Angewandte Chemie International Edition in English

Cover image for Vol. 16 Issue 7

July 1977

Volume 16, Issue 7

Pages 423–492

Currently known as: Angewandte Chemie International Edition

    1. Cover Picture (Angew. Chem. Int. Ed. Engl. 7/1977)

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.197704231

    2. Graphical Abstract (Angew. Chem. Int. Ed. Engl. 7/1977)

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.197704232

  1. Reviews

    1. Top of page
    2. Reviews
    3. Communications
    4. Abstracts
    5. Book Reviews
    1. The Wittig Reaction in Industrial Practice (pages 423–429)

      Prof. Dr. Horst Pommer

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.197704233

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      The synthesis of active compounds and fine chemicals in industrial research has become a very important application of the Wittig reaction. Examples are vitamin A, β-carotene, juvenile hormone, as well as aromas and flavors. The equation shown below is a facsimile from Wittig's original publication.

    2. Steric Interactions in Organic Chemistry: Spatial Requirements of Substituents (pages 429–441)

      Dr. Hans Förster and Prof. Dr. Fritz Vögtle

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.197704291

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      How “big” are substituents, and how can the relative sizes of a series of substituents be established? A promising approach seems to lie in the analysis of conformational processes, particularly in the biphenyl, triptycene, and phane systems.

    3. Photodielectric Polymers for Holographic Use (pages 441–448)

      Dr. Shimon Reich

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.197704411

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      Holograms can be recorded on photographic plates or special polymers: in the former case the holographic information is stored by deposited silver and in the latter by local changes in the refractive index.

    4. Entropy, Binding Energy, and Enzymic Catalysis (pages 449–459)

      Dr. M. I. Page

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.197704491

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      The rate and specificity of enzyme-catalyzed reactions still raise many questions. The study of entropy and binding energy can contribute to their solution.

  2. Communications

    1. Top of page
    2. Reviews
    3. Communications
    4. Abstracts
    5. Book Reviews
    1. (A[RIGHTWARDS ARROW]D)-Cyclization of a Nickel(II) Δ18-Dehydro-1-methylidene-1,19-secocorrinate (pages 459–461)

      Dipl. sc. nat. Vittorio Rasetti, Dr. Bernhard Kräutler, dipl.-sc. nat. Andreas Pfaltz and Prof. Dr. Albert Eschenmoser

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.197704591

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      In connection with the biosynthesis of vitamin B12 the exceptional ease of linkage of rings A and D in the nickel(II) secocorrinate (1) warrants particular interest.

    2. Difluorooxobromine(v) Ion, BrOFmath image (page 461)

      Dr. Manfred Adelhelm and Dr. Eberhard Jacob

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.197704611

      BrO2F and PtF6 surprisingly afford the salt BrOFmath imagePtFmath image. So far this appears to be the only case in which oxygen is partially eliminated from an oxide fluoride by PtF6.

      • equation image
    3. Homologization of Aldehydes and Ketones to Thiiranes or S-Vinyl Thiocarbamates via 2-Alkylimino-1,3-oxa-thiolanes (pages 462–463)

      Dr. Dieter Hoppe and Dipl.-Chem. Rainer Follmann

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.197704621

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      A general synthesis of thiiranes(1) starting from carbonyl compounds and a dithiocarbonic acid derivative involves direct formation of the C[BOND]C bond. One of the intermediates can be converted into the vinyl thiocarbamate (2).

    4. Phenyl-[2,2-dimethyl-1-(trimethylsiloxy) propylidene]-arsane, and Arsane with an Isolated As[DOUBLE BOND]C Bond (pages 463–464)

      Doz. Dr. Gerd Becker and Dipl.-Chem. Gerhard Gutekunst

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.197704631

      The first open-chain arsane with an isolated As[DOUBLE BOND]C double bond, (2), has now been prepared by rearrangement of the pivaloylarsane (1). Compound (1) is obtainable from phenylbis(trimethylsilyl)arsane.

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    5. [C5H5(CO)2Mn[BOND]N2H2[BOND]Cr(CO)5], a Complex with a Diazene Bridge and Two Different Coordination Centers (pages 464–465)

      Dr. Dieter Sellmann and Dr. Klaus Jödden

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.197704641

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      The first heteronuclear diazene-transition metal complex(1) containing the M[BOND]HN[DOUBLE BOND]NH[BOND]M′ unit has now been prepared via the hydrazine complex. According to the coupling constants of the NH protons, compound (1) exists in the trans form.

    6. Synthesis of Alkyne-Bridged Dinuclear Complexes by Reaction of trans-Halotetracarbonyl(methylcarbyne)-tungsten with Methylenebis(diphenylarsane) (pages 465–466)

      Prof. Dr. Ernst Otto Fischer, Dipl.-Chem. Alexander Ruhs, Dipl.-Chem. Peter Friedrich and Doz. Dr. Gottfried Huttner

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.197704651

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      Formation of dimethylacetylene from two [TRIPLE BOND] C[BOND]CH3 moieties is found to take place on reaction of the methylcarbyne complex X(CO)4W[TRIPLE BOND]C[BOND]CH3 (X[DOUBLE BOND]Cl, Br) with the donor ligand methylenebis(diphenylarsane). The dinuclear complex (1) is obtained. Phenylcarbyne complexes react differently.

    7. Temperature Dependence of the Selectivity of the Halogen Donors XCCl3 (pages 466–467)

      Priv.-Doz. Dr. Bernd Giese and Dipl.-Chem. Klaus Jay

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.197704661

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      Perhalomethanes like BrCCl3 and CCl4 are frequently used as halogenation reagents. The temperature dependence of the stereoselectivity of halogen transfer from XCCl3 to the norbornyl radical has now been established. The isoselective temperature is 90°C.

    8. 2,3,11,12-Tetraphenyl-1,4,7,10,13,16-hexaoxa-2,11-cyclooctadecadiene: A New Crown Ether from Benzoin (pages 467–468)

      Dr. Andreas Merz

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.197704671

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      The first macrocyclic crown ether containing double bonds in the ring has now become readily available. The double bodns should permit facile derivatization of the molecule.

    9. η-Cyclopentadienyl(η-diborolenyl)nickel—A Diamagnetic Nickelocene Analog (page 468)

      Dr. Walter Siebert and Manfred Bochmann

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.197704681

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      The first complex of a deprotonated diborolene has now been synthesized as orange-red platelets. The electron balance in the sandwich complex can be described by assuming its construction from two aromatic rings (Cmath image, C3Bmath image) and the Ni d6 cation.

    10. Halogenonitrosylmolybdates—Isolation of the First Classical MoI Complex (pages 468–469)

      Dr. Sabyasachi Sarkar and Prof. Dr. Achim Müller

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.197704682

      A “classical” complex chemistry of lower valent molybdenum (Mo0, MoI, MoII) can be systematically developed now that the first NO-stabilized complex (1) of Mo in the formal oxidation state I has been obtained.

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    11. Formation of Benzocyclobutenone by Gas-Phase Pyrolysis (pages 469–470)

      Prof. Dr. Peter Schiess and Dipl.-Chem. Markus Heitzmann

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.197704691

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      Production of benzocyclobutenones on a preparative scale is possible by gas-phase pyrolysis of toluoyl chlorides (1), R5[DOUBLE BOND]H. Only C3H5-substituted benzaldehydes are formed when R5[DOUBLE BOND]C2H5.

    12. A Geometrically Isomeric Bilatriene-abc (pages 470–471)

      Prof. Dr. Heinz Falk and Mag. rer. nat. Karl Grubmayr

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.197704701

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      The first ZE isomerization of a bile pigment has been accomplished with (Z,Z,Z,-etiobiliverdin-IV-γ. The (E,Z,Z))-isomer could be isolated and characterized.

    13. Vinylenedionium Salts Containing Different Onium Groups (pages 471–472)

      Dr. Heinz Braun, Anton Amann and Manfred Richter

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.197704711

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      Vinylenesulfonium-ammonium and vinylenesulfonium-pyridinium salts of type (4) have been synthesized as the first representatives of their class. They react differently from the analogous disulfonium slats. Thus tertiary amines do not substitute either of the two onium groups in (4), R[DOUBLE BOND]Alkyl, but selectively demethylate the sulfonium group.

    14. Reactions of (2-Dialkylsulfoniovinyl)trialkylammonium Salts (pages 473–474)

      Dr. Heinz Braun and Anton Amann

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.197704731

      Thumbnail image of graphical abstract

      Vinylenesulfonium-ammonium and vinylenesulfonium-pyridinium salts of type (4) have been synthesized as the first representatives of their class. They react differently from the analogous disulfonium slats. Thus tertiary amines do not substitute either of the two onium groups in (4), R[DOUBLE BOND]Alkyl, but selectively demethylate the sulfonium group.

    15. Lithium 7bH-Indeno [1,2,3-jk] fluorenide, an Organolithium Compound Having a “Sandwich” Structure (pages 474–475)

      Dipl.-Chem. Dieter Bladauski, Prof. Dr. Hans Dietrich, Dr. Hans-Jürgen Hecht and Prof. Dr. Dieter Rewicki

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.197704741

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      The organolithium compound(1) displays a variety of special features. Thus (1) is the first Li salt of a hydrocarbon having extreme charge delocalization in the carbanion, which crystallizes without heteroatom bases. Compound (1) is the first example of a substance in which Li is linearly coordinated with two hexahapto-bonded six-membered ring ligands. Moreover, there is no preferential orientation of the Li atoms on the C centers having the highest charge density.

    16. 5-Methoxysemibullvalene (page 475)

      Prof. Dr. Reinhard W. Hoffmann, Dipl.-Chem. Norbert Hauel and Dr. Fritz Frickel

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.197704751

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      The first semibullvalene to have an electrondonor substituent has now been synthesized. The substitutent expectedly prefers position 5. The 1-isomer predominates in longer-known semibullvalene derivatives.

    17. Synthesis and Chemistry of Alkylidenediaziridines (pages 475–477)

      Prof. Dr. Gerrit L'abbé, Chih-Chou Yu and Dr. Suzanne Toppet

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.197704752

      Thumbnail image of graphical abstract

      The first alkylidenediaziridines(2) have now been synthesized by the reaction shown below. On heating they rearrange with cleavage of the N[BOND]N bond; oxazolidinimines are formed with phenyl isocyanate.

    18. Phosphoranes as Intermediates in the Michaelis-Arbusov Reaction (pages 477–478)

      Prof. Dr. Gert Bauer and Dr. Gerhard Hägele

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.197704771

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      Phosphoranes of type(1) (X[DOUBLE BOND]Cl, Br, I) can occur as intermediates in the Michaelis-Arbusov reaction, as has now been demonstrated. Compounds (1) were prepared in almost quantitative yield and converted into the expected products.

    19. New Pathways to Four-Membered Boron-Nitrogen Heterocycles (pages 478–479)

      Dr. Wolfgang Storch, Wolfgang Jackstiess, Prof. Dr. Heinrich Nöth and Gerhard Winter

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.197704781

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      Four-membered ring systems containing boron and nitrogen are now readily accessible by two new Syntheses. (1), E[DOUBLE BOND]Me2Si, MeP, Me(O)P, or Me(S)P, R[DOUBLE BOND]Me, is formed by intramolecular cyclization; (2), R′[DOUBLE BOND]Me or Cl, R[DOUBLE BOND]Me, can be obtained by Sn/B exchange. Thermodynamically favored formation of the six-membered borazines can thus be circumvented.

    20. μ-(η-Biphenyl)-bis[(η-benzene)chromium(0)], the Arenechromium Analog of Biferrocene (pages 479–480)

      Prof. Dr. Christoph Elschenbroich and Jürgen Heck

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.197704791

      Thumbnail image of graphical abstract

      A dinuclear sandwich complex containing only chromium atoms and benzene rings, viz. the biferrocene analog (1), has been synthesized from lithiated bis(η-benzene)chromium and o-bromoanisole. It should prove an interesting compound for spectroscopic studies.

    21. Synthesis and Properties of Tris(trimethylsilyl)aluminum (page 480)

      Dr. Lutz Rösch

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.197704801

      The AlSi compound(1) has now been prepared for the first time in about 90% yield. The thermolysis products of (1) suggest the intermediacy of dimethyl-silanediyl [(CH3)2Si].

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    22. Reaction of Dicyanocobyrinic Heptamethyl Ester with Ascorbic Acid (pages 481–482)

      Doz. Dr. Albert Gossauer, Dipl.-Chem. Burghard Grüning, Dr. Ludger Ernst, Dipl.-Chem. Wulf Becker and Doz. Dr. William S. Sheldrick

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.197704811

      Stable yellow corrinoids can arise as by-products in reactions of vitamin B12 involving a change in the oxidation state of the cobalt. The structure of the pigment from a vitamin B12 analog and ascorbic acid has now been elucidated by X-ray structure analysis.

    23. Novel Monobridged Dinuclear Platinum Species (pages 482–484)

      Prof. E. A. V. Ebsworth, Hugh M. Ferrier, Dr. Bernard J. L. Henner, Dr. David W. H. Rankin, Dr. Francis J. S. Reed, Dr. Heather E. Robertson and John D. Whitelock

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.197704821

      Thumbnail image of graphical abstract

      Platinum complexes containing the Pt—Exn—Pt unit were hardly known for PtII and not at all for PtIV. The synthesis of several representatives with E[DOUBLE BOND]P, S, or Se, X[DOUBLE BOND]H or F, and n[DOUBLE BOND]1 or 2 has now been accomplished. The cation (1) and the neutral compound (2) are examples.

    24. Coordination Number 3 in Oxozincates: Rb8 [OZnO2ZnO2ZnO2ZnO] and K2 [Zn6O7] (pages 484–485)

      Dipl.-Chem. Karl-Rainer Wambach and Prof. Dr. Rudolf Hoppe

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.197704841

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      Anions having an unusual structure occur in two oxozinacates, in which zinc has the coordination 3 towards oxygen. In the first oligozincate [Zn4O8]8− half of the zinc atoms are in a tetrahedral oxygen environment (o) and the other half in a trigonal-planar oxygen environement.

    25. Hexameric KN2Co [P(CH3)3]3—A Novel Potassium-Dinitrogen Cluster (pages 485–486)

      Dr. Reinhard Hammer, Doz. Dr. Hans-Friedrich Klein, Dipl.-Chem. Peter Friedrich and Prof. Dr. Gottfried Huttner

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.197704851

      A bimetallic dinitrogen complex(2) with a double cube skeleton made up of six K atoms and six N2 groups is surprisingly formed from ethereal solutions of (1) under 1 bar of N2. The complex crystallizes without ether or alkoxide donor ligands (olefin = propene, cyclopentene).

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    26. cis-2-Telluro-1,3,2λ5, 4λ3-diazadiphosphetidine—A Fluxional Redox System (page 486)

      Prof. Dr. Otto J. Scherer and Dr. Günter Schnabl

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.197704861

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      A fluxional phosphorus-chalcogen compound of type (1), the exceptionally stable tellurium-substituted four-membered ring (3), has now been synthesized by Te addition to (2). Temperature-dependent 1H- and 31P-NMR spectra prove the intramolecular reversible shift of Te.

    27. Synthesis of a Secondary Aminophosphane (pages 486–487)

      Priv.-Doz. Dr. Edgar Niecke and Dipl.-Chem. Gerhard Ringel

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.197704862

      Thumbnail image of graphical abstract

      Secondary aminophosphanes lacking complex stabilization were formerly considered incapable of existence. Compound (1), R[DOUBLE BOND]SiMe3, has now been synthesized as shown below.

    28. Reaction of Arsonium Ylides with Carbonyl Compounds—Effect of Substituents at Arsenic (pages 487–488)

      Dr. Ian Gosney, Dr. Terence J. Lillie and Dr. Douglas Lloyd

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.197704871

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      Alkenes and/or epoxides are formed on reaction of arsonium ylides with aldehydes. The product ratio can be influenced by variation of the substituents. Phosphonium ylides give only alkenes, and sulfonium ylides only epoxides.

    29. Regiospecific Synthesis of Mono-and Polyiodo Derivatives of Benzene (pages 488–489)

      Dr. Guy Félix, Dr. Jacques Dunoguès, Dr. Francoise Pisciotti and Prof. Raymond Calas

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.197704881

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      Replacement of trimethylsilyl groups by iodine atoms has proved of value in the synthesis of mono-and polyiodinated derivatives of benzene. Orienting substituents have hardly any effect upon the reaction course.

  3. Abstracts

    1. Top of page
    2. Reviews
    3. Communications
    4. Abstracts
    5. Book Reviews
    1. ABSTRACTS (page 490)

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.197704901

  4. Book Reviews

    1. Top of page
    2. Reviews
    3. Communications
    4. Abstracts
    5. Book Reviews
    1. Book Review: Principles of Pyrometallurgy. By C. B. Alcock (pages 491–492)

      Norbert Nowack

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.197704912

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