Angewandte Chemie International Edition in English

Cover image for Vol. 25 Issue 5

May 1986

Volume 25, Issue 5

Pages 383–486

Currently known as: Angewandte Chemie International Edition

    1. Cover Picture (Angew. Chem. Int. Ed. Engl. 5/1986)

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198603831

      Thumbnail image of graphical abstract

      The Cover picture clearly demonstrates that good quality high resolution 15N-NMR spectra (0.1 Hz resolution) can now be measured even at natural isotope abundance (0.37%). Top: Proton-coupled INEPT 15N-NMR spectrum of 2-acetylpyridine (nonselective polarization transfer of the protons). Bottom: The same spectrum with selective decoupling of the methyl protons. In view of the ubiquitous occurrence of nitrogen and its indispensability for all living processes it can be safely predicted that 15N-NMR spectroscopy will rapidly increase in importance. Further details are reported by W. von Philipsborn et al. in a review on p. 383.

  1. Reviews

    1. Top of page
    2. Reviews
    3. Communications
    4. Book Reviews
    1. 15N-NMR Spectroscopy—New Methods and Applications [New Analytical Methods (28)] (pages 383–413)

      Prof. Dr. Wolfgang von Philipsborn and Dipl.-Chem. Raffaello Müller

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198603833

      15N-NMR spectroscopy commends itself as a very promising method; whether the mechanism of nitrogen fixation or the interaction between enzymes and inhibitors is under study, whether elucidation of the constitution of complex N-heterocycles or the configuration of diazenido complexes is called for—be it in solution or in the solid state — 15N-NMR spectroscopy is a valuable new tool for the chemist. Thanks to modern high-field NMR instruments and newly developed recording techniques, sensitivity problems have become a thing of the past.

    2. Organic Synthesis at High Temperatures. Gas-Phase Flow Thermolysis [New Synthetic Methods (57)] (pages 414–430)

      Priv.-Doz. Dr. Martin Karpf

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198604141

      Thumbnail image of graphical abstract

      High-temperature reactions have a long tradition in organic chemistry; however, their potential in directed syntheses first emerged only a few years ago. A striking example is the α-alkynone cyclization, which finds application in the synthesis of the carbon backbone of cyclopentanoid natural products.

    3. The Pentagonal Column and the ReO3-Type Structure (pages 431–442)

      Dr. Bengt-Olov Marinder

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198604311

      Thumbnail image of graphical abstract

      A structural feature with unusual symmetry obtains when pentagonal columns occur together with networks of the ReO3-type. These columns consist of a pentagonal bipyramid MX7 which is linked at the five equatorial edges with MX6 octahedra. On the right a model of the unit cell of LiNb6O15F with two pentagonal columns is shown as example.

  2. Communications

    1. Top of page
    2. Reviews
    3. Communications
    4. Book Reviews
    1. Synthesis and Redox Properties of Compounds with Several Separated Anthracene Electrophores (pages 443–444)

      Dipl.-Chem. Jürgen Fiedler, Dr. Walter Huber and Prof. Dr. Klaus Müllen

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198604431

      Thumbnail image of graphical abstract

      Three anthracene units and one or two electrons—where do these reside? Reduction of the new compound 1 with potassium in methyltetrahydrofuran (MTHF) furnishes 1⊕ ⊕/K, in which the spin density is localized in the central anthracene fragment; in DME/HMPT, on the other hand, the spin density is delocalized over all anthracene fragments. In the case of the dianion 12 ⊕/2K in MTHF-glass one electron is contained in the central, and one in a terminal anthracene unit; in DME/HMPT-glass, another dianion is also formed. 16 ⊖ can be detected cyclovoltammetrically.

    2. Poly(anthrylenetrimethylene) and 9,10-Bridged Anthracenes by Reductive Alkylation (pages 444–446)

      Dipl.-Chem. Dietmar Bender, Dr. Heinz Unterberg and Prof. Dr. Klaus Müllen

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198604441

      Thumbnail image of graphical abstract

      Polymers 1 with anthracene units or bridged anthracenes 2 are obtainable from anthracene carbanions and 1,n-dibromoalkanes. The carbanion 3, which has both electrophilic as well as nucleophilic properties, functions as key intermediate.

    3. Evidence for Equilibria between μ-Alkyne and Alkylidyne Complexes of Tungsten Alkoxides: [W2(OR)6(μ-C2R′2)] ⇌ 2[(RO)3W ≡ CR′] (pages 446–447)

      Prof. Malcolm H. Chisholm, Brian K. Conroy, Dr. John C. Huffman and Nancy S. Marchant

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198604461

      The cleavage of alkynes in the coordination sphere of metals forms the basis of a new synthesis of alkylidyne-capped W3-complexes. Reaction of the alkynes R′C [TRIPLE BOND] CR′with [W2(OCH2tBu)6(py)2] in the molar ratio 1:3 leads to formation of the complexes [W33-CR′)(OCH2tBu)9]; the rate of formation of these complexes depends on R′(Et ∼ ph > Me)—evidence for the equilibria formulated in the title.

    4. Cphenyl[BOND]H ċ O and Cphenyl[BOND]H ċ N Interactions: Crystal Structure of (Z)-4-Benzylidene-2-methyl-5(4H)-oxazolone, an Intermediate for Dehydropeptide Synthesis (pages 447–448)

      Mohamed Souhassou, Dr. André Aubry, Dr. Guy Boussard and Dr. Michel Marraud

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198604471

      Thumbnail image of graphical abstract

      A phenyl ring as proton-donor to carbonyl oxygen atoms and doubly bonded nitrogen atoms is present in the crystal of the title compound 1. Compound 1 forms almost completely planar “dimers”. These findings are of interest, inter alia, in connection with the conformation of aromatic side chains in peptides.

    5. Synthesis of Cyclic, Vicinal Tetraketones (pages 449–450)

      Prof. Dr. Rolf Gleiter and Dipl.-Chem. Gerhard Krennrich

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198604491

      Thumbnail image of graphical abstract

      Cyclic tetraketones without electron donors as substituents should be obtainable in two ways from the starting compound 1 (R [DOUBLE BOND] OH). The route via 2 leads to the desired product 3, whereas the equally interesting “dimers” 5 are obtained via 4.

    6. Synthesis of “C-Disaccharides” by Radical C[BOND]C Bond Formation (pages 450–451)

      Prof. Dr. Bernd Giese and Dipl.-Ing. Tom Witzel

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198604501

      Thumbnail image of graphical abstract

      The first disaccharides linked by a CH2 group can be synthesized by addition of carbohydrate radicals to “carbohydrate alkenes”. An example of these molecules, which are of interest because of their possible enzyme-inhibitor properties, is the species 1.

    7. 4,5-Bis(dimethylamino)phenanthrene and 4,5-Bis(dimethylamino)-9,10-dihydrophenanthrene: Syntheses and “Proton Sponge” Properties (pages 451–453)

      Dr. Thomas Saupe, Claus Krieger and Prof. Dr. Heinz A. Staab

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198604511

      Thumbnail image of graphical abstract

      Strong, almost linear N ċ H ċ N hydrogen bonds are present in 1-perchlorate and its 9,10-dihydro derivative. The N ċ N distance is even shorter and the H/CH3 bridge coupling stronger than in the analogue with a fluorene skeleton. Unprotonated 1 could be generated via a dichlorinated seven-membered dibenzosulfone.

    8. [Pd2S28]4⊖: A 30-Membered Cage Containing an Entrapped Cation (pages 453–454)

      Prof. Dr. Achim Müller, Klaus Schmitz, Erich Krickemeyer, Michael Penk and Dr. Hartmut Bögge

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198604531

      Thumbnail image of graphical abstract

      “Ammonium ion in a golden cage” would be how to describe the novel anion of the compound (PPh4)2(NH2Me2)[Pd2(NH4)(S7)4], if the compound were not to be red. The purely inorganic host-guest complex is not only aesthetically attractive, its coordination chemistry is also interesting: The “golden cage” consists of two PdS4 planes, which form an almost square antiprism and are coupled by four polysulfide chains.

    9. A 2-Phosphonio-Substituted 1-Phospha-1-alkene: Resonance between PIII Alkene and PV Ylide (pages 454–455)

      Priv.-Doz. Dr. Hans H. Karsch, Dipl.-Chem. Hans-Ulrich Reisacher and Dr. Gerhard Müller

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198604541

      Thumbnail image of graphical abstract

      How realistic is a resonance of the type A [LEFT RIGHT ARROW] B [LEFT RIGHT ARROW] C? This question could be answered from the NMR spectroscopic data of 1, the first representative of the 2-phosphonio-substituted 1-phospha-1-alkenes. A considerable amount of the resonance structures B and C was found in the actual structure of 1 (R = 2,4,6-tBu3C6H2).

    10. Phosphorus Analogues of Unsaturated Carbon Compounds: an (s-trans)-1,3-Diphospha-4-metallabutadiene and Its (s-cis)-Fe(CO)3 Complex (pages 455–456)

      Priv.-Doz. Dr. Hans H. Karsch, Dipl.-Chem. Hans-Ulrich Reisacher, cand. Chem. Brigitte Huber, Dr. Gerhard Müller, Prof. Dr. Wolfgang Malisch and Dipl.-Chem. Klaus Jörg

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198604551

      Thumbnail image of graphical abstract

      s-trans Configurated 1,3,-diphospha-4-metallabutadienes 1 form green, air-stable crystals (M = Mo, W; R = 2,4,6-tBu3C6H2). When M = W, 1 reacts like butadiene itself with Fe(CO)3 to give the stable complex 2, in which the WPCP moiety is almost planar.

    11. Dioxides of C-Amino-Substituted Phosphaalkenes and Phosphaallyl Cations (pages 457–458)

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

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198604571

      Thumbnail image of graphical abstract

      Reaction of the phosphaallyl cation 1 with oxygen transfer agents is reminiscent of enamine epoxidations and the ring-opening of amino-oxiranes. Even the perchlorate counterion can effect this oxidation in acetonitrile at 60 °C. No kind of conjugation between the two amidinio moieties is detectable in the product 2.

    12. Facile Entry to Geminally Dialkylated Chlorins (pages 458–459)

      Prof. Dr. Franz-Peter Montforts and Dr. Gottfried Zimmermann

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198604581

      Thumbnail image of graphical abstract

      Patially reduced porphinoid pigments such as Factor I 1 and sirohydrochlorin are of great biochemical importance. It has now been possible, on model compounds, to carry out the geminal dialkylsubstitution in the saturated pyrrole rings (such as A) — this was achieved remarkably simply by Claisen rearrangement of amide acetals.

    13. Thioketone S-Oxides by [2 + 2]-Cycloaddition of Ynamines to N-Sulfinyltosylamide (pages 459–460)

      Dipl.-Chem. Steffen Kosack, Prof. Dr. Gerhard Himbert and Prof. Dr. Gerhard Maas

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198604591

      Thumbnail image of graphical abstract

      The thioketone oxides 3 are heteroatom-rich synthetic building blocks that can be prepared by [2 + 2]-cycloaddition from ynamines 1 and the C-free heteroallene 2. Both E-as well as Z-configuration is found at the C = S bond (R1 = Me, Et, Ph; R2 = Et, Ph; R3 = H, Me, Ph).

    14. Unusual Behavior of the Stable Paramagnetic Dihydridoiridium(IV) Complex [Ir(H)2(Cl)2(iPr3P)2] in Solution (pages 460–462)

      Dr. Pasquale Mura and Dr. Annalaura Segre

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198604601

      Thumbnail image of graphical abstract

      A temperature-dependent equilibrium between para-1A and diamagnetic species 1B in solution was deduced from the surprisingly sharp 1H- and 13P-NMR spectra of the title compound 1. A kind of bonding could exist between 1B and H2. 1 is certainly present as 1A.

    15. Stereospecific Reductions with Hydrogen Gas, Modified Metal Catalysts, Methyl Viologen and Enzymes or Microorganisms (pages 462–463)

      Dr. Iordanes Thanos and Prof. Dr. Helmut Simon

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198604621

      The coupling of reductases and microorganisms for bioreductions on hydrogen gas has been accomplished with the system mentioned in the title. Decisive for this is the modification of palladium, platinum, and Raney nickel with a commercially available fluorine-containing surfactant. 2-Enoates and 2-oxo-carboxylates are reduced highly enantioselectively. The reduction systems are especially simple, and the greater expense involved in electrochemical reductions is circumvented.

    16. Unusual Bridging of the Metal Centers in Dimeric Bis(η-methylcyclopentadienyl)-phenylethynylzirconium (pages 463–465)

      Prof. Dr. Gerhard Erker, Dipl.-Chem. Wolfgang Frömberg, Dr. Richard Mynott, Ing. Grad. Barbara Gabor and Prof. Dr. Carl Krüger

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198604631

      Thumbnail image of graphical abstract

      A delocalized metallacyclic system is present in the title compound 1, which was prepared from Cpmath imageZr(C[TRIPLE BOND]CPh)2 and the thermally generated bent metallocene Cpmath imageZr with transfer of a phenylethynyl unit. The diamagnetic product 1 has no metal-metal bond; the formally d1-configurated zirconium centers are linked exclusively via the σ, π-alkynyl ligands (Cp* = η-C5H4CH3).

    17. Superactive Alkali Metal Hydride Metalation Reagents: LiH, NaH, and KH (pages 465–466)

      Peter A. A. Klusener, Prof. Dr. Lambert Brandsma, Hermann D. Verkruijsse, Prof. Dr. Paul von Ragué Schleyer, Thomas Friedl and Dr. Rafael Pi

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198604651

      Alkali metal hydrides would be ideally suitable for the synthesis of carbanions, since only H2 would be formed as second product; unfortunately, however, they are normally not very reactive. A synthesis of LiH, NaH and KH by hydrogenation of BuM (M = Li, Na, K) in hexane is now described here which leads to highly reactive metal hydrides. In addition, they deprotonate more selectively than other metalation reagents.

    18. Synthesis of a Dicyclopenta[a, e]pentalene by [6 + 2]-Cycloaddition of 1,3-Di-tert-butyl-5-vinylidenecyclopentadiene and Consecutive 8π-Electrocyclic Reaction (pages 466–468)

      Dipl.-Ing. Bernd Stowasser and Prof. Dr. Klaus Hafner

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198604661

      Thumbnail image of graphical abstract

      The first non-benzenoid, linearly annelated, tetracyclic system with [4n + 2]-perimeter and [4n]-partial structures was obtained by dimerization of the allene derivative 1 via [6 + 2]-cycloaddition. Subsequent 8π-electrocyclization yielded a tetraquinane, which could be dehydrogenated to the title compound 2.

    19. Bicyclo[3.2.1]octa-2,6-dienyllithium (pages 468–469)

      Dipl.-Chem. Norbert Hertkorn, Prof. Dr. Frank H. Köhler, Dr. Gerhard Müller and Dipl.-Chem. Gabriele Reber

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198604681

      Thumbnail image of graphical abstract

      The first isolable, crystalline compound containing the bishomoaromatic anion bicyclo[3.2.1]octa-2,6-dienide, the tetramethyl-ethylenediamine adduct of the title compound 1, has Cs symmetry in solution. In crystalline 1, however, the lithium is bonded unsymmetrically to all five sp2 C-atoms. The C2- and C3-bridges are surprisingly close to each other, as is required for bishomoaromaticity; lithium has the unusual coordiation number 7.

    20. Synthesis and Structure of the First Arsaalkenyl Complex with FeAs Single Bond (pages 469–471)

      Prof. Dr. Lothar Weber, Georg Meine and Dr. Roland Boese

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198604691

      Thumbnail image of graphical abstract

      The structural unit Fe[BOND]As[DOUBLE BOND]C is the characteristic feature of the title compounds 2. They were prepared from 1 as outlined below. The Fe—As = C—O skeleton of 2a, R = tBu, is planar; the As = C bond has a length of 182.1 pm.

    21. P6tBu4O and P7tBu5O— the First Polycyclophosphane Oxides (pages 471–473)

      Prof. Dr. Marianne Baudler, Dr. Michael Michels, Dr. Manfred Pieroth and Dr. Josef Hahn

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198604711

      Thumbnail image of graphical abstract

      In the oxidation of polycyclophosphanes, oxygen is bound exocyclically and is not inserted into the PP bonds. The P skeleton of the educts remains intact during the oxidation. l a and its isomer, with oxygen on P3 of the five-mem-bered ring, and 2a and 2b are obtained from P6,tBu4, and P,tBu, respectively. Proof of the constitution of the compounds followed from the 31P{1H}-NMR spectra, which could be taken from an NMR handbook.

    22. Reactivity of Anionic Pentacoordinated Silicon Complexes towards Nucleophiles (pages 473–474)

      Alain Boudin, Dr. Geneviève Cerveau, Dr. Claude Chuit, Prof. Dr. Robert J. P. Corriu and Dr. Catherine Reye

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198604731

      Thumbnail image of graphical abstract

      Steric hindrance seldom plays a role in nucleophilic substitutions at silicon, since the pentacoordinated Si anions of 1, R, R = Me, Ph, 1-naphthyl, react far more rapidly with nucleophiles, e.g. PhMgBr, than the neutral compound 2. “By-products” of the reactivity study are new synthetic methods for RSiH3, RR′2SiH, and RSiR′3 (R′ = alkyl, aryl).

    23. Reaction of Grignard Reagents with Dianionic Hexacoordinated Silicon Complexes: Organosilicon Compounds from Silica Gel (pages 474–476)

      Alain Boudin, Dr. Geneviève Cerveau, Dr. Claude Chuit, Prof. Dr. Robert J. P. Corriu and Dr. Catherine Reye

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198604741

      Thumbnail image of graphical abstract

      The pyrocatechol complexes 1 are the central intermediates in the synthesis of R3SiR′ (R = Et, nBu; R′ = H, Cl, SiPh3, GePh3, CH2CH = CH2) and R4Si (R = CH2CH = CH2, Ph, C[TRIPLE BOND]C—CH3) from silica gel. Characteristic of these reactions is that they can be carried out under mild conditions and high yields are obtained.

    24. Enantioselective Robinson Annelations via Phase-Transfer Catalysis (pages 476–477)

      Dr. Apurba Bhattacharya, Dr. Ulf-H. Dolling, Dr. Edward J. J. Grabowski, Dr. Sandor Karady, Kenneth M. Ryan and Dr. Leonard M. Weinstock

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198604761

      Thumbnail image of graphical abstract

      Alkaloids as chiral phase transfer catalysts effect enantioselective alkylation of 1, R = Pr, with the methyl vinyl ketone synthetic equivalent 1,3-dichloro-2-butene to give 2, R1 = Pr, R2 = CH2CH = C(Cl)CH3. The two enantiomers are obtained with 92 and 78% ee, respectively, and, in each case, in 99% yield; cinchoninium and cinchonidinium derivatives serve as catalysts. The results are explained in terms of an intermediate formation of a tight ion pair.

    25. A Transition Metal Atom as Building Block of a Cyclic Phosphazene– Synthesis and Structure of [Cl3WN3(PPh2)2] (pages 477–478)

      Prof. Dr. Herbert W. Roesky, Dr. Kattesh V. Katti, Dipl.-Chem. Ulrich Seseke, Dr. Michael Witt, Dr. Ernst Egert, Regine Herbst and Prof. George M. Sheldrick

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198604771

      Thumbnail image of graphical abstract

      A six-membered planar WN3P2 ring characterizes the structure of the title compound 3; probably a chlorine-bridged polymer is present in the solid state. The yellow phosphazene 3 is formed upon reaction of tungsten hexachloride 1 with the salt 2 in chloroform.

    26. Synthesis of Alkyl Azides with a Polymeric Reagent (pages 478–479)

      Prof. Dr. Alfred Hassner and Dr. Meir Stern

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198604781

      Thumbnail image of graphical abstract

      Many desirable features of an alkyl azide synthesis—among other things reaction at rom temperature in organic solvents, work-up without introduction of heat—are combined in the use of the novel “azidizing” polymer 1. The polymer 1 was prepared from Amberlite IR-400 and NaN3, allowed to react in ca. tenfold excess with alkyl halides or tosylates (almost always quantitative) and simply filtered from the solutions of the alkyl azides. Even the synthesis of CH2(N3)2 from CH2Cl2 could be achieved with this method.

    27. Diastereoselective Transformations on Heterometal Clusters (pages 479–480)

      Dipl.-Chem. Christine von Schnering, Dipl.-Chem. Thomas Albiez, Dipl.-Chem. Wolfgang Bernhardt and Prof. Dr. Heinrich Vahrenkamp

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198604791

      Thumbnail image of graphical abstract

      The diastereoselective acetylene-vinylidene rearrangement 1 [RIGHTWARDS ARROW] 2 surprisingly has no steric, but probably electronic causes. The stereoselectivity of the reaction depends on the nature of the metal atoms forming the cluster skeleton and on the residue R.

    28. ESR Observation of Thermally Produced Triplet Nitrenes and Photochemically Produced Triplet Cycloheptatrienylidenes (pages 480–482)

      Dr. Martin Kuzaj, Dr. Holger Lüerssen and Prof. Dr. Curt Wentrup

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198604801

      Thumbnail image of graphical abstract

      The fascinating carbene-nitrene rearrangement can be observed directly by ESR spectroscopy. In the thermal decomposition of the carbene precursor 4 (via 3) with subsequent matrix isolation, the product gave the same ESR signal as phenylnitrene 2 from phenylazide 1! In the aza-analogous system, the seven-membered carbene 5 is probably formed as intermediate of the rearrangemet.

  3. Book Reviews

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

SEARCH

SEARCH BY CITATION