Angewandte Chemie International Edition in English

Cover image for Vol. 24 Issue 9

September 1985

Volume 24, Issue 9

Pages 719–798

Currently known as: Angewandte Chemie International Edition

    1. Cover Picture (Angew. Chem. Int. Ed. Engl. 9/1985)

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198507191

      Thumbnail image of graphical abstract

      The cover page shows two macrocycles—a hexamer and an octamer—in which chiral spirobifluorene moieties are linked via crown ether structural groups. These well-defined compounds with 78 (m [DOUBLE BOND] 1) and 104 ring members (m [DOUBLE BOND] 3) are obtained together with the di- and the tetramer, as well as some analogues, under the conditions of phase transfer catalysis. There are very few known examples of such chiral, yet highly symmetrical molecules. They exhibit a wide range of possible applications. Further details are reported by V. Prelog et al. on page 792.

    2. Graphical Abstract (Angew. Chem. Int. Ed. Engl. 9/1985)

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198507192

  1. Reviews

    1. Top of page
    2. Reviews
    3. Communications
    4. Book Reviews
    1. Applications of Synthetic Peptides (pages 719–727)

      Dipl.-nat. Rudolf Moser, Dipl.-nat. Stephan Klauser, Dipl.-nat. Thomas Leist, Dipl.-nat. Hanno Langen, Thomas Epprecht and Prof. Dr. Bernd Gutte

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198507193

      A synthetic, DDT-binding and degrading polypeptide containing 24 amino acid residues is only one of many biologically and medicinally important peptides which have been prepared in the last few years. Synthetic peptides find use in investigations of structure-function relations of polypeptides, as peptide hormones and hormone analogues, in the preparation of cross-reacting antibodies, and in the design of novel enzymes.

    2. Host/Guest Chemistry of Organic Onium Compounds—Clathrates, Crystalline Complexes, and Molecular Inclusion Compounds in Aqueous Solution (pages 727–742)

      Prof. Dr. Fritz Vögtle, Dr. Hans-Gerd Löhr, Dr. Joachim Franke and Dipl.-Chem. Detlev Worsch

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198507271

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      Inclusion ability and selectivity predestine organic ammonium, phosphonium, and other suitably structured onium compounds as chelate formers. Macrocyclic oxonium compounds of the phane type can function as receptor and enzyme models. Catalytic activity has already been obtained with synthetic compounds having large cavities.

    3. Transition Metal Polysulfides: Coordination Compounds with Purely Inorganic Chelate Ligands (pages 742–757)

      Dr. Mark Draganjac and Prof. Thomas B. Rauchfuss

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198507421

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      A host of new complexes containing polysulfido chelate ligands Smath image (n = 2, 3, 4…), e.g., the thorium complex 1, have been isolated and characterized in the past few years. These complexes are of interest not only regarding their structure but also in view of their potential. They are suitable as building blocks, e.g., for cyclopolysulfanes, and there are indications that they could also find use in catalysis.

  2. Communications

    1. Top of page
    2. Reviews
    3. Communications
    4. Book Reviews
    1. Synthesis of Cyclohepta[a]phenalene-6,12-dione (pages 757–758)

      Dr. Shigeyasu Kuroda, Yuriko Fukuyama, Tomohiko Tsuchida, Eishi Tanaka and Prof. Dr. Syuzi Hirooka

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198507571

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      Tetracyclic dications 2, which exhibit a diamagnetic ring current, were obtained from the non-benzenoid quinones 1, R [TRIPLE BOND] H or Br, with conc. H2SO4. The dications contain 16 π-electrons in the ring system.

    2. 1,2-Bis(diisopropylamino)-1,2-dihydro-1,2-diborete (pages 759–760)

      Manfred Hildenbrand, Dr. Hans Pritzkow and Prof. Dr. Walter Siebert

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198507591

      Thumbnail image of graphical abstract

      The first 1,2-dihydro-1,2-diborete 1 (R1 [DOUBLE BOND] NiPr2, R2 [DOUBLE BOND] H) has been isolated in the form of colorless crystals. The C2B2 ring is planar. At 120°C, 1 rearranges into the thermodynamically more stable 1, 3-dihydro-1, 3-diborete 2.

    3. The X-Ray Crystal Structures of Two 1, 2, 4, 5-Tetrathia-3,6-diazacyclohexanes (pages 760–761)

      Ray Jones, Dr. David J. Williams and Dr. J. Derek Woollins

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198507601

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      Six-membered sulfur-nitrogen rings with pyramidal N atoms, the title compounds 1 (R [DOUBLE BOND] Et) and 2 (R [DOUBLE BOND] CH2Ph), unlike analogous compounds, do not exhibit pπ-dπ interactions. The substituents are arranged axially.

    4. UV and CD Spectroscopic Evidence of the Self-Association of a Schiff Base of all-trans-Retinal (pages 761–763)

      Dipl.-Chem. Ute Wingen, Dipl. Lab. Chem. Lothar Simon, Dipl.-Chem. Michael Klein and Prof. Dr. Volker Buß

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198507611

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      Splitting of the retinylidene absorption into two exciton excitations is deduced from the CD spectrum of the dimer of 1. The dimer contains a ten-membered ring with two hydrogen bonds; as a result the chromophores are rigidly fixed (R1 [DOUBLE BOND] CH2OH, R2 [DOUBLE BOND] CH(CH3)2).

    5. Photochemistry of 1-Methoxybicyclo[2.2.2] octenones; Photolytic Cyclopropane Cleavage of the Initially Formed Tricyclo [3.3.0.02,8]octan-3-ones (pages 763–764)

      Dr. Martin Demuth, Dr. Bernhard Wietfeld, Dr. Bipin Pandey and Prof. Dr. Kurt Schaffner

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198507631

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      The mechanism of the photochemical conversion of the bicyclic ketone 1. R [DOUBLE BOND] CH2CH2OCH3, into the 1, 4-diketone 3 has been elucidated. The intermediate involved in the conversion is the tricycle 2 (R′[DOUBLE BOND]OCH3), which reacts further via a diradical to give the diquinane 3; such compounds are valuable synthetic building blocks, e.g. for natural products.

    6. How is Phosphorus Bound in 2-Phospha- and 2-“Phosphoniaallyl” Cations? (pages 764–765)

      Dr. Roberta O. Day, Dipl.-Chem. Angela Willhalm, Joan M. Holmes, Prof. Dr. Robert R. Holmes and Prof. Dr. Alfred Schmidpeter

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198507641

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      The conjugation in the 2-phosphaallyl cation 1 is removed upon methylation to the doubly positively charged species 2, a phosphane with two cationic substituents.

    7. Allylation of Aldehydes with Etherification by Dialkoxydichlorotitanium/Allyltrimethylsilane; an Asymmetric Variant of the Sakurai Reaction (pages 765–766)

      Dipl.-Chem. René Imwinkelried and Prof. Dr. Dieter Seebach

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198507651

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      A single step synthesis of homoallyl ethers 1 is possible by reaction of aldehydes with Cl2Ti(OR′)2 generated in situ and allyltrimethylsilane. With OR′ [DOUBLE BOND] (S)-1-phenylethoxy, chiral homoallyl ethers could be obtained with 90% ds via an open-chain acetal derivative.

    8. A New Type of Sandwich Complex Formed by Ag1 and [Pt32-CO)3(PiPr3)3] (pages 766–767)

      Prof. Alberto Albinati, Dipl.-Chem. Klaus-Hermann Dahmen, Dr. Antonio Togni and Prof. Luigi M. Venanzi

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198507661

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      One of the lesser known heteronuclear Ag clusters is the sandwich complex cation 1, in which two [Pt32-CO)3(PiPr3)3] moieties are coupled by a Ag+ ion. 1 could be isolated as the CF3SOmath image salt in the form of air-stable, dark-red, prismatic crystals.

    9. Novel High-Nuclearity HgCoRu and HgCoFe Sandwich Complexes. Synthesis and Structure of [Hg{RuCo3(μ-CO)3(CO)9}2] (pages 767–768)

      Dr. Pierre Braunstein, Dr. Jacky Rosé, Prof. Antonio Tiripicchio and Prof. Marisa Tiripicchio Camellini

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198507671

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      Two RuCo3 tetrahedra, which are joined by a Hg2+ ion, are present in the sandwich complex 1. The complex 1 is formed—along with HgBr2—in the disproportionation of BrHg[RuCo3(CO)12]; crystals suitable for an X-ray structure analysis are obtained directly.

    10. Reductive Carbonylation of o-Nitrophenol with a Fe-Pd Cluster-Derived Heterogeneous Catalyst; CO Migration in [FePdPt(CO)4(Ph2PCH2PPh2)2] (pages 768–770)

      Dr. Pierre Braunstein, Dr. Jacques Kervennal and Jean-Luc Richert

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198507681

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      High activity and selectivity is exhibited by the FePd cluster 1 on SiO2 in the reductive carbonylation of o-nitrophenol to benzoxazol-2-one. A conventional catalyst prepared from iron oxalate and palladium acetate is far less effective. The catalyst prepared from 1 retains its activity even after repeated use.

    11. New Donor-Substituted Vinyl- and Alkynylcyclopropanes as Synthetic Building Blocks (pages 770–771)

      Dr. Schahab Keyaniyan, Michael Apel, Dr. Joe Pierce Richmond and Prof. Dr. Armin de Meijere

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198507701

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      The enhancement of the rate of the vinylcyclopropane-cyclopentene rearrangement by donor substituents has been used for the construction of the triquinane skeletal structure. The vinylcyclopropane 1 is first converted into the corresponding ethynyl derivative, which, upon reaction with cyclopentene and CO, yields the vinylcyclopropane derivative 2. Flash thermolysis leads to 3.

    12. Heterogeneous Redox Catalysis on Ti/TiO2 Cathodes—Reduction of Nitrobenzene (pages 771–772)

      Prof. Dr. Fritz Beck and Dipl.-Chem. Wolfgang Gabriel

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198507711

      A novel ceramic electrode for redox catalysis was prepared from etched titanium sheet which was covered with a solution of titanium acetylacetonate in HNO3 and heated at 450°C. Noteworthy are the current densities recorded (for example 5 A/dm2) on such an activated electrode. This electrode has been used for the reduction of nitrobenzene. It proceeds as follows with reformation of Ti(OH)4:

      • equation image
    13. Decabenzylgermanocene: Synthesis and Structure of a Monomeric, Air-Stable Germanocene (page 773)

      Prof. Dr. Hebert Schumann, Dipl.-Chem. Christoph Janiak, Dr. Ekkehardt Hahn, Dipl.-Chem. Jörg Loebel and Prof. Dr. Jerold J. Zuckerman

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198507731

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      Three of the benzyl groups in the germanocene 1 form a kind of protective shield for the lone pair electrons of the central germanium atom. This has been demonstrated by an X-ray structure analysis. 1 is the first germanocene that, despite non-parallel cyclopentadienyl ring planes, is air stable.

    14. Synthesis of the Immunologically Essential Saccharide Sequence of the “Enterobacterial Common Antigen” (pages 773–775)

      Prof. Dr. Hans Paulsen and Dipl.-Chem. Jens Peter Lorentzen

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198507732

      A trisaccharide containing an aminouronic acid moiety is the repeat unit of an oligosaccharide that represents the family-specific immunodeterminant structure of Enterobacteriaceae. The synthesis of the derivative 1 of this trisaccharide has now been accomplished, which should enable the preparation of the corresponding synthetic antigens.

      • equation image
    15. Total Synthesis of (±)-Bonellin Dimethyl Ester (pages 775–776)

      Priv.-Doz. Dr. Franz-Peter Montforts and Dipl.-Chem. Ulrich M. Schwartz

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198507751

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      The sex-differentiating pheromone of the marine animal Bonellia viridis, the porphyrin derivative bonellin, could be synthesized as the rac-dimethyl ester 1. The starting materials were four monocyclic building blocks and a selectively cleavable malonic ester (R1[DOUBLE BOND]CH3).

    16. Distortional Isomers of [LWOCl2]+ in the Solid State and in Solution; Crystal Structures of the Blue and Green Forms of [LWOCl2]PF6 (pages 777–778)

      Prof. Dr. Karl Wieghardt, Dr. Gabriele Backes-Dahmann, Dr. Bernhard Nuber and Prof. Dr. Johannes Weiss

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198507771

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      The two distortional isomers of the title compound 1 have almost identical crystal structures but are different in color. The blue form of 1 has a shorter W[DOUBLE BOND]O bond length than the green form. 1 is the first compound in which the distortional isomerism occurs in the solid state and in solution (L[DOUBLE BOND]N, N′, N″-trimethyl-1,4,7-triazacyclononane).

    17. [L2Femath image(μ-OH)(μ-CH3CO2)2](ClO4)·H2O, a Model Compound for the Diiron Centers in Deoxyhemerythrin (pages 778–779)

      Dr. Phalguni Chaudhury, Prof. Dr. Karl Wieghardt, Dr. Bernhard Nuber and Prof. Dr. Johannes Weiss

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198507781

      The active center of deoxyhemerythrin and the title compound 1 have similar structures and similar magnetic and spectroscopic properties. In both cases, two FeII centers are bridged by two carboxylato ligands and one hydroxo ligand.

      • equation image
    18. Cleavage of an Ether Bond via β-Elimination of Ethanol from [(H2O)5CrCH2CH2OC2H5]2+ in Aqueous Solutions; A Pulse Radiolysis Study (pages 779–781)

      Dr. Haim Cohen and Prof. Dr. Dan Meyerstein

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198507791

      β-Elimination with cleavage of an ether bond has been observed in studies with the title compound. The rate constant for this reaction (4.6 × 103 M−1 s−1) is similar to that for the elimination of the β-OH group from the analogous CH2C(CH3)2OH complex and related compounds.

      • equation image
    19. Selectivity and Mechanism of Diene Cyclodimerization on Iron(0) Complexes (pages 781–783)

      Prof. Dr. Heindirk tom Dieck and Dr. Jörg Dietrich

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198507811

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      The cyclodimerization of butadiene can be promoted by 1,4-diaza-1,3-dieneiron(0) catalysts. At the moment of product formation, at least three diene units are present on the metal center; codimerizations suggest the presence of even four dienes.

    20. Novel Retro-Ene Reactions of β-Hydroxyacetylenes (pages 783–784)

      Prof. Dr. Henning Hopf and Dipl.-Chem. Reinhard Kirsch

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198507831

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      The thermal fragmentation of 3-alkyn-1-ols provides a general method for the synthesis of allenes. Allene aldehydes and allene ketones 2 are obtainable from cyclic compounds of this type such as 1.

    21. Highly Enantioselective Intramolecular Hetero Diels-Alder Reactions for the Synthesis of Enantiomerically Pure Tricyclic Lactones (pages 784–786)

      Prof. Dr. Lutz-F. Tietze, Siegbert Brand and Thomas Pfeiffer

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198507841

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      An intramolecular cycloaddition with 98% ds can be achieved with the heterodiene 1, R1[DOUBLE BOND]R2[DOUBLE BOND]H. The cis-annelated (7aS, 13bR)-tetracycle 2 thus obtained affords the lactone 3 upon cleavage of the chiral auxiliary group.

    22. Cyclodextrins as Second Sphere Ligands for Transition Metal Complexes—The X-Ray Crystal Structure of [Rh(cod)(NH3)2·α-cyclodextrin][PF6]·6H2O (pages 786–787)

      David R. Alston, Alexandra M. Z. Slawin, Dr. J. Fraser Stoddart and Dr. David J. Williams

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198507861

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      The structure of the 1:1 adduct of [Rh(cod)(NH3)2][PF6] (cod = 1,5-cyclooctadiene) and α-cyclodextrin (α-CD) has been elucidated by an X-ray structure analysis. The tub-shaped cod ligand lies almost exactly above the center of the α-CD cavity, into which it partilly protudes. The two NH3 ligands interact with four secondary OH groups.

    23. Stereoselective Nucleophilic Additions to a Bicyclic Ketone Controlled by a Remote Tricarbonyl(diene)iron Moiety (pages 787–788)

      Jean-Christophe Zwick and Prof. Dr. Pierre Vogel

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198507871

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      Electronic and not steric factors are the cause of the stereoselective course of the reduction of the ketone 1 with hydrides to give the alcohol 2. The Fe(CO)3 group favors the preferred syn-attack of the nucleophile (Z, R[DOUBLE BOND]H).

    24. Diboriranides and a 1,3-Diboraallyl System with B[BOND]H[BOND]B Bridge (pages 788–790)

      Rolf Wehrmann, Harald Meyer and Prof. Dr. Armin Berndt

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198507881

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      The first three-membered ring anions 1a, b containing two B atoms and one C atom have been isolated as the potassium salts. Surprisingly, Protonation leads to formation of isolable H-bridged species 2 (R[DOUBLE BOND]SiMe3, R′[DOUBLE BOND]tBu).

    25. Chemoselective Multicomponent Synthesis of α,β-Unsaturated Esters and Lactones and of Their Diels-Alder Adducts (pages 790–791)

      Prof. Dr. Hans Jürgen Bestmann and Dipl.-Chem. Rainer Schobert

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198507901

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      The “one-pot reaction” of alcohols 1 (also chiral), aldehydes 2, and ketenylidenetriphenylphosphorane 3 yields α,β-unsaturated esters 4. With γ-hydroxyaldehydes the reaction leads to formation of macrocyclic α,β-unsaturated lactones. Four-component reactions between 1, 2, 3, and a diene lead immediately to Diels-Alder adducts of 4.

    26. Oxidation of α,β-Unsaturated Esters and Lactones with Selenium Dioxide to γ-Oxo or γ-Hydroxy Derivatives; Synthesis of (±)-A 26771 B and Norpyrenophorin (pages 791–792)

      Prof. Dr. Hans Jürgen Bestmann and Dipl.-Chem. Rainer Schobert

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198507911

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      The γ-oxo α,β-unsaturated lactone moiety [BOND]CO[BOND]CH[DOUBLE BOND]CH[BOND]CO[BOND]O[BOND], which occurs in many macrolide antibiotics, can be synthesized by multicomponent reaction (see previous communication) and oxidation of the lactones thus obtained with SeO2. An example is norpyrenophorin 1. The Oxidation with SeO2/3% H2O yields γ-hydroxy derivatives.

    27. Chiral Poly(9,9′-spirobifluorene) Crown Ethers (pages 792–794)

      Priv.-Doz. Dr. Max Dobler, Dr. Miljenko Dumić, Dipl.-Chem. Martin Egli and Prof. Dr. Vladimir Prelog

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198507921

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      26- to 104-membered rings are the distinguishing features of the title compounds 1, which are obtainable in good yields by phase transfer catalysis. The crystal structures of the known species with n[BOND]1, m[BOND]2 and n[BOND]m[BOND]2 differ greatly from each other. The novel compounds with n[BOND]1, m[BOND]4, 6, 8 and n[BOND]2, m[BOND]4 have also been isolated.

    28. First Sixfold Bridge-Formation in one Step (pages 794–795)

      Dipl.-Chem. Wolfram Kissener and Prof. Dr. Fritz Vögtle

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198507941

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      The polycyclic hexasulfide 2 was obtained in a one-step reaction from the hexaphenylbenzene derivatives 1a, X[DOUBLE BOND]Br, and 1b, X[DOUBLE BOND]SH. 2 has a rigid, helical, six-bladed propeller structure.

  3. Book Reviews

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

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