Angewandte Chemie International Edition in English

Cover image for Vol. 24 Issue 2

February 1985

Volume 24, Issue 2

Pages 77–138

Currently known as: Angewandte Chemie International Edition

    1. Cover Picture (Angew. Chem. Int. Ed. Engl. 2/1985)

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198500771

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      The cover page shows a stereograph of the structure of cyclosporine. This natural cyclopeptide contains a novel amino acid, a threonine derivative with a butenyl group which quasi bridges the ring. This amino acid is essential for the immunosuppressive activity of cyclosporine. More about the structure-activity relationships and about the synthesis of cyclosporine and analogues are reported by R. M. Wenger in a review article on page 17.—An optimal picture of the spatial architecture of the molecule is obtained if the stereograph is viewed through a mirror stereoscope; the three-dimensional structure in Figure 2 on page 79 can be seen quite readily with the aid of a lens stereoscope or even with the naked eye.

  1. Reviews

    1. Top of page
    2. Reviews
    3. Communications
    4. Book Reviews
    1. Synthesis of Cyclosporine and Analogues: Structural Requirements for Immunosuppressive Activity (pages 77–85)

      Dr. Roland Maurice Wenger

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198500773

      Unusual structure and unusual activity characterize cyclosporine 1, a neutral, hydrophobic cyclopeptide consisting of eleven amino acids. No more than ten years have passed since its discovery and it is already being employed clinically as an immunosuppressant. Among other things it prevents graft rejection following bone-marrow and organ transplantations.

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    2. Basic Principles of Protease-Catalyzed Peptide Bond Formation (pages 85–93)

      Prof. Dr. Hans-Dieter Jakubke, Dr. Peter Kuhl and Dr. Andreas Könnecke

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198500851

      The direct reversal of the mode of action of proteases—formation instead of degradation of peptides—has been achieved by use of physicochemical principles. The advantages of protease-catalyzed peptide synthesis include the stereospecificity and the rare necesity of having to protect the side chain; disadvantageous is that the proteases are sometimes substrate specific. The method is used, inter alia, in the synthesis of the sweetener aspartame and in the conversion of porcine insulin into human insulin.

    3. Synthesis and Biological Activity of α-Methylene-γ-butyrolactones (pages 94–110)

      Prof. H. M. R. Hoffmann and Dr. Jürgen Rabe

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198500941

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      Some 10% of the structurally elucidated natural products belong to the α-methylene-γ-butyrolactones, e.g. germacranolides, eudesmanolides, and guaianolides. Of special importance are the cytotoxic properties of some of the compounds of this group of substances. The syntheses of these lactones containing the structural unit 1 are not only of practical interest but also important as examples for the construction of compounds with unusual arrangement of the functional groups.

  2. Communications

    1. Top of page
    2. Reviews
    3. Communications
    4. Book Reviews
    1. Phenyl Silaisocyanide: The First Organosilicon Compound with a Formal Si[TRIPLE BOND]N Triple Bond (pages 111–112)

      Prof. Dr. Hans Bock and Dipl.-Chem. Ralph Dammel

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198501111

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      The presumably linear C[BOND]N[TRIPLE BOND]Si group is present in phenyl silaisocyanide 3, an organosilicon compound with terminal silicon of coordination number 1. 3 was generated pyrolytically from the triazidosilane 2 and characterized by photoelectron spectroscopy.

    2. Concerning the Mechanism of the Asymmetric Diels-Alder Reaction: First Crystal Structure Analysis of a Lewis Acid Complex of a Chiral Dienophile (pages 112–114)

      Dipl.-Chem. Thomas Poll, Dipl.-Chem. Joachim O. Metter and Prof. Dr. Günter Helmchen

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198501121

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      A seven-membered ring chelate structure, hitherto unknown in the case of titanium compounds, characterizes the complex 1. Presumably, this complex is the reactive species in solution in the TlCl4-catalyzed Diels-Alder reaction of allyl lactates with dienes. An X-ray structure analysis of the complex shows that the Re-side of the CC double bond is well shielded by one of the chlorine atoms.

    3. Synthesis of the First Linear (o-Phenyleno)naphthalenes; a New Class of Benzenoid Aromatics (pages 114–115)

      Harold E. Helson, Prof. Dr. K. Peter C. Vollhardt and Dr. Zhen-Yu Yang

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198501141

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      Novel benzenoid hydrocarbons such as 1 can be obtained from a naphthalene derivative in several cobalt-catalyzed steps. Although 1 contains a [4n + 2]π-system, its electronic structure must by described in terms of cyclobutadiene units. Compounds such as 1 are of interest for the synthesis of “organic metals”.

    4. Amino(imino)phosphanes as Face-Bridging Complex Ligands (pages 115–117)

      Prof. Dr. Otto J. Scherer, Dipl.-Chem. Richard Walter and Prof. Dr. William S. Sheldrick

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198501151

      A similar coordination behavior as isocyanide ligands is exhibited by R2N[BOND]P[DOUBLE BOND]NR ligands, since bridging isocyanide ligands are replaced by trivalent phosphazenes in the synthesis of the cluster 2 from the cluster 1. 2 represents the first cluster in which an amino(imino)phosphane is found to function as face-bridging ligand; a μ32-C[TRIPLE BOND]N[BOND]CMe3 ligand is also present.

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    5. [Mn(S2C6H3Me)2]n−: Mononuclear Manganese Complexes with Square-Planar (n = 1) and Distorted Tetrahedral (n = 2) Sulfur Coordination (pages 117–118)

      Dr. Gerald Henkel, Dipl.-Chem. Klaus Greiwe and Prof. Dr. Bernt Krebs

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198501171

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      The unusual planar manganese(III)-sulfur complex [Mn(S2C6H3Me)2]1 is formed on reaction of MnCl2·4H2O with toluene-3,4-dithiolate in methanol in the presence of atmospheric oxygen. A further product is the square-pyramidal complex containing an additional apical MeOH group. Reaction under anaerobic conditions leads to formation of the manganese(II)-sulfur complex [Mn(S2C6H3Me)2]2−, which differs from 1 through its strongly distorted tetrahedral coordination.

    6. Ag2O3, a Novel Binary Silver Oxide (pages 118–119)

      Dipl.-Chem. Burkhard Standke and Prof. Dr. Martin Jansen

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198501181

      Crystalline silver(III) oxide, which is stable over prolonged periods at −20°C, was obtained by anodic oxidation of AgClO4, AgBF4 or AgPF6 (not AgNO3) in aqueous solution. The oxide of definite composition Ag2O3 was hitherto unknown. It arouses interest as a possible component of the anodes in zinc/silver oxide primary cells. According to an X-ray structure analysis, the silver atoms in Ag2O3 are coordinated by an almost square-planar array of oxygen atoms. The AgO4 groups are coupled via common oxygen atoms to give a three-dimensional network.

    7. Nonacarbonylbis(μ3-fluoromethylidyne)triiron: Formation of a Biscarbyne Cluster from Carbonyliron and Tribromofluoromethane (pages 119–120)

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

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198501191

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      The synthesis of the first bis(fluoromethylidyne) cluster, [Fe3(CO)93-CF)2], was accomplished quite easily by reaction of Fe(CO)5 or Fe2(CO)9 with CFBr3. The two CF-ligands and the Fe3-unit form a trigonal bipyramid with the CF-ligands in the apical positions. The formation of a FC[TRIPLE BOND]CF-complex could be ruled out.

    8. Synthesis and structure of [Pt2(μ-H)(μ-CHCH2Ph)(diphos)2][BF4] (pages 120–121)

      Prof. Dr. Giovanni Minghetti, Dr. Alberto Albinati, Dr. Anna Laura Bandini and Dr. Guido Banditelli

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198501201

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      The first compound in which a hydride- and an alkylidene-ligand bridge two Pt-atoms is present in the complex cation 2, which is formed on reaction of the complex 1 with styrene. 2 was characterized NMR spectroscopically and by an X-ray structure analysis. the Pt[BOND]Pt distance of 2.735(1) Å indicates that there is bonding interaction between the two metal atoms.

    9. Cationic 2-Azaallenylidene Complexes, Novel Compounds with Unusual Photochemical Properties (pages 121–123)

      Priv.-Doz. Dr. Helmut Fischer, Dr. Friedrich Seitz, Jürgen Riede and Dr. Jürgen Vogel

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198501211

      [C[DOUBLE BOND]N[DOUBLE BOND]CR2], a cation unknown in the free state, is present as terminal ligand bound to a metal in the salts 1, M[DOUBLE BOND]Cr, W, R[DOUBLE BOND]Ph. On exposure to low-energy radiation (λ>300 nm) the complexes 1 fragment with cleavage of CR2; with exclusively short-wave radiation, however, they are stable. The complexes 1 thus belong to the few compounds in which fluorescence from higher ecited states is observed.

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    10. 1, 3, 4-Thiazaphospholes (pages 123–124)

      Prof. Dr. Alfred Schmidpeter, Dipl.-Chem. Konstantin Karaghiosoff, Cornelia Cleve and Dr. Dietmar Schomburg

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198501231

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      Novel simple heteroarenes, the title compounds 1, can be prepared from thiocarboxamides by alkylation at the sulfur and a subsequent condensation with phosphorus trichloride. 1, R[DOUBLE BOND]R′[DOUBLE BOND]Ph, crystallizes isomorphically with the N-analogue.

    11. 1,2,3,5-Diazadiphospholes — The First 1,3-Diphospha-1,3-diene System (pages 124–125)

      Prof. Dr. Alfred Schmidpeter, Dipl.-Chem. Christian Leyh and Dipl.-Chem. Konstantin Karaghiosoff

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198501241

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      A five-membered ring containing two phosphorus atoms of coordination number two is present in the novel heteroarenes 2. Remarkably, even triethylamine is suitable for the reaction 1 [RIGHTWARDS ARROW] 2. The two double bonds can be formed only pairwise.—Acyclic analogues of 2 are unknown.

    12. Reactions of Tricarbonyl(sorbaldehyde)iron with Carbanions: A Repeatable Organometallic Reaction with Fe(CO)3-Migration (pages 126–127)

      Dipl.-Chem. Andreas Hafner, Prof. Dr. Wolfgang von Philipsborn and Priv.-Doz. Dr. Albrecht Salzer

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198501261

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      Functionalized polylefins can be synthesized from the title compound 1; uncomplexed sorbaldehyde is a poor candidate for such syntheses (side reactions). Depending on the substituents and conditions, the products of type A or—with Fe(CO)3 migration—type B are formed. The triolefin B, R1[DOUBLE BOND]CHO, R2[DOUBLE BOND]H, can undergo further reaction.

    13. Synthesis of 1,4-Dihydropyridine Nucleosides by Photochemical Cycloaddition (pages 127–128)

      Prof. Dr. Lutz F. Tietze and Dipl.-Chem. Andreas Bergmann

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198501271

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      The 1,4-dihydropyridine nucleosides 4 are formed in almost quantitative yield when 2-hydroxytetrahydropyridines 3 are heated in toluene in the presence of a (4 Å) molecular sieve. The tetrahydropyridines 3 are likewise formed almost quantitatively on irradiation of a mixture of a N-glycosyl enaminecarbaldehyde 1 and an alkene 2. The method enables wide variation of the substituents and labeling of the dihydropyridine ring (R1=sugar residue, R2, R3=H, CH3, CO2CH3, CO2tBu).

    14. Preparation of an N-Acetylneuraminic Acid-Containing Trisaccharide and Its Use in Oligosaccharide Syntheses (pages 128–129)

      Prof. Dr. Hans Paulsen and Dr. Holger Tietz

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198501281

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      The trisaccharide building block 1, which is capable of linkage and suitable for glycoside synthesis, is formed on reaction of N-acetylneuraminic acid with lactosamine. For glycoside couplings with 1, the trimethylsilyl triflate method can be used; this allows the N-acetylneuraminic-containing building block to be coupled to any desired saccharide.

    15. “Dimers” of Aldosterone (pages 130–131)

      Dr. Klaus Lichtwald and Dr. Michael Przybylski

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198501301

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      Two isomeric “dimers” are formed from aldosterone 1 on proton-catalyzed cleavage of two water molecules. The dimers could be characterized mass spectroscopically. With the prerequisite that they are also formed under physiological conditions, the existence of such aldosterone derivatives had to be taken into account when considering molecular events in aldosterone activity.

    16. Stereospecific Synthesis of 3-Substituted Hexahydroindane Derivatives (pages 131–132)

      Dr. Hans-Eckart Radunz and Günter Schneider

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198501311

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      3-Substituted hexahydroindane derivatives are of interest as starting compounds for the synthesis of rigid prostaglandin analogues. They could be obtained with unexpectedly high stereoselectivity from the carboxylic acid 1. The acid 1 reacts with N-bromosuccinimide to give the bromide 2. This is converted into the acetate 3, which has the same relative configuration at the centers 3, 3a, and 7a as in the naturally occurring prostaglandins.

    17. Synthesis of [(C5Me5)2Mo2XS3Co(CO)2] Clusters (X = P, As) and Structural Characterization of a μ2, η2-AsS Ligand (pages 132–133)

      Prof. Dr. Henri Brunner, Dipl.-Chem. Heike Kauermann, Dr. Ulrich Klement, Dr. Joachim Wachter, Dipl.-Chem. Thomas Zahn and Prof. Dr. Manfred L. Ziegler

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198501321

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      The first complex with AsS as ligand, the trinuclear cluster 1, was obtained from the dinuclear complex [(C5Me5)2Mo2As2S3] and Co2(CO)8 and characterized by X-ray structure analysis. It is concluded from the bond lengths that AsS has a bond order of 1 and functions as a 5e-donor.—The cluster 2 was prepared analogously.

    18. Novel MoFeS Clusters from [(C5Me5)2Mo2S4] and Fe(CO)5 or Fe2(CO)9 (pages 133–135)

      Prof. Dr. Henri Brunner, Norbert Janietz, Dr. Joachim Wachter, Dipl.-Chem. Thomas Zahn and Prof. Dr. Manfred L. Ziegler

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198501331

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      The synthesis of novel tri- and tetranuclear clusters in the Mo[BOND]Fe[BOND]S system can be accomplished by addition of Fe(CO)5 or Fe2(CO)9 to the complex [(C5Me5)2Mo2S4]. An example is 1, a 62e-“heterocubane”. It contains five M[BOND]M bonds (not shown); the Fe[BOND]Fe distance (no bonding) is 3.334 Å.

    19. Diamminebis(1,5-cyclooctadiene)(μ-1,4,10,13-tetraoxa-7, 16-diazacyclooctadecane-N7, N16)dirhodiumbis-(hexafluorophosphate): An Example of Simultaneous First and Second Sphere Coordination (pages 135–136)

      Dr. Howard M. Colquhoun, Simon M. Doughty, Alexandra M. Z. Slawin, Dr. J. Fraser Stoddart and Dr. David J. Williams

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198501351

      The first example of a nitrogen-containing crown ether acting as both a first and second sphere ligand towards a transition metal is found in the rhodium complex 1. This complex contains a crystallographic center of symmetry and is stabilized by intramolecular hydrogen bridges.

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  3. Book Reviews

    1. Top of page
    2. Reviews
    3. Communications
    4. Book Reviews
    1. Book Review: Atomabsorptionsspektrometrie. By B. Welz (page 137)

      Harald Berndt

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198501371