Angewandte Chemie International Edition in English

Cover image for Vol. 24 Issue 8

August 1985

Volume 24, Issue 8

Pages 617–718

Currently known as: Angewandte Chemie International Edition

    1. Cover Picture (Angew. Chem. Int. Ed. Engl. 8/1985)

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198506171

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      The cover shows an unfolded phase tetrahedron with the base A, B, C and the apex E. Such diagrams facilitate the understanding of the phase relationships in quaternary systems A-B-C-E at constant temperature. Quaternary systems containing water (A), oil (B), amphiphile (C), and electrolyte (E) are of importance for the tertiary recovery of petroleum as well as for the preparation of concentrated solutions of pharmaceuticals. The phase tetrahedron is valid for temperatures below the temperature of the three-phase body in the system A-B-C. cpα and cpε are critical points. Further details are reported by M. Kahlweit et al. on page 654ff.

  1. Reviews

    1. Top of page
    2. Reviews
    3. Communications
    4. Book Reviews
    1. Enzymes as Catalysts in Synthetic Organic Chemistry [New Synthetic Methods (53)] (pages 617–638)

      Prof. Dr. George M. Whitesides and Prof. Dr. Chi-Huey Wong

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198506173

      The use of esterases, lipases, and other enzymes in organic synthesis is becoming increasingly common. In addition to the obvious advantages of enzymes is the fact that the intermediates in multistep reactions often do not need to be purified since the enzyme transforms only a specific substrate. Thus, the treatment of a reaction mixture with an enzyme is also a form of form of purification.

    2. The Construction of New Proteins and Enzymes-a Prospect for the Future? (pages 639–653)

      Prof. Dr. Manfred Mutter

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198506391

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      The unique properties of proteins and enzymes are largely determined by their three dimensional structure. In order to design artificial proteins, it is therefore crucial to find sequences of amino acids that undergo specific folding to form stable tertiary structures. Investigations on model peptides indicate that this goal can be reached.

    3. Phase Behavior of Ternary Systems of the Type H2O[BOND]Oil[BOND]Nonionic Amphiphile (Microemulsions) (pages 654–668)

      Prof. Dr. Manfred Kahlweit and Dr. Reinhard Strey

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198506541

      The investigation of the phase behavior of multicomponent systems is of interest in both pure and applied research. An example of a practical application is the preparation of stable, homogeneous solutions of pharmaceuticals or insecticides in mixtures of water, nonpolar solvents (“oils”), and amphiphiles. Such solutions must be able to undergo dilution without separating into two phases. Knowledge of the phase behavior of these systems permits the amount of amphiphile to be minimized.

    4. Selective Reactions Using Organoaluminum Reagents [New Synthetic Methods (54)] (pages 668–682)

      Dr. Keiji Maruoka and Prof. Dr. Hisashi Yamamoto

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198506681

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      Organoaluminum compounds are characterized by oxyphilicity and ambiphilic behavior. These properties have been used to develop new synthetic methods with excellent selectivities. One example is the variant of the Beckmann rearrangement shown below.

  2. Communications

    1. Top of page
    2. Reviews
    3. Communications
    4. Book Reviews
    1. Tridentate Oxygen Ligands as Cyclopentadienyl Equivalents: Structure and Properties of [LRh(μ-CO)3RhL], L = [(C5H5)Co{P(O)R2}3] (pages 683–684)

      Prof. Dr. Wolfgang Kläui, Prof. Dr. Mario Scotti, Prof. Dr. Mauricio Valderrama, Soledad Rojas, Prof. George M. Sheldrick, Priv.-Doz. Dr. Peter G. Jones and Tina Schroeder

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198506831

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      The anionic half-sandwich complexes L(R[DOUBLE BOND]OMe, OEt) act as tridentate ligands. They form inert complexes with metals in low oxidation states, an unusual behavior for oxygen ligands. For example, the Co2Rh2 complex [LRh(μ-CO)3RhL], R[DOUBLE BOND]OEt, was prepared and its structure determined by X-ray analysis.

    2. Extremely Long-Wavelength Charge-Transfer Absorptions of Binuclear Complexes with Azo-Modified 2,2′-Bipyridyl Ligands (pages 684–685)

      Dipl.-Chem. Stephan Kohlmann, Dipl.-Chem. Sylvia Ernst and Priv.-Doz. Dr. Wolfgang Kaim

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198506841

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      Intense charge-transfer absorptions at wavelengths up to the near-infrared region (700–950 nm) are exhibited by binuclear complexes such as 1 and 2, which contain the low-spin d6 metal-complex fragments Mo(CO)4, W(CO)4, Mn(CO)3Br, and [Ru(bpy)2]2⊕. This is due to very low lying π-acceptor levels of the heteroarene ligands and to the chelation.

    3. Three-Phase Synthesis of Oligonucleotides (pages 685–687)

      Prof. Dr. Hartmut Seliger and Dr. Kailash Chand Gupta

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198506851

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      Polymer-bound reagents of the nucleoside phosphoramidite type, such as 1 (P = Merrifield resin, B = thymin-1-yl, DMTr = dimethoxytrityl) are superbly suitable for the chemical synthesis of oligonucleotides. Upon activation with tetrazole, they are released and can be coupled with polymerbound nucleosides. 1 is stable upon storage and reacts after 15 months with the same yields.

    4. Calculation of the Charge Distribution in Conjugated Systems by a Quantification of the Resonance Concept (pages 687–689)

      Priv.-Doz. Dr. Johann Gasteiger and Dipl.-Chem. Heinz Saller

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198506871

      The assignment of weights to the resonance structures of organic compounds and the determination of the resulting charge distribution can be rapidly accomplished using a new calculation procedure. The method takes into consideration, among other things the π-orbital electronegativities and changes in the bonding structure.

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    5. (NEt4)2[Cl3Mo(μ-S2)(μ-Cl)2MoCl3], a Paramagnetic Molybdenum(IV) Compound with a Metal-Metal Bond (pages 689–690)

      Prof. Dr. Ulrich Müller, Dipl.-Chem. Paul Klingelhöfer, Doz. Dr. Claus Friebel and Doz. Dr. Jürgen Pebler

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198506891

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      A MoMo single bond and one unpaired electron per metal atom are present in the binuclear complex anion 1. This follows from the metal-metal distance, the magnetic susceptibility, and the ESR spectra. The tetraethylammonium salt of 1 was synthesized from molybdenum pentachloride and NEt4SH.

    6. Simplification of Spectra for the Determination of Coupling Constants from Homonuclear Correlated 2D NMR Spectra (pages 690–692)

      Prof. Dr. Horst Kessler and Dipl.-Chem. Hartmut Oschkinat

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198506901

      Without additional measurements having to be made, coupling constants can be determined from H,H-COSY spectra using the DISCO (Difference and Sums in COSY spectra) method. The structure elucidation of compounds with complicated 1H-NMR spectra, e.g., natural products, is thereby facilitated.

    7. Marked Increase in the Regioselectivity of Radical Substitution: Minisci Reaction in a Two-Phase System (pages 692–693)

      Prof. Dr. Gottfried Heinisch and Mag. pharm. Gerhard Lötsch

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198506921

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      The regioselectivity of radical ethoxycarbonylation of π-electron-deficient N-heteroarenes such as 4-pyridinecarbonitrile and pyrazine can be markedly increased in a two phase system. As shown by the synthesis of the esters 1 and 2, R′ [DOUBLE BOND] COOEt, monosubstitution is also achieved when the radicals are present in large excess.

    8. Proton Exchange between Arenium Ions and Arenes in the Gas Phase (pages 693–695)

      Dr. Dietmar Kuck, Dr. Steen Ingemann, Leo J. de Koning, Prof. Dr. Hans-Friedrich Grützmacher and Prof. Dr. Nico M. M. Nibbering

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198506931

      A new application of Fourier transform ion cyclotron resonance mass spectrometry is the investigation of the proton exchange reaction in the collision complexes formed between simple arenium ions and arenes. Only for degenerate reactions (R [DOUBLE BOND] R′) is a (surprisingly slow) exchange process observed (R [DOUBLE BOND] R′ [DOUBLE BOND] H or CH3; R [DOUBLE BOND] H, R′ [DOUBLE BOND] CH3).

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    9. Reaction of Ethylene Oxide with Sulfur Dioxide in the Presence of Cesium Ions: Synthesis of 1,3,6,9,2λ4-Tetraoxathia-2-cycloundecanone (page 695)

      Prof. Dr. Herbert W. Roesky and Hans Georg Schmidt

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198506951

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      The eleven-membered sulfur-containing heterocycle 1 is formed from ethylene oxide and SO2 in the presence of cesium salts in 20% yield. The structure of 1 was determined by X-ray diffraction analysis. Compounds such as 1 are interesting because the complexing properties of crown ethers can be finely tuned by the introduction of other heteroatoms.

    10. Dilithio(phenylsulfonyl)trimethylsilylmethane: Synthesis, 13C/1H-NMR Characterization, and Lithium-Titanium Exchange (pages 696–697)

      Dipl.-Ing. Jürgen Vollhardt, Priv.-Doz. Dr. Hans-Joachim Gais and Dr. Karl L. Lukas

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198506961

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      The first dilithioalkyl sulfone, the title compound 2, was obtained by stepwise lithiation of the trimethylsilyl sulfone 1 with nBuLi. Compounds such as 2 are of interst with respect to their structure and their synthetic potential, e.g., for the preparation of novel functionalized organometallic compounds.

    11. Synthesis and Structure of the [Ni38Pt6(CO)48H6−n]n− (n=5, 4) Ions: Ni-Pt Clusters as Models for “Cherry” Crystallites (pages 697–698)

      Alessandro Ceriott, Francesco Demartin, Prof. Dr. Giuliano Longoni, Mario Manassero, Mario Marchionna, Gianluigi Piva and Mirella Sansoni

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198506971

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      A Pt6 octahedron surrounded by a second octahedron containing 38 Ni atoms forms the metal framework of the cluster ions [Ni38Pt6(CO)48H6−n]n− (n=3–6), which are easily synthesized from [Ni6(CO)12]2−, PtCl2, and H+. Such clusters are molecular models for “cherry” crystallites, which are known from catalyst research.

    12. Reactive Metabolites of Carcinogenic Polycyclic Hydrocarbons: Synthesis and Trapping Reaction of 9-Hydroxybenzo[a]pyrene 4,5-Oxide (pages 699–700)

      Dipl.-Chem. Werner Bochnitschek, Dipl.-Chem. Albrecht Seidel, Prof. Dr. Horst Kunz and Prof. Dr. Franz Oesch

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198506991

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      In the Ames test, 9-hydroxybenzo[a]pyrene is mutagenic. The labile 4,5-oxide 1 is presumed to be the reactive species. It has been synthesized from 9-benzo[a]pyrenyl acetate and trapped with ethanethiol. The nucleophilic attack of the thiolate takes place regioselectively at C-5 of 1. In contrast, benzo[a]pyrene 4,5-oxide, which lacks a hydroxyl group, is attacked at both C-4 and C-5.

    13. Allene Claisen Rearrangement with 1,4-Chirality Transfer (pages 700–701)

      Prof. Dr. Dieter Hoppe, Charlotte Gonschorrek, Dr. Ernst Egert and Dieter Schmidt

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198507001

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      A simple route to the highly substituted enantiomerically pure 1,3-alkadienes 3 is provided by the rearrangement of the adduct prepared from the allene 1 (Cb[BOND]C([BOND]O)NiPr2, R′ =; (C6H5CH2)) and the ketene N,O-acetal 2 (R[BOND]CH3). The transition state for the rearrangement could be determined from knowledge of the absolute configurations of the educt 1 and the product 3.

    14. Synthesis and Structure of the Spirocluster [(η5-C5H5)3Mo3As(CO)6{CHP(C6H5)3}] (pages 702–703)

      Dipl.-Chem. Klaus Blechschmitt, Dipl.-Chem. Thomas Zahn and Prof. Dr. Manfred L. Ziegler

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198507021

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      An alkylidene group that bridges a maingroup element and a transition-metal element is present in the spiro cluster 1. Complex 1 was prepared from [(η5-C5H5)3 Mo3(CO)63-As)] and the Wittigreagent (C6H5)3P[DOUBLE BOND]CH2.

    15. Cleavage of a C[BOND]C Bond in the Catalytic Hydrosilylation of Camphor Oxime (pages 703–704)

      Prof. Dr. Henri Brunner and Richard Becker

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198507031

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      Surprisingly, metal-catalyzed hydrosilylation of camphor oxime 1 does not lead to bornylamine but rather, enantioselectively, to 1-(2-aminoethyl)-2,2,3-trimethylcyclopentane 2. The bond between the bridgehead C atom and the oxime C atom is cleaved in the reaction.

    16. Dinuclear Nickel Complexes with Bridging Allyl Ligands (pages 704–705)

      Dr. Rudolf Hanko

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198507041

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      The first synthesis of an allyl-bridged Ni-Ni complex such as 1 (R, R′[DOUBLE BOND] alkyl, X[DOUBLE BOND] halogen, C3H5) was achieved by reaction of Ni0 and Ni11 complexes in the presence of triorganophosphanes. Analogous Pd and Pt complexes have long been known.

    17. Selective 1H, 13C-NOE Difference Spectroscopy for the Elucidation of Structures (pages 705–706)

      Dr. Peter Bigler and Dr. Matthias Kamber

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198507051

      Structure elucidations are also possible for compounds with strongly overlapping 1H-NMR signals employing a new procedure based on the use of the heteronuclear Overhauser effect. This 1D procedure requires only relatively short measuring times, and a knowledge of the coupling constants is not necessary. The capability of the method is demonstrated on a tricyclic β-Keto ester containing a lactone bridge.

    18. Novel Cobalt- and Nickel-Clusters with S and PPh3 as Ligands; Crystal Structures of [Co7S6(PPh3)5Cl2], [Co6S8(PPh3)6]+[CoCl3(THF)], [Ni8S6Cl2(PPh3)6], and [Ni8S5(PPh3)7] (pages 706–709)

      Prof. Dr. Dieter Fenske, Dipl.-Chem. Johannes Hachgenei and Dipl.-Chem. Johannes Ohmer

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198507061

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      A cube lacking one corner is one way to describe the structure of the cluster 1, which can be prepared from [CoCl2 (PPh3)2] and S(SiMe3)2 in tetrahydrofuran. All Co atoms are coordinated in a distorted tetrahedral fashion, either by three S atoms and the P atom of the PPh3 ligand or by three S ligands and a Cl ligand.

    19. Crinipellins, the First Natural Products with a Tetraquinane Skeleton (pages 709–711)

      Prof. Dr. Timm Anke, Dr. Jutta Heim, Dr. Falk Knoch, Dipl.-Chem. Ursula Mocek, Dr. Bert Steffan and Prof. Dr. Wolfgang Steglich

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198507091

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      The range of cyclopentanoid natural products that exhibit antibiotic activity is expanded by the isolation of the crinipellins, for example, crinipellin A 1a and its O-acetyl derivative 1b. These diterpenoids, which contain an α-methylene ketone group, are produced by cultures of the fungus Crinipellis stipitaria.

    20. A Simple Approach to the Naphthol[1,8-bc]pyrandione System (pages 711–712)

      Prof. Dr. Wolfgang Steglich, Dipl.-Chem. Hans-Theo Huppertz and Dr. Bert Steffan

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198507111

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      Model studies of the biosynthesis of the bolete pigments badione A and B indicate that their naphthopyradine partial structure 4 is formed as follows: Diels-Alder dimerization of 1 and subsequent oxidation lead to 2, which, after base-induced cleavage, gives 3; this cyclizes finally to 4.

    21. Monomeric, Mononuclear Enediolate Complexes of Zirconium: Molecular Geometry and Electronic Structure of the Products of Reductive CO Coupling on the Metal (pages 712–713)

      Prof. Dr. Peter Hofmann, Dipl.-Chem. Martin Frede, Dipl.-Chem. Peter Stauffert, Dipl.-Chem. Wiltraud Lasser and Prof. Dr. Ulf Thewalt

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198507121

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      A transition from σ2, π to σ2 coordination occurs in going from R [DOUBLE BOND] Me to R [DOUBLE BOND] tBu in the zirconium complexes 1, Cp* = C5Me5. The chelate ring is folded in the first case and planar, for steric reasons, in the second. This observation is in accord with the predictions of MO theory.

    22. Can 1,2,3-Oxadiazole be Stable? (pages 713–715)

      Dr. Minh Tho Nguyen, Prof. Dr. Anthony F. Hegarty and Prof. Dr. Jose Elguero

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198507131

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      No is the answer to the question posed in the title of the article. According to an ab initio study, 1,2,3-oxadiazole 1 is 8.9 Kcal/mol higher in energy than the isomer formyldiazomethane 2 (R[BOND]H).

    23. Phosphorus-Substituted Thioformamides and Thioformimidates: Molecular Structure and Solid State 13C-NMR Spectra (pages 715–716)

      Dr. Klaus Albert, Dr. Andreas Bruns, Dr. Hans Förster, Dr. Wolfgang Hiller and Prof. Dr. Udo Kunze

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198507151

      The presence of two symmetry-independent molecules in the unit cell-not E/Z isomerism in the crystal-is responsible for the existence of two N-methyl signals in the solid-state 13C-NMR spectrum of the thioamide 1. Even small conformational differences in the molecule in the solid state have a considerable effect on the chemical shift.

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  3. Book Reviews

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