Angewandte Chemie International Edition in English

Cover image for Vol. 23 Issue 7

July 1984

Volume 23, Issue 7

Pages 467–538

Currently known as: Angewandte Chemie International Edition

    1. Cover Picture (Angew. Chem. Int. Ed. Engl. 7/1984)

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198404671

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      The cover shows a photograph of moldy orange halves. Instinct warns us not to consume mold-infected foodstuffs. This is of vital importance since many of the metabolic products of molds—in the picture Aspergillus and Penicillium species—are highly toxic for human beings. The danger presented by mycotoxins was long underestimated, and natural-product chemists became interested in this class of substances only relatively recently. That today we nevertheless already know many of the structures, biological effects, and biosyntheses of mycotoxins as well as the precautions to be taken against them is shown in the review by B. Franck on p. 493 ff.

    2. Graphical Abstract (Angew. Chem. Int. Ed. Engl. 7/1984)

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198404672

  1. Reviews

    1. Top of page
    2. Reviews
    3. Communications
    4. Book Reviews
    1. Analysis of Enzyme Structure and Activity by Protein Engineering (pages 467–473)

      Prof. Dr. Alan R. Fersht, Jian-Ping Shi, Anthony J. Wilkinson, Prof. David M. Blow, Paul Carter, Dr. Mary M. Y. Waye and Dr. Greg P. Winter

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198404673

      The systematic alteration of proteins by site-directed mutagenesis of the corresponding gene is facilitated, on the one hand, by recombinant DNA technology and, on the other, by the chemical synthesis of DNA fragments. The altered activity of the mutant enzymes can then be directly correlated with structural changes, which in the ideal case can be investigated by high-resolution X-ray crystallography. For example, with tyrosyl-tRNA synthetase from Bacillus stearothermophilus it has been possible to tailor-make an enzyme with increased substrate specificity.

    2. Organolanthanoid Compounds (pages 474–493)

      Prof. Dr. Herbert Schumann

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198404741

      An enormous potential for catalysis and organic synthesis is offered by the title compounds, whose chemistry has been investigated over the last ten years. Derivatives of all the lanthanoids with organic ligands have been prepared and characterized. The full series of compounds of type 1 are known; 2 is shown as an example of the homoleptic type of compound.equation image

    3. Mycotoxins from Mold Fungi — Weapons of Uninivited Fellow-Boarders of Man and Animal: Structures, Biological Activity, Biosynthesis, and Precautions (pages 493–505)

      Prof. Dr. Burchard Franck

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198404931

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      Epidemic-like mycotoxicoses can be instigated by molds which spread aggressively on foodstuffs and, hence, lead to formation of mycotoxins, e.g. aflatoxin 1 and ergotamine 2. The manifold types of structures displayed by mycotoxins are derived from only three groups of key biogenetic building blocks: polyketides, isopentenyl pyrophosphate, and amino acids.

  2. Communications

    1. Top of page
    2. Reviews
    3. Communications
    4. Book Reviews
    1. Thin-Layer Chromatographic Enantiomeric Resolution via Ligand Exchange (page 506)

      Dr. Kurt Günther, Dr. Jürgen Martens and Maren Schickedanz

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198405061

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      Racemic amino acids can be resolved straightforwardly and rapidly using thinlayer chromatography. Decisive in this respect is that the TLC plates are impregnated with the chiral selector 1. The method also enables the determination of the enantiomeric purity of amino acids.

    2. Topological Charge Stabilization and the Equilibrium between P4S3 and As4S3 (pages 506–507)

      Prof. Dr. Benjamin Gimarc and P. J. Joseph

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198405062

      The cage molecule PS3As3, a beautiful example of the operation of the rule of topological charge stabilization, is formed upon mixing P4S3 and As4S3 in the molar ratio 1:3. The rule states that particularly stable structures result from substitution of electronegative heteroatoms at sites where electron charges are more negative in the homoatomic, isoelectronic reference frame (here Pmath image).

    3. [(Me2N)2SF2]2⊕, a Sulfur(VI) Dication (pages 507–508)

      Dr. Hartmut Henle, Reinhard Hoppenheit and Prof. Dr. Rüdiger Mews

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198405071

      The ability to electrophilically methylate a cation such as 2 demonstrates the extraordinary preparative potential of [CH3OSO]X. The reagent methylates 1 exclusively at the thiazyl nitrogen, and the salts 3 of the sulfur(VI) dication are obtained via salts 2. Compounds 3a, X = AsF6, and 3b, X = SbF6, are stable solids.

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    4. A Facile Route to Benzoannelated Centrotriquinanes (pages 508–509)

      Dr. Dietmar Kuck

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198405081

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      The fascinating centropolyquinane group of compounds is characterized by a central, common C atom. The title compounds, 1 and 2, can be obtained surprisingly simply from 2,2-disubstituted 1,3-indanediols.

    5. 1,2,3-Benzoxadiazole — Detection in an Argon Matrix and in Solution (pages 509–511)

      Dr. Reinhard Schulz and Prof. Dr. Armin Schweig

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198405091

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      The existence of 1,2,3-benzoxadiazole 1 in an argon matrix at 15 K and in non-polar solvents at room temperature could be established by IR and UV/VIS spectroscopy, respectively. Even the radiation from the Nernst glower induces the isomerization 1 [RIGHTWARDS ARROW] 2.

    6. Asymmetric Synthesis of a Novel Enantiomerically Pure Prostaglandin Building Block (pages 511–512)

      Priv.-Doz. Dr. Hans-Joachim Gais, Dr. Thomas Lied and Dr. Karl L. Lukas

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198405111

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      A general route to prostaglandins is opened up by the synthesis of the chiral compound 2, R = tBuMe2Si, from the readily accessible keto ester 1. Compound 2 can be linked to various side chains by means of a 1,4-addition-carbonyl-olefination strategy.

    7. The First C4B6 Carbaborane (pages 512–514)

      Prof. Dr. Roland Köster, Günter Seidel and Dr. Bernd Wrackmeyer

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198405121

      A novel type of organocarbaborane, the nido-cluster 2, was prepared from the “monomeric” organo-closo-carbaborane 1 using a redox method, which should be generally applicable. The positions of the ten skeletal atoms in 2 can be assigned by NMR spectroscopy.

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    8. [Cu6I11]5⊖—a Polyanion with Trigonal-Prismatic Arrangement of Six Metal Atoms (pages 514–515)

      Dipl.-Chem. Farbod Mahdjour-Hassan-Abadi, Prof. Dr. Hans Hartl and Prof. Dr. Joachim Fuchs

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198405141

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      A rare arrangement of metal atoms, previously not observed in copper compounds, occurs in the iodocuprate(I) ion in [Cu6I11]5⊖. The Cu atoms form a trigonal prism to whose six edges and five faces the eleven iodine atoms are bonded.

    9. Chemistry of the Novel Oxo Half-Sandwich Complex (η5-C5Me5)ReO3: Functionalization and Aggregation (pages 515–517)

      Prof. Dr. Wolfgang A. Herrmann, Dr. Ricardo Serrano, Ulrich Küsthardt, Prof. Dr. Manfred L. Ziegler, Dr. Ernst Guggolz and Thomas Zahn

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198405151

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      The manifold reactivity of the title compound has led to a vast number of novel rhenium complexes. A selection is shown below.

    10. A Rational Synthetic Method for 2H-Isoindoles (pages 517–518)

      Prof. Dr. Richard P. Kreher and Norbert Kohl

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198405171

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      2H-Indoles 2 with specific substitution pattern are obtained by the retro-ene reaction of N-propynyl compounds 1. The educts are readily accessible and only a few volatile side products are formed in the thermolysis.

    11. α-Keto Esters and α-Keto Nitriles via Ruthenium-Catalyzed Dehydrogenation of α-Hydroxy Esters and Cyanohydrins with tert-Butyl Hydroperoxide (page 518)

      Dr. Masato Tanaka, Dr. Toshi-aki Kobayashi and Toshiyasu Sakakura

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198405181

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      A new method for dehydrogenation of functionalized alcohols 1, Z[DOUBLE BOND]CO2-alkyl or CN, is their Ru-catalyzed reaction with tBuOOH. The reaction proceeds under extremely mild conditions; for 1, R[DOUBLE BOND](E)-PhCH[DOUBLE BOND]CH, the double bond is not epoxidized.

    12. Synthesis of Substituted, Partially Hydrogenated [1,2,4]Triazino[4,5-a]indoles and Pyrrolo[1,2-d][1,2,4]triazines (pages 518–519)

      Dr. Henning Böttcher and Bernd Arzt

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198405182

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      A novel cycloaddition with the Mitsunobu reagent (diethyl azodicarboxylate/PPh3) converts the hydroxyalkylindoles 1 into the triazinoindoles 2. Derivatives without an annelated benzene ring can be obtained analogously. Generalization of the synthesis ought to lead to further interesting heterocycles.

    13. Synthesis of Enantiomerically Pure 1,7-Dioxaspiro[5.5]undecanes, Pheromone Components of the Olive Fly (Dacus oleae) (pages 519–520)

      Priv.-Doz. Dr Hartmut Redlich and Priv.-Doz. Dr Wittko Francke

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198405191

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      Spiroacetals occurring as volatile communication substances of insects are attracting increasing interest. By starting from D-glucose, both enantiomers of 1,7-dioxaspiro[5.5]undecane 1 can now be synthesized. A dithioacetal is the key intermediate.

    14. Nitrosoferrocene (pages 521–522)

      Prof. Dr. Max Herberhold and Dr. Ludwig Haumaier

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198405211

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      “Ferrocenylation” of an NO ligand in the coordination sphere of a chromium complex led to generation of nitrosoferrocene 1 and, after removal of the metal, to its isolation. Solid 1 decomposes slowly at room temperature; the violet solutions are more stable.

    15. Pentamethylcyclopentadienyllutetium Derivatives of Dimethylphosphoniobis(methanide) (pages 522–523)

      Prof. Dr. Herbert Schumann, Ilse Albrecht, Dr. Friedrich-Wilhelm Reier and Dipl.-Chem. Ekkehardt Hahn

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198405221

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      The first X-ray structure analysis of a lanthanoid-phosphorus ylide complex has been carried out on the lutetium derivative 1. Compound 1, which is extremely sensitive to air and moisture, was synthesized from (C5Me5)2LuCl2Na(Et2O)2 and Li(CH2)2P(CH3)2.

    16. Mechanism of the Cyclocotrimerization of Diethyl(hydrido)thiophosphorus with Alkynes (pages 523–524)

      Prof. Dr. Ekkehard Lindner, Claus-Peter Krieg, Dr. Wolfgang Hiller and Riad Fawzi

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198405231

      All the intermediates in the (σ-C3F7)Fe(CO)4I-catalyzed reaction of S[DOUBLE BOND]PHEt2 with electron-deficient alkynes could be characterized by complete elemental analysis and by IR, 31P-NMR, and mass spectroscopy: X-ray structure analyses could also be performed on some of these complexes. The reaction affords highly substituted heterocycles. All intermediates contain the fragment (σ-C3F7)Fe(CO)2.

    17. F3CN[DOUBLE BOND]C[DOUBLE BOND]C[DOUBLE BOND]NCF3, a New Bridge Ligand: Formation by CC Linkage of Two CF3NC Ligands and Cleavage of a Mo[TRIPLE BOND]Mo Bond (pages 525–526)

      Dr. Dieter Lentz, Irene Brüdgam and Prof. Dr. Hans Hartl

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198405251

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      The molybdenum complex 2 with the novel heterocumulene bridge was obtained by reaction of CF3NC with [Mo(C5H5)2(CO)2]2. 1 is initially formed with η2-bonded CF3NC. Addition of another molecule of CF3NC to 1 then leads to formation of a C[DOUBLE BOND]C bond and to cleavage of the Mo—Mo bond. In 2, one molybdenum atom is part of a five-membered ring, while the other is part of a three-membered ring.

    18. Hindered Rotation of tert-Butyl Groups in Radical Cations of Highly Substituted Alkenes (pages 526–527)

      Dr. Horst Eierdanz, Siegfried Potthoff, Dr. Rudolf Bolze and Prof. Dr. Armin Berndt

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198405261

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      The free rotation of two closely neighboring tert-butyl groups bonded to sp2-C atoms can be partially removed. Hindered rotation of this sort was already known for 1,8-di-tert-butylnaphthalene; novel is the detection of this phenomenon in the radical cations of type 1 and 2.

    19. Phosgene as a Reagent for the Enantiomeric Resolution of 1,2- and 1,3-Diols, α-Amino Alcohols, α-Hydroxy Acids, and N-Methyl-α-Amino Acids by Gas Chromatography (pages 527–528)

      Prof. Dr. Wilfried A. König, Eberhard Steinbach and Karin Ernst

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198405271

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      The enantiomeric compositions of chiral diols can be determined by gas chromatography. 1,2- and 1,3-Diols, respectively, are converted by phosgene-containing solutions into 1 and 2, which are separated on the chiral stationary phase XE-60-L-valine-(R)-α-phenylethylamide. Additional classes of compounds which can also be resolved analogously are mentioned in the title.

    20. High-Pressure Phases of KSi, KGe, RbSi, RbGe, CsSi, and CsGe with the NaPb-Type Structure (pages 528–529)

      Dr. habil. Jürgen Evers, Gilbert Oehlinger, Dipl.-Ing. Gerhard Sextl and Prof. Dr. Armin Weiss

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198405281

      Six novel phases of the 1:1-silicides and -germanides of K, Rb, and Cs have been synthesized using a high-temperature method (4 GPa, 600°C); under normal conditions they are metastable. The six compounds crystallize in the cubic KGe-type at normal pressure; the nine phases belong to the tetragonal NaPb-type, which have previously only been found in stannides and plumbides of the alkali metals. The constant axes ratio c/a ≈ 1.63 suggests geometrical relationships of the NaPb-type.

    21. Hydridoplatinum(II) Complexes with Phosphites and Phosphonites and their Reactions with Methyl Acrylate (pages 529–530)

      Dipl.-Natw. Werner R. Meyer and Prof. Dr. Luigi M. Venanzi

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198405291

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      High reactivity and regioselectivity in alkene insertions characterize the novel complexes 1, L[DOUBLE BOND]P(OMe)3 or PMe(OMe)2. They can readily be prepared by reduction of cis-PtCl2L2 with NaBH4. Irrespective of the solvent used, methyl acrylate always adds to 1 as a branched ligand. Apart from 2, complexes 1 L[DOUBLE BOND]PEt3, also afford the isomer with the linear ligand.

    22. Synthesis and Determination of the Absolute Configuration of (+)-Delesserine, a Metabolite of the Red Marine Alga Delesseria sanguinea (Lamouroux) (pages 530–531)

      Prof. Dr. Dieter Seebach, Dr. Matthias Dust, Dr. Reto Naef and Dipl.-Chem. Markus Bänziger

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198405301

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      A straightforward synthesis of (+)-delesserine 2 starts from the lactic acid building block 1 and diethyl (R,R)-tartrate. In this way, the absolute configuration of the natural product could be established. The blood anticoagulant-effect of Delesseria sanguinea, a red marine alga found on the European Atlantic coast, is not ascribable to 2.

    23. Carbonyl Olefinations with Methylenemolybdenum Reagents in Aqueous or Ethanolic Media (pages 531–532)

      Prof. Dr. Thomas Kauffmann, Petra Fiegenbaum and Raphael Wieschollek

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198405311

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      Selective carbonyl olefinations of aldehydes or ketones with OH groups, e.g. 1, are facilitated by the readily accessible compounds Cl(O)Mo[DOUBLE BOND]CH2 and Cl3Mo[DOUBLE BOND]CH2. In contrast to Ti and Zn reagents, these Mo compounds can even be used in the presence of water or ethanol.

    24. Selective Synthesis of Carbonyl Olefinating or Alkylating Reagents from MoCl5 and MeLi by Changing the Solvent or the Rate of Addition of MeLi (pages 532–533)

      Prof. Dr. Thomas Kauffmann and Gudrun Kieper

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198405321

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      The simple change from rapid to slow admixture of the educts is decisive in determining whether carbonyl olefinating reagents (1, 2) + CH4 or carbonyl alkylating reagents (3, 4) + ethane are formed from MoCl5 and MeLi in tetrahydrofuran.

    25. 25Mg-NMR: A Method for the Characterization of Organomagnesium Compounds, their Complexes, and Schlenk Equilibria (pages 534–535)

      Dr. Reinhard Benn, Prof. Dr. Herbert Lehmkuhl, Klaus Mehler and Dr. Anna Rufińska

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198405341

      Predominantly covalent Mg—C bonds are present in dicyclopentadienylmagnesium, as indicated by 25Mg-NMR spectroscopy. The large range of the 25Mg chemical shifts (ca. 200 ppm) also facilitates clarification of other controversial bonding behavior. For the investigation of Schlenk equilibria [eq. (a)], the method has the advantage that all three species can be identified directly.

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  3. Book Reviews

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