Angewandte Chemie International Edition in English

Cover image for Vol. 23 Issue 1

January 1984

Volume 23, Issue 1

Pages 1–88

Currently known as: Angewandte Chemie International Edition

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

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198400011

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      The cover shows the structure of a novel hydrocarbon, which, contrary to the Hückel rule is aromatic, despite its 16π-electron periphery. The electronic properties in this “bicalicene” can be described in terms of three mesomeric structures. Further details are reported by Z. Yoshida et al. on page 63.

  1. Reviews

    1. Top of page
    2. Reviews
    3. Communications
    4. Book Reviews
    1. The Cycloaddition of Allyl Cations to 1,3-Dienes: General Method for the Synthesis of Seven-Membered Carbocycles. New Synthetic Methods (40) (pages 1–19)

      Prof. H. M. R. Hoffmann

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198400013

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      The formation of seven-membered rings by cycloaddition of allyl cations to 1,3-dienes is of special preparative interest. The synthesis of bicycles such as 1 is underscored. Division of the reactions into three classes enables product type and stereochemistry to be related to the electrophilicity of the allyl cation, to the nucleophilicity of the diene, and to the donor strength of the substituent Y.

    2. Destabilized Carbocations (pages 20–32)

      Prof. Thomas T. Tidwell

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198400201

      The destabilization of carbocations can depend on structural effects, e.g. reduction of the bond angle at the trigonal planar cationic center. The stability can also be reduced by antiaromatic character such as in the case of the cyclopentadienyl cation. Probably the most detailed study has been carried out on the destabilization by electron withdrawing substituents.—Information gained about these cations also contributes, last, but not least, to a further understanding of the principles of organic chemistry.

    3. Nodal Nomenclature II—Specific Nomenclature for Parent Hydrides, Free Radicals, Ions, and Substituents (pages 33–46)

      Prof. Noël Lozac'h and Dr. Alan L. Goodson

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198400331

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      The uniform naming of all organic compounds is possible with the aid of nodal nomenclature. The name of the structure graph is derived for the corresponding hydrocarbon and, if necessary, modified. There are only a few simple rules (almost) without alternatives. Examples: 1: 2,5-diaza[7.12.15]nonane-2,5-diium; 2: [7.24]nonane-4(8)-en-1-ol. 1 can be named according to the IUPAC rules only with difficulty.

  2. Communications

    1. Top of page
    2. Reviews
    3. Communications
    4. Book Reviews
    1. N,N-Bis(trimethylsilyl)aminomethylation of Grignard Compounds — A Versatile Amine Synthesis (page 53)

      Prof. Dr. Hans Jürgen Bestmann and Dipl.-Chem. Gerhard Wölfel

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198400531

      The conversion of Grignard compounds into homologous amines has proven possible by aminomethylation with the alkoxymethylamine 1. The reaction is widely applicable; R = alkyl, alkenyl, alkynyl, aryl.

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    2. Stable Cyclopentadienylium Salts (pages 53–54)

      Prof. Dr. Rudolf Gompper and Dipl.-Chem. Heinrich Glöckner

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198400532

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      A cyclopentadienyl cation is contained in the blue, crystalline tetrafluoroborate 1. This compound can be used as precursor for the preparation of further cyclopentadienyl derivatives, e.g. 2, the first stable cyclopentadienethione.

    3. Hydroxide Ion-Initiated Deuteration of Very Weak CH Acidsunder Phase Transfer Catalysis Conditions (pages 54–55)

      Marc Halpern, David Feldman, Dr. Yoel Sasson and Prof. Mordecai Rabinovitz

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198400541

      The deuteration of organic compounds with pKa values of up to ca. 34 has been achieved by a special type of phase transfer catalysis. As is well known, hydroxide ions can be extracted into an organic phase from aqueous sodium hydroxide in the presence of quaternary ammonium salts. It has now been shown that these extracted hydroxide ions are more basic than the hydroxide ions at the interface. Exploiting this observation, diphenylmethane, 10,11-dihydrodibenzo[a,d]cycloheptene and xanthene (pKa = 34, 31, and 27, respectively) could be deuterated quantitatively.

    4. Structure of Tetracyclo[6.2.1.13,6.02,7]dodeca-4,9-diene: A Diolefin with Close Double Bonds (pages 55–57)

      Priv. Doz. Dr. Otto Ermer, Dr. Claus-Dieter Bödecker and Dr. Hans Preut

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198400551

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      The distance between the almost parallel double bonds in 1 has been calculated with a consistent force field to be 2.756 Å. A value 0.165 Å higher, however, was determined for the phthalic acid semiester of 1 coupled via C-11. The increased separation is attributed to orbital-symmetry effects.

    5. Radical Anion-Substituted Crown Ethers as Cages for Metal Cations (pages 57–58)

      Prof. Dr. Hans Bock, Dipl.-Chem. Bernhard Hierholzer, Prof. Dr. Fritz Vögtle and Dr. Günter Hollmann

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198400571

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      The fixation of metal cations in a solvent cage—such as in 1—has been achieved by reduction of the corresponding neutral compound with alkali metals M. The spin distribution, which is dependent on the charge and the radius of the cations, has been investigated for the first time by ESR and ENDOR spectroscopy.

    6. Heterometal Binuclear Complexes with Thio- and Selenoformaldehyde as Bridge Ligands (pages 58–59)

      Prof. Dr. Helmut Werner and Wilfried Paul

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198400581

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      Two different metal-ligand groups and a CH2Se- (or CH2S-)bridge are contained in the novel compounds 1. The synthetic concept—addition of MLn(THF) to the corresponding mononuclear Rh-complex—appears to be capable of generalization.

    7. 1,3-Bis(tri-tert-butylsilyl)triazene (pages 59–60)

      Prof. Dr. Nils Wiberg, Dr. Gerd Fischer and Petros Karampatses

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198400591

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      The first silyl derivative of triazene is unusually stable (up to 150°C!) due to the two extraordinarily bulky tri-tert-butylsilyl substituents. It follows from the 1H-NMR spectrum that the N-bonded H atom migrates at 55°C.

    8. Preparation of Enantiomerically Pure Chiral Alcohols by Asymmetric Alkylation of Glycolates (pages 60–61)

      Prof. Dr. Günter Helmchen and Dipl.-Chem. Reiner Wierzchowski

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198400601

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      Partially protected chiral 1,2-diols 3 are obtained enantiomerically pure unsuing the chiral reagent 1, R1 [DOUBLE BOND] COCH2OBn. Lithiation/alkylation leads with diastereoselectivites of ca. 90% to 2, R2 [DOUBLE BOND] Me, Et, n-decyl, which can be reduced to the alcohols (S)-3; exo-1 reacts analogously.

    9. Novel Structures Containing Germanium(II): Germanocene Dimeric Tricarbonyl(di-tert-butoxygermylene)nickel(0) (pages 61–63)

      Dr. Mario Grenz, Dipl.-Chem. Ekkehardt Hahn, Prof. Dr. Wolf-Walther du Mont and Prof. Dr. Joachim Pickardt

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198400611

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      The X-ray structure analysis of germanocene 1—prepared for the first time in pure form from NaC5H5 and GeCl2·dioxane, and stable for weeks at −30°C—shows that it is present as the monomer. 1 is an excellent educt for the synthesis of GeII compounds, e.g., alcoholysis leads to 2.

    10. A Novel Aromatic Hydrocarbon with 16π-Electron Periphery: “Cyclic Bicalicene” (pages 63–64)

      Prof. Dr. Shigeo Yonedo, Mitsuhiro Shibata, Shuji Kida, Prof. Dr. Zen-ichi Yoshida, Dr. Yasusi Kai, Dr. Kunio Miki and Prof. Dr. Nobutami Kasai

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198400631

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      An exception to the Hückel rule in conceivable in the case of the 16π-electronics species 1: it reacts, e.g., with N-bromosuccinimide with substitution, electrochemical reduction leads to the 18π-system, and the 1H-NMR signals are not shifted to high field. The aromatic stabilization of 1 rests on the resonance of two Kekulé structures and a polarized structure.

    11. Enzymatic Syntheses of Chiral Building Blocks from Racemates: Preparation of (1R,3R)-Chrysanthemic, -Permethrinic and -Caronic Acids from Racemic, Diastereomeric Mixtures (pages 64–66)

      Prof. Dr. Manfred Schneider, Dr. Norbert Engel and Heike Boensmann

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198400641

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      The use of enantioselectivley reactive enzymes on the laboratory scale offers great advantages. With procine liver esterase, for example, chrysanthemic acid (1R,3R)-1 can be prepared from a mixture of the four esters with (1S,3R)-, (1R,3S)- (1S,3S)-, and (1R,3R)-configuration. Diastereoselective hydrolysis of the mixture affords the trans-acids (1S,3S)-1 and (1R,3R)-1. Enantioselective hydrolysis of the trans-ester leads to (1R,3R)-1, which is of interest in connection with the pyrethroid insecticides.

    12. Enzymatic Synthesis of Chiral Building Blocks from Prochiral Substrates: Enantioselective Synthesis of Monoalkyl Malonates (page 66)

      Prof. Dr. Manfred Schneider, Dr. Norbert Engel and Heike Boensmann

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198400661

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      The enantioselective hydrolysis of the prochiral malonic ester 1 to the chiral monoesters 2 has been accomplished with porcine liver esterase. Selective secondary reactions at the ester or the carboxy group open up the directed entery to both enantiomeric series of potential target molecules.

    13. Enzymatic Syntheses of Chiral Building Blocks from Prochiral meso-Substrates: Preparation of Methyl(hydrogen)-1,2-cycloalkanedicarboxylates (pages 67–68)

      Prof. Dr. Manfred Schneider, Dr. Norbert Engel, Petra Hönicke, Gerd Heinemann and Priv.-Doz. Dr. Helmut Görisch

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198400671

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      Chiral cis-monoesters 2 have been obtained from prochiral meso-diesters 1 of 1,2-cycloalkanedicarboxylic acids by enantioselective hydrolysis with procine liver esterase. In most cases the enantioselectivity is high. [BOND]R[BOND] is, e.g., [BOND]CMe2[BOND], [BOND](CH2)2[BOND], or [BOND](CH2)4[BOND].

    14. Hydrozirconation of Nitriles: Proof of a Linear Heteroallene Structure in (Benzylideneamido)zirconocene Chloride (pages 68–69)

      Priv.-Doz. Dr. Gerhard Erker, Wolfgang Frömberg, Prof. Dr. Jerry L. Atwood and Dr. William E. Hunter

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198400681

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      The structural similarity of carbenium ions 1 and the neutral zirconocene derivative 2 in the ground state is surprising only at first glance; the isolobal model gives an explanation. 2, R. [DOUBLE BOND] Ph, contains the shortest Zr[BOND]N bond known so far in molecular Zr compounds (2.013 Å).

    15. The Scope of Radical CC-Coupling by the “Tin Method” (pages 69–70)

      Prof. Dr. Bernd Giese, Dipl.-Ing. Juan Antonio González-Gómez and Dipl.-Ing. Tom Witzel

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198400691

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      The widely useful tributyltin hydride as catalyst (in the presence of NaBH4) effects the radical chain lengthening of alkyl iodides with acrylonitrile or alkenes which contain, e.g. ketone aldehyde, ester or phenyl substituents. As reagent, tributyltin hydride enables a convenient synthesis of C-branched deoxy sugars. A sugar such as 1, Y [DOUBLE BOND] OH, is converted into a xanthogenate or thiourethane, which e.g., reacts with acrylonitrile to give 2, R [DOUBLE BOND] CH2CH2CN.

    16. The Allyl Group as Mildly and Selectively Removable Carboxy-Protecting Group for the Synthesis of Labile O-Glycopeptides (pages 71–72)

      Prof. Dr. Horst Kunz and Dipl.-Chem. Herbert Waldmann

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198400711

      Biologically important O-glycopeptides contain inter alia, the acid- and baselabile glycosyl-serine or glycosyl-threonine bond; to link these bounds, it has proven useful to protect the carboxy group of the glycopeptide with an allyl group. The deblocking can be carried out selectivley, almost quantitatively, an extremely mildly with tetrakis (triphenylphosphane)palladium(0) in the presence of morpholine.

    17. Unusual Components of the Toadstool Lyophyllum connatum (Agaricales) (pages 72–73)

      Dipl.-Chem. Burkhard Fugmann and Prof. Dr. Wolfgang Steglich

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198400721

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      Before consuming the toadstool Lyophyllum connatum a warning should be given: Compounds similar to the components of connatin 1 (main chromogen) and lyophyllin 2 react strongly mutagenically. The structure of 2, the first alkylazooxycarboxamide, has been confirmed by synthesis.

    18. Mechanism of the Cyclopropane “Walk” Rearrangement: Synthesis and Properties of the 2-Diazopropane Adduct of Cyclooctatetraene (pages 73–74)

      Prof. Dr. Frank-Gerrit Klärner and Dipl.-Chem. Volker Glock

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198400731

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      Does the “walk” rearrangement 1 ⇌ 1′ poceed via a diradical of type 2? To check this, the title compound cis-3, a precursor of 2, X = Y = Me, was thermolyzed. Suprisingly, the strongly strained trans-4 was formed, which was previously obtainable only with difficulty. Since the cis-configuration is retained in the “walk” rearrangement 11′, 2 separates out as an intermediate.

    19. Macrocycles by Intramolecular Diels-Alder Reaction—Regioselective Synthesis of Anthracycline Precursors (pages 74–75)

      Dr. Joaquin Tamariz and Prof. Dr. Pierre Vogel

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198400741

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      The key step in the synthesis of the anthracyclin precursor 2, the simultaneous formation of the ring A and the 18-membered lactone ring, proceeds astonishingly in 58% yield by intramolecular Diels-Alder reaction of 1, R[DOUBLE BOND](CH2)6OCOCH[DOUBLE BOND]CH2.The analogue of 1 with three instead of six methylene groups does not cyclize.

    20. Preparation and Structure of (η6-Hexamethylbenzene)gallium(I) Tetrabromogallate(III): π-Complex and nido-Cluster (pages 76–77)

      Prof. Dr. Hubert Schmidbaur, Prof. Dr. Ulf Thewalt and Dr. Theodore Zafiropoulos

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198400761

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      The first monoarene complexes of gallium(I) were obtained by reaction of Ga2X4 (X = Cl, Br), suspended in toluene, with hexamethylbenzene. In 1b, C-1 and C-4 of the arena ligand are shifted towards the GaI; 1b can thus be regarded both as a π-complex as well as nido-cluster.

    21. Hydrolysis Products of the Monomeric Amine Complex (C6H15N3)FeCl3: The Structure of the Octameric Iron(III) Cation of {[(C6H15N3)6Fe83-O)22-OH)12]Br7(H2O)}Br·8H2O (pages 77–78)

      Prof. Dr. Karl Weighardt, Dipl.-Chem. Klaus Pohl, Ibrahim Jibril and Prof. Dr. Gottfried Huttner

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198400771

      An extraordinary cation with eight FeIII centres is contained in the title compound. It has been characterized X-ray crystallographically as the first FeIII-oligomer with more than three centres. Besides the strong bridging by oxo- and hydroxo-groups the “hydrophobization” of the surface by the six amine ligands is worthy of note. In the crystal, seven of the eight Br ions and a H2O molecule are associated with the cation—it can thus be regarded as a bromide-ion bearing complex monocation.

    22. Stable Olefin Complexes of Pt(II) Containing Trichlorostannate(II) Ligands: Structure of [Ph4As][Pt(SnCl3)3(1,5-cod)] (pages 78–79)

      Prof. Alberto Albinati, Priv.-Doz. Dr. Paul S. Pregosin and Dipl.-Chem. Heinz Rüegger

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198400781

      Fivefold coordinated platinum(II) is contained in the novel complex 1. It is the first square-pyramidal platinum-tin complex; one of the three Sn atoms adops the axial position. 1 has a dynamic structure in solution.

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    23. Oxidative Cleavage of Pyrocatechol at the meta-Position; A Model Reaction for Cleavage by Pyrocatechol-2,3-dioxygenase? (pages 79–80)

      Dr. Rudolf Müller and Dr. Franz Lingens

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198400791

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      The first nonenzymatic meta-cleavage of pyrocatechol 1 was achieved with KO2 in dimethyl sulfoxide. The unstable yellow 2-hydroxymuconaldehyde acid 2 was converted into picolinic acid. Since 1 is not cleaved to give 2 under N2, Omath image as well as O2 might participate in the reaction.

    24. Sulfur Imide as bisdihapto-Bridging Ligand in the Complex Fe2(CO)6(HNS) (pages 80–81)

      Prof. Dr. Max Herberhold and Wolfgang Bühlmeyer

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198400801

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      The stabilization of sulfur imide (HNS), which is not known in the free state, was accomplished for the first time by coordination to iron centres. In the complex 1, HNS functions as a six-electron ligand.

    25. Sterically Fixed Retinal-Analogue Prevents Proton-Pumping Activity in Bacteriorhodopsin (pages 81–82)

      Dipl. Chem. Elisabeth Kölling, Dr. Wolfgang Gärtner, Prof. Dr. Dieter Oesterhelt and Doz. Dr. Ludger Ernst

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198400811

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      The mode of action of bacteriorhodopsin has been studied using an all-trans and the 13-cis isomers of the retianl analogue 1. Compound 1 is the first retianl analogue whose 13-cis isomer does not fit into the binding site of the apoprotein. Since the all-trans/13-cis isomerization in the protein cannot take place, the reconstituted chromophore with the all-trans isomer is not functionable.

    26. Hexa-O-alkanoyl-scyllo-inositols, the First Alicyclic, Saturated, Discotic Liquid Crystals (pages 82–83)

      Dr. Bernd Kohne and Prof. Dr.-Ing. Klaus Praefcke

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198400821

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      The “nucleus” of liquid crystals having a disc-shaped molecular structure has almost always involved the use of a benzene ring. Since the title compounds 1 have broad mesophase regions, it would appear to rest less on the unsaturation than on the space filling, planarity and rigidity of the molecule.

    27. The Electrochemical Reduction of Benzene—First Direct Determination of the Reduction Potential (pages 84–85)

      Dr. John Mortensen and Priv.-Doz. Dr. Jürgen Heinze

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198400841

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      The reduction potential of benzene is −3.42±0.05 V vs. SCE. This value was measured cyclovoltammetrically at −60°C under “super-dry” conditions. The step observed corresponds to two-electron transfer.

  3. Book Reviews

    1. Top of page
    2. Reviews
    3. Communications
    4. Book Reviews
    1. Book Review: Covalent Catalysis by Enzymes. By L. B. Spector (page 87)

      Hermann Eggerer

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198400871

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