5′-(α-D-glucopyranosyl)diphosphate (pages 571–572)

      Dipl.-Chem. Astrid Zervosen, Dr. Lothar Elling and Prof. Dr. Maria-Regina Kula

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199405711

      Thumbnail image of graphical abstract

      The preparation of primary nucleotide sugars like 1 with sucrose synthase, a glycosyl transferase in plants, provides an alternative in enzymatic synthesis to the use of highly specific pyrophosphorylases. In an enzyme membrane reactor a continuous synthesis can be performed on preparative scale.

    11. Phenothiazinyl-Substituted Cyanines: Model Compounds for Molecular Switches (pages 572–575)

      Dipl.-Chem. Agnes Ehmann, Prof. Rudolf Gompper, Prof. Horst Hartmann, Dr. Thomas J. J. Müller, Dr. Kurt Polborn and Dr. Reiner Schütz

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199405721

      Thumbnail image of graphical abstract

      Almost orthogonal to the vinamidinium system, the phenothiazine unit in salts of type 1 is electronically “disconnected” from the conjugated system. By flash excitation of 1 an electron is transferred from the phenothiazine to the vinamidinium moiety, which gives rise to a relatively long-lived T1 state, most likely corresponding to the radical dication in 2. Compounds of type 1 are thus models for a molecular switch. X = BFmath image, ClOmath image.

    12. Reactions of C3O2 with Stabilized Triphenylphosphoranes Ph3P[DOUBLE BOND]CHX (X[DOUBLE BOND]CN, COMe, COPh) (pages 576–578)

      Dr. Luciano Pandolfo, Dr. Giacomo Facchin, Dr. Roberta Bertani, Prof. Paolo Ganis and Dr. Giovanni Valle

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199405761

      Thumbnail image of graphical abstract

      Linear neutral compound like 1 or zwitterionic heterocycles like 2 form exclusively from the reaction of C3O2 with the phosphorus ylides Ph3P [DOUBLE BOND] CHX (X [DOUBLE BOND] CN for 1, and COMe or COPh for 2) bearing an H atom on the ylidic C atom. In contrast to earlier investigations, neither Wittig reactions nor the formation of cyclobutanediones were observed.

    13. Reactivity of a Phosphanylcarbene (λ5-Phosphaacetylene) with Lewis Acids: X-Ray Crystal Structures of the First Carbene-Gallane Complex and C-Gallyl-Substituted Phosphorus Ylide (pages 578–580)

      Prof. Alan H. Cowley, François P. Gabbaï, Prof. Carl J. Carrano, Ladd M. Mokry, Dr. Marcus R. Bond and Dr. Guy Bertrand

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199405781

      Thumbnail image of graphical abstract

      A remarkably diverse reactivity toward Lewis acids is exhibited by the phosphanylcarbene (R2N)2PC̈SiMe3 (R [DOUBLE BOND] c-C6H11). The methylated Lewis acids MMe3 (M [DOUBLE BOND] Al, Ga, In) undergo 1,2 addition reactions to form the C-substituted phosphorylides 1 (X [DOUBLE BOND] Me), while the corresponding chlorides MCl3 form the first stable phosphanylcarbene–Lewis acid complexes 2 (X [DOUBLE BOND] Cl).

    14. [2 + 2]Cycloaddition of Norbornenes with Alkynes Catalyzed by Ruthenium Complexes (pages 580–581)

      Prof. Dr. Take-aki Mitsudo, Hiroshi Naruse, Dr. Teruyuki Kondo, Yoshihiko Ozaki and Prof. Dr. Yoshihisa Watanabe

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199405801

      Thumbnail image of graphical abstract

      The first C[BOND]C coupling catalyzed by a neutral Cp*Ru complex ([Cp*RuCl(cod)]) is reported in the reactions of norbornenes and norbornadiene (1) with different alkynes (2). Besides the [2 + 2] cycloadducts 3, the reaction with terminal alkynes and 1 unexpectedly also yields the 1,3-benzene derivatives 4.

    15. Activation of Glutathione Reductase by Light: A Novel Approach to Design Redox Photo-Enzymes (pages 581–583)

      Prof. Itamar Willner and Eran Zahavy

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199405811

      Light-induced electron transfer within a protein, coupled with chemical transformations, was achieved with the glutathione reductase modified by eosin isothiocyanate. The dye functions both as an initiator for the electron transfer and as a relay unit in the protein backbone that facilitates the electrical communication with the redox center at which the oxidized glutathione is reduced.

  4. Book Reviews

    1. Top of page
    2. Reviews
    3. Highlights
    4. Communications
    5. Book Reviews