Angewandte Chemie International Edition in English

Cover image for Vol. 25 Issue 2

February 1986

Volume 25, Issue 2

Pages 115–196

Currently known as: Angewandte Chemie International Edition

    1. Cover Picture (Angew. Chem. Int. Ed. Engl. 2/1986)

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198601151

      Thumbnail image of graphical abstract

      The cover shows the structure of the first highly symmetrical star cluster, [Ni2Pt2W43-CPh)4(CO)8(η-C5H5)4]. The drawing clearly reveals the unusual and novel structural features: tungsten (•), mickel (•), and platinum (•) form an eight-membered ring, which fixes the four phenylcarbyne ligands in a starlike formation. Ni[BOND]Pt bonds are either absent or very weak. The large cavity is empty. Further details regarding this complex and isomers with related structures are reported by F. G. A. Stone et al. on page 190.

    2. Graphical Abstract (Angew. Chem. Int. Ed. Engl. 2/1986)

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198601152

  1. Reviews

    1. Top of page
    2. Reviews
    3. Communications
    4. Book Reviews
    1. Physicochemical and Cytochemical Investigations on the Binding of Ethidium and Acridine Dyes to DNA and to Organelles in Living Cells (pages 115–130)

      Prof. Dr. Herbert W. Zimmermann

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198601153

      Thumbnail image of graphical abstract

      The specific staining of mitochondria in living cells may be achieved with 10-alkyl-acridinium orange dyes; as shown in the picture on the right, neither the cytoplasm nor the cell nucleus shows up in fluorescence microscopy when this dye is used. The specific binding of substances to the mitochondrial membranes, where oxidative phosphorylation takes place, is especially of pharmacological interest.

    2. Resonance Raman Spectroscopy, and Its Application to Inorganic Chemistry. New Analytical Methods (27) (pages 131–158)

      Prof. Dr. Robin J. H. Clark and Dr. Trevor J. Dines

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198601311

      Increased theoretical understanding and improved equipment (lasers) have expanded the scope of application of resonance Raman spectroscopy in recent years. A large number of molecules, from the simplest diatomic inorganic compounds to biochemically important complexes such as the metalloporphyrins, have been studied in detail.

  2. Communications

    1. Top of page
    2. Reviews
    3. Communications
    4. Book Reviews
    1. The Ferrocenylmethyl(Fem) Group as a Highly Lipophilic and Chromophoric Group for the Masking of Peptide Bonds (pages 159–160)

      Dr. Heiner Eckert and Christoph Seidel

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198601591

      Thumbnail image of graphical abstract

      The ferrocenylmethyl (Fem) group may be used to influence the secondary structure of peptide derivatives. It can be incorporated directly and easily during the synthesis of peptides. The severe solubility problems often encountered in peptide chemistry can be solved by the use of the Fem group. Furthermore, its strong yellow color facilitates the preparative workup, especially the chromatographic purification, of the products.

    2. α-Deprotonation of an α-Chiral 2-Alkenylcarbamate with Retention and Lithium-Titanium Exchange with Inversion— the Homoaldol Reaction with 1,3-Chirality Transfer (pages 160–162)

      Prof. Dr. Dieter Hoppe and Thomas Krämer

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198601601

      Thumbnail image of graphical abstract

      One approach to asymmetric homoaldol reactions may be provided by the surprising finding that the lithium compound 1 racemizes only very slowly at − 78°C. Compound 1 reacts with ClTi(Net2)3 with inversion to give a species that can add to carbonyl compounds with 1,3-chirality transfer.

    3. Novel Octahedral Si and Ge Complexes with a Hexadentate Diphenol Ligand (pages 162–163)

      Dipl.-Chem. Bernardo Wolff and Prof. Dr. Armin Weiss

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198601621

      Thumbnail image of graphical abstract

      Finely divided SiO2 dissolves in boiling methanol upon addition of the diphenol ligand 2 and excess sodium acetate along with sodium fluoride as catalyst. The sodium salt of 1, M[DOUBLE BOND]Si, which contains hexacoordinated Si, is formed. The anion 1, M[DOUBLE BOND]Si, is particularly stable. Thus, after 24 h in acetic acid at room temperature, its [HNEt3] salt is practically unchanged. The simple catechol complex decomposes completely under the same conditions.

    4. Decamethylsilicocene—Synthesis and Structure (page 164)

      Prof. Dr. Peter Jutzi, Dipl.-Chem. Dieter Kanne and Prof. Dr. Carl Krüger

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198601641

      The first molecular compound of divalent silicon that is stable under normal conditions and the first π-complex with silicon as the central atom is decamethylsilicocene 2. It was prepared by reduction of 1 with naphthalenelithium, naphthalenesodium, or naphthalenepotassium. Two conformers in the ratio 1:2 are present in the unit cell.

      • equation image
    5. Synthesis of Anionic Triple-Decker Complexes Having Closed 30e Valence Shells by Stacking of Sandwich Anions with Cr(CO)3 Fragments (page 165)

      Prof. Dr. Gerhard E. Herberich, Dr. Bernd Hessner, Dr. Judith A. K. Howard, Dipl.-Chem. Dieter P. J. Köffer and Dipl.-Chem. Roland Saive

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198601651

      Thumbnail image of graphical abstract

      The addition of a 12e metal carbonyl fragment to an 18e sandwich anion, which was predicted to be facile, gave the first 30e triple-decker anion. Thus, [CpFe(C4H4BPh)] reacted regiospecifically with the fragment Cr(CO)3, prepared from [Cr(CO)3(NH3)3], to give the 30e anion 1, which could be isolated as its [NMe3Ph] salt. The 30 valence electron rule plays the same role for triple-decker complexes as the 18e rule for mononuclear organometallic complex. For example, neutral, stable 30e complexes are known.

    6. The Three-Dimensionally Non-Molecular Polyadamantanoid Structure of Cd(SPh)2 (pages 165–166)

      Don Craig, Prof. Dr. Ian G. Dance and Robert Garbutt

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198601652

      Crystalline Cd(SPh)2 is math image{(μ-SPh)6Cd4(μ-SPh)4/2}, an inorganic polymer. It consists of Cd4(SPh)6 cages having adamantane-like structure, each of which is linked with four surrounding cages by four SPh bridges. The three-dimen-113Cd-NMR spectrum indicates that the polymer forms Cd10(SPh)20 molecules having tetraadamantanoid structure upon solution in dimethylformamide.

    7. Vicinal Dilithioalkenes by Addition of Lithium to Simple Cyclic and Acyclic Alkynes (pages 167–168)

      Prof. Dr. Adalbert Maercker, Dipl.-Chem. Thomas Graule and Ulrich Girreser

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198601671

      Thumbnail image of graphical abstract

      The use of 1,2-dilithio(cyclo)alkenes on a preparative scale in organic synthesis is made possible by the title reaction. The addition of lithium to cyclooctyne in ether (− 35°C, 2h) results in the formation of a yellow solution of cis-1,2-dilithiocyclooctene. Acyclic alkenes react much more slowly with lithium (20°C, 48 h) to give trans-dilithioalkenes, which are insoluble in ether.

    8. 1,2-Dilithioethylene Isomers and Their Mechanisms of Interconversion: an Ab Initio Study (pages 169–170)

      Prof. Dr. Paul von Ragué Schleyer, Dipl.-Chem. Elmar Kaufmann, Dr. Alexander J. Kos, Dr. Timothy Clark and Prof. Dr. John A. Pople

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198601691

      Thumbnail image of graphical abstract

      The unusual structures of polylithium compounds are of interest to both exprimental and theoretical chemists. Ab initio MO calculations have now shown that for 1,2-dilithioethylene the twisted trans isomer 1 is most stable. The nonplanar cis isomer 2 is somewhat less stable. The inversion of a CH group is the favored mechanism for the cis-trans interconversion.

    9. Synthesis of the all-L-Configurated Cyclotetradepsipeptide cyclo[-L-Val-L-Lac-]2 by the Combined Protection/Activation Method with the 2,4-Bis(methylthio)phenoxycarbonyl Group (pages 170–171)

      Prof. Dr. Horst Kunz and Dr. Hans-Jürgen Lasowski

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198601701

      The first chemical cyclization of tetradepsipeptides such as 1, which contain only building blocks with the same configuration and without N-methyl groups, has been achieved with the new, activatable 2,4-(MeS)2C6H4[BOND]O[BOND]CO (Bmpc) protecting group. The initially formed cyclic mixed anhydride spontaneously eliminates CO2 to give 2.

      • equation image
    10. A Simple Route to the Intramolecular Quinhydrone of [2.2]Paracyclophanediene (pages 171–173)

      Dipl.-Chem. Michael Stöbbe, Dipl.-Chem. Stephan Kirchmeyer, Dr. Gunadi Adiwidjaja and Prof. Armin de Meijere

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198601711

      Thumbnail image of graphical abstract

      Molecules exhibiting intramolecular charge transfer serve, among other things, as rigid models for the experimental determination of the dependence of this interaction (which is important in photosynthesis) on distance. The title compound 1 is particularly suitable for such studies. Compound 1 was obtained via a very short route by twofold addition of singlet oxygen to [2.2]paracyclophanediene.

    11. The Tetrasilabicyclo[1.1.0]butane System: Structure of 1,3-Di-tert-butyl-2,2,4,4-tetrakis-(2,6-diethylphenyl)tetrasilabicyclo[1.1.0]butane (pages 173–174)

      Ray Jones, Dr. David J. Williams, Dr. Yoshio Kabe and Prof. Satoru Masamune

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198601731

      Thumbnail image of graphical abstract

      The weak central Si-Si bond in 1 is surprisingly short (2.373 Å)—its length is almost the same as that of the Si[BOND]Si bonds in trans,trans,trans-(tBuMeSi)4 (2.377 Å). The Si1[BOND]Si3 bond was expected to be particularly long owing to the high p-character and in analogy to the bonding in bicyclobutanes.

    12. [2.2]Indenophane Dianion: A Novel Double-Layered Dianion (pages 174–175)

      Ron Frim, Dipl.-Chem. Friedrich-Wilhelm Raulfs, Prof. Dr. Henning Hopf and Prof. Mordecai Rabinovitz

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198601741

      Thumbnail image of graphical abstract

      The first examples of a new class of anionic stacked compounds are provided by the surprisingly stable anions 1 and 2. Considerable through-space interactions between the two stacked fragments are presents in 1, as shown by 1H[BOND] and 13C-NMR data.

    13. [Co43-As)3)(μ33-As3)(PPh3)4], a Product of the Reaction of [CoCl2(PPh3)2] with PhAs(SiMe3)2 (pages 175–177)

      Prof. Dr. Dieter Fenske and Dipl.-Chem. Johannes Hachgenei

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198601751

      Thumbnail image of graphical abstract

      A ring containing three As atoms (white) is linked in a novel fashion to a tetrahedron of four Co atoms (black) in the Co4As6 core of the title cluster compound. The other As atoms cap the remaining three faces of the tetrahedron. (The four PPh3 groups bonded to the Co atoms are omitted).

    14. The First Evidence of Endogenous Pyridoxyl Isoquinoline Alkaloids in Mammalian Organisms (pages 177–178)

      Priv.-Doz. Dr. Gerhard Bringmann and Dr. Stephan Schneider

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198601771

      Thumbnail image of graphical abstract

      The “animal alkaloids” 1, R[DOUBLE BOND]H, CO2H, can be detected in rats after intravenous administration of therapeutically common doses of vitamin B6 (pyridoxine) and L-dopa. To accomplish this, it was necessary to develop a method for the analysis of extremely polar substances.

    15. Preparation of Optically Active Alcohols from 1,3-Dioxan-4-ones. A Practical Version of the Asymmetric Synthesis with Nucleophilic Substitution at Acetal Centers (pages 178–180)

      Prof. Dr. Dieter Seebach, Dipl.-Chem. René Imwinkelried and Dipl.-Chem. Gerhard Stucky

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198601781

      Thumbnail image of graphical abstract

      Aliphatic alcohols 3 in ≥90% ee may be prepared via the dioxanones 1, which are readily accessible from aldehydes inexpensive (R)-3-hydroxybutanoic acid. The cyclic acetals 1 react with silyl nucleophiles Me3SiRNu in the presence of Cl3TiX to give, with ≥95% ds, the 3-alkoxy acids 2, from which the alcohols 3 are released by base-induced elimination.

    16. Ferrocene-Modified Polypyrrole Films by Electrochemical Copolymerization (pages 180–181)

      Dipl.-Chem. Alfred Haimerl and Prof. Dr. Andreas Merz

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198601801

      Thumbnail image of graphical abstract

      The preparation of ferrocene-containing polypyrrole layers on platinum electrodes has been achieved by anodic copolymerization of pyrrole with N-(2-ferrocenylethyl)pyrrole. The novel, chargeable redox polymer 1, R[DOUBLE BOND]H and (CH2)2Fc, might be used, for example, for reference microelectrodes.

    17. A Facile Synthesis of a New Class of Eight-Membered Heterocycles from 1-Azabutadienes (pages 181–182)

      Prof. Dr. José Barluenga, Dr. Miguel Tomás, Alfredo Ballesteros, Prof. Dr. Vicente Gotor, Prof. Dr. Carl Krüger and Yi-Hung Tsay

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198601811

      Thumbnail image of graphical abstract

      The regioselective synthesis of substituted 1,5-diazocin-2(1H)-ones 3 has been achieved for the first time by reaction of the azabutadienes 1 with dichlorosilanes to give 2, which are then allowed to react with esters of acetylene dicarboxylic acid (E = CO2R3).

    18. Stable Selenocarbonyl Ylides (pages 183–184)

      Prof. Dr. Rudolf Allmann, Apotheker Franz-Josef Kaiser, Magda Krestel and Prof. Dr. Gunther Seitz

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198601831

      Thumbnail image of graphical abstract

      The first selenium-bridged three-membered-ring compounds of type 1,2, and 3 have been synthesized and isolated. Of particular interest with regard to the synthesis of purely organic conductors is the “push-pull”-substituted, zwitterionic title compound 2 (e.g., R[DOUBLE BOND]iPr, A[DOUBLE BOND]C(CN)2, N[BOND]CN).

    19. Synthesis of Bis(trifluoromethyl)-Analogues of the Pyrethroids (pages 184–185)

      Dr. Helmut Mack and Prof. Dr. Michael Hanack

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198601841

      Thumbnail image of graphical abstract

      Structural variations of the natural, insecticidal pyrethroids have so far involved primarily the ester component and the side chain. Compounds of type 1, in which the geminal CH3 groups are replaced by CF3, have now been prepared. A Wittig reaction with 2 plays the central role in these syntheses.

    20. CF2-Bridged Metal Complexes (pages 185–187)

      Dr. Wolfgang Schulze, Prof. Dr. Hans Hartl and Prof. Dr. Konrad Seppelt

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198601851

      Thumbnail image of graphical abstract

      The stepwise decarbonylation of difluoromalonyl metal complexes such as 1 proved to be an efficient route for the synthesis of complexes containing CF2 bridges. An example is 2. The educt 1 was generated from Na[Mn(CO)5] and CF2(COCl)2.

    21. Laticyclic 1,5-Conjugation between Parallel, Neighboring Azo-Groups and Phenyl Groups (pages 187–188)

      Dipl.-Chem. Karin Beck and Prof. Dr. Siegfried Hünig

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198601871

      Thumbnail image of graphical abstract

      The first [2+6] photocycloaddition between an azo group and a benzene ring was realized by the reaction 1 [RIGHTWARDS ARROW] 2. The significance of the basic skeleton is revealed by 3, which, under the same conditions, does not undergo photocyclization.

    22. Thianthrene 5-Oxide as Mechanistic Probe in Oxygen Transfer Reactions: Substrate Complexation in Oxidations with Transition Metal Peroxides (pages 188–189)

      Prof. Dr. Waldemar Adam and Dr. B. Bhushan Lohray

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198601881

      Thumbnail image of graphical abstract

      Whether complexation of the substrate is involved in oxidations with transition metal peroxides is still unclear. The findings illustrated below — SSO2:SOSO ≈ 1:1, only cis-SOSO—can be interpreted by assuming complexation of the sulfide sulfur of SSO and subsequent transannular transfer of oxygen.

    23. Optically Active α-Chloro-(E)-crotylboronate Esters by Allyl Rearrangement (pages 189–190)

      Prof. Dr. Reinhard W. Hoffmann and Dipl.-Chem. Stefan Dresely

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198601891

      Thumbnail image of graphical abstract

      Good chirality transfer to anti-homoallyl alcohol 3 is observed in the addition of the chiral α-chlorocrotylboronate 2 to aldehydes. The title reaction 1 [RIGHTWARDS ARROW] 2 is effected by SOCl2.

    24. Heteronuclear ‘Star Clusters’: [Ni2Pt2W43-CPh)4(CO)8(η-C5H5)4] and [Ni2Pt2W42-CR)(μ3-CR)3(CO)8(η-C5H5)4] (R = Ph or p-C6H4Me) (pages 190–192)

      Gregory P. Elliott, Dr. Judith A. K. Howard, Dr. Takaya Mise, Christine M. Nunn and Prof. Dr. F. Gordon A. Stone

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198601901

      Thumbnail image of graphical abstract

      An eight-membered ring of metal atoms forms the skeleton of the novel title compounds, the first of which is characterized by a special symmetry. The ring is held to gether in a starlike arrangement by four PhC ligands (only the carbyne C atom is shown).

    25. Synthetic Equivalent for Aminocarboxycarbene; Synthesis of 1-Amino-1-cyclopropanecarboxylic Acid Methyl Esters (pages 192–193)

      Prof. Dr. Ulrich Schöllkopf, Dipl.-Chem. Manfred Hauptreif, Dr. Joachim Dippel, Martin Nieger and Dr. Ernst Egert

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198601921

      Thumbnail image of graphical abstract

      The carbene route to cyclopropane amino acids such as 1a, the parent compound of which is important in the biosynthesis of ethylene, has been employed for the first time. The carbene 4, which is derived from the bislactim ether of a diketopiperazine, was used as synthetic equivalent for 2.

  3. Book Reviews

    1. Top of page
    2. Reviews
    3. Communications
    4. Book Reviews
    1. Book Review: Chemistry of the Elements. By N. N. Greenwood and A. Earnshaw (pages 194–195)

      Hubert Schmidbaur

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198601942

SEARCH

SEARCH BY CITATION