Angewandte Chemie International Edition in English

Cover image for Vol. 18 Issue 7

July 1979

Volume 18, Issue 7

Pages 493–561

Currently known as: Angewandte Chemie International Edition

  1. Reviews

    1. Top of page
    2. Reviews
    3. Communications
    4. Book Reviews
    1. Synthesis and Biosynthesis of Alkoxylipids (pages 493–503)

      Prof. Dr. Helmut K. Mangold

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.197904933

      Animal tissues contain alkoxylipids in which the fatty acid group R CH2 CO O attached to C-1 of glycerol is replaced by R CH2 CH2 O or R CH CH O. The biological function of these alkoxylipids is still unknown—they are used in biomedical investigations.

    2. Ureas as Solvents for Chemical Investigations (pages 503–507)

      Prof. Dr. Barbara J. Barker, Dr. Joseph Rosenfarb and Dr. Joseph A. Caruso

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.197905031

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      Four urea derivatives useful as nonaqueous solvente.g. for electrochemical and analytical studies. have the formulas shown below. These stable compounds have a wide liquid range and favorable dipole moments and dielectric constants.

    3. The Chemistry of Iodine Azide (pages 507–514)

      Prof. Dr. Kurt Dehnicke

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.197905071

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      Hantzsch's warning about the use of IN3has been widely observed for decades: only recently has the pure compound been isolated. Safe handling of this highly labile reagent opens up new perspectives in synthetic chemistry.

    4. Pyrolysis of Sulfones as a Synthetic Method [New synthetic methods (28)] (pages 515–529)

      Prof. Dr. Fritz Vögtle and Dipl.-Chem. Ludovica Rossa

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.197905151

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      C[BOND]C linkage on extrusion of SO2 from cyclic sulfones containing structural elements such as aromatic rings, hetero atoms, functional groups—including further SO2 groups—as ring members leads to sterically handicapped systems, e.g of phane type, in preparatively simple manner.

  2. Communications

    1. Top of page
    2. Reviews
    3. Communications
    4. Book Reviews
    1. Generation of the triangulo-Group MOV-η-S2 in the “Condensation” of [MoVIO2S2]2 to [Momath imageO2S2(S2)2]2 (pages 530–531)

      Dr. Walter Rittner, Prof. Dr. Achim Müller, Dipl.-Chem. Axel Neumann, Wolfgang Bäther and Dr. Ramesh Chandra Sharma

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.197905301

      Formation of the η-disulfidomolybdenum(V) group by a novel intramolecular redox process has been observed on warming aqueous solutions of dithiomolybdate(VI). The structure of the anion in the orange-red crystals of (1) was determined by X-ray methods.

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    2. FeCoMoWS(AsMe2)Cp2(CO)7: The First Cluster to Contain Four Different Metal Atoms (page 531)

      Dipl.-Chem. Felix Richter and Prof. Dr. Heinrich Vahrenkamp

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.197905311

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      A novel tetranuclear cluster having a tetrahedral FeCoMoW skeleton(1) has been obtained in a directed synthesis. The chiral complex contains six different metal-metal bonds

    3. (Diazomethyl)cyclopropenes–Synthesis, Isomerization, and Carbene Reactions (pages 531–533)

      Prof. Dr. Manfred Regitz, Dipl.-Chem. Annemarie Heydt and Dr. Berndt Weber

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.197905312

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      Electrophilic substitution of diazo compounds with cyclopropenylium and other Hückel-aromatic cations affords products of versatile reactivity: e.g (1), R1 = R2 = Ph, isomerizes to the pyridazine (2); on irradiation (1) forms the carbene.

    4. Homogeneous Catalytic Vinylation of Cyclic Imides and Lactams for the Synthesis of N-Vinyl Monomers (pages 533–534)

      Prof. Dr. Ernst Bayer and Dr. Kurt Geckeler

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.197905331

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      A general synthesis of monomeric N-vinylimides and-lactams has been found in the homogeneously catalyzed recation with vinyl acetate. The recation proceeds in one step and gives high yeilds on use of Na2PdCl4 as catalyst.

    5. Manganese-Containing Heterocycles Having a λ4-Thia-λ5-phosphanorbornadiene Skeleton (pages 534–535)

      Prof. Dr. Ekkehard Lindner, Dipl.-Chem. Axel Rau and Dipl.-Chem. Sigurd Hoehne

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.197905341

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      A new pathway leading to metallacycles of type (2) consists in the reaction of inorganic heterocycles such as (1) with acetylene derivatives. Compounds (2) (R1 [DOUBLE BOND] Me, Ph;R2 [DOUBLE BOND] CO2Me, CO2Et) have been characterized by X-ray structure analysis. Such heterocycles are of importance in organic synthesis, especially in catalytic processes.

    6. Synthesis of Metallacycles with Reactive Metal-Carbon σ Bonds (page 535)

      Prof. Dr. Ekkehard Lindner, Dipl.-Chem. Guido Funk and Dipl.-Chem. Sigurd Hoehne

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.197905351

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      Metallacycloalkane derivatives such as (1) play an important role in the activation of C H bonds and transition-metal catalyzed reactions. A new procedure of general validity now also permits the first syntheses of compounds (1)e.g with metals of Group 7.

    7. Preferred β-Glycoside Formation by Phase Transfer Catalysis in the Synthesis of D-Arabinofuranosyl-7-deazapurine Nucleosides (page 536)

      Prof. Dr. Frank Seela and Dipl.-Chem. Dieter Winkeler

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.197905361

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      The ratio of α-to β-glycoside [(3a):(4a)] obtained in the phase-transfer recation of (1) with (2) can be modified by means of the catalyst: it is 8:2 for PhCH2Etmath imageNCI and 6:4 for Bu4NHSOmath image.

    8. Fully Active Insulin by Selective Formation of the Disulfide Bridges between a Sythetic A-Chain and Natural B-Chain (pages 536–538)

      Priv.-Doz. Dr. Christian Birr and Phil. cand. Rüdiger Pipkorn

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.197905362

      Directed formation of the three disulfide bridges in insulin is a decisive synthetic step. Only 10% of insulin is formed on random recombination of A- and B- chains (1:1). An A-chain synthesized with selectively removable sulfur protecting groups on a polymeric carrier was allowed to react with a natural B-chain. The yield of fully active insulin increases to 25%.

    9. Boat Conformation of cyclo-[L-Pro2-D-Pro] (pages 538–539)

      Dr. Jan Willem Bats, Dipl.-Chem. Axel Friedrich, Prof. Dr. Hartmut Fuess, Prof. Dr. Horst Kessler, Dipl.-Chem. Werner Mästle and Prof. Dr. Manfred Rothe

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.197905381

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      Conformational studies on small cyclic peptides are particulary informative because such compounds have model character owing to their limited flexibility. In cyclotripeptides made up of three chiral amino acids, the same chirality leads to the crown from, whereas differing chirality should lead to the boat from. This was confirmed for cyclo-[L-Pro2-D-Pro] in solution and in the solid state.

    10. Use of Biogenetic Key Compounds for the Biomimetic Synthesis of Natural Products: (S)-Elenolide from Secologanin (pages 539–540)

      Prof. Dr. Lutz-F Tietze and Dipl.-Chem. Horst C. Uzar

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.197905391

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      Mimicry of nature has considerable advantages in the synthesis of alkaloids and similar substances; just a few reaction steps generally lead to enantiomerically pure products. The three-step synthesis of (S)-elenolide (2) from secologanin (1) is an example.

    11. Synthesis of 1,4-Dihydronicotinic Acid Derivatives by Photochemical Cycloaddition (pages 540–541)

      Prof. Dr. Lutz-F Tietze and Dipl.-Chem. Klaus Brüggemann

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.197905401

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      1,4-Dihydronicotinic acid derivatives of type(2) are of interest in connection with their action on the circulatory system and their occurrence in oxidoreductases. A new synthesis of (2) has the advantage of ready starting material availability

    12. Fragmentation of γ-Hydroxyammonium Compounds to Unsaturated Aldehydes by Flash Thermolysis (pages 541–542)

      Prof. Dr. Lutz-F. Tietze, Dr. Günther Kinast and Dipl.-Chem. Horst C. Uzar

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.197905411

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      Unsaturated aldehydes such as (2) are multifunctional starting materials for numerous syntheses. Flash thermolysis of the readily accessible compounds (1) containing the HO[BOND](CR2)3[BOND]equation imageMe3OH structural element is of general applicability and leads to good yields of (2).

    13. CoII with Coordination Number 3: Na4[CoO3]–The First Oxocobaltate(II) with an Island Structure (pages 542–543)

      Dipl.-Chem. Wilfried Burow and Prof. Dr. Rudolf Hoppe

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.197905421

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      “Cation-rich” oxides of alkali metals exhibit surprising structural characteristics. The bright red compound Na4[CoO3] now synthesized (Na2O+CoO,Na:Co[DOUBLE BOND]4.4:1, sealed Co tube 550°C, 20 d under dry argon) contains an “anion” analogous to COmath image.

    14. The First Stable Derivative of 7-Stannanorbornane and Its Thermolysis (pages 543–544)

      Dr. Christian Grugel, Prof. Dr. Wilhelm P. Neumann and Dipl.-Chem. Michael Schriewer

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.197905431

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      Free dimethylstannanediyl (“dimethylstannylene”) (2)—to be regarded as truly free because of its synthesis—has been generated by thermolysis of the adduct (1) which is stable at −30°C. A concerted mechanism is proposed to account for the formation of (2).

    15. 1,3-Di-tert-butylcyclooctatetraene (page 544)

      Dipl.-Chem. Gregory Wells, Dr. Yuji Hanzawa and Prof. Dr. Leo A. Paquette

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.197905441

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      The first directed and generalizable synthesis of 1,3-disubstituted cyclooctatetraenes such as (4) was accomplished as shown below. Surprisingly, only one compound having this substitution pattern was previously known. viz. the dimethyl derivative (obtained by pyrolsis of 2,8-dimethylsemibullvalene).

    16. Heptalenebis(tricarbonyliron) (pages 545–546)

      Prof. Dr. Emanuel Vogel, Dipl.-Chem. Dimitrios Kerimis, Dr. Neil T. Allison, Dr. Robert Zellerhoff and Dr. Jürgen Wassen

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.197905451

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      The synthesis of substituted heptalenes, e.g(3) and (4), can be accomplished via the bis(tricarbonyliron) derivative (2) formed from (1) and benzylideneacetone(tricarbonyliron). This entry into the chemistry of substituted heptalenes is facilitated by a new heptalene synthesis involving protection of the central double bond of isotetralin by epoxidation.

    17. An Expeditious Synthesis of Heptalene from Naphthalene via a Bis(bicyclo[1.1.0]butane) Intermediate (pages 546–547)

      Prof. Dr. Leo A. Paquette, Dr. Alan R. Browne and Dr. Ernest Chamot

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.197905461

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      A new expeditious entry to heptalene involves six steps starting from naphthalene via isotetralin and the polyclic hydrocarbon (1). The method capitalizes on the regiospecificity of double carbene insertion to give (1) and the ability of Ag+ to isomerize bicyclobutanes.

    18. Tellurium-Catalyzed Reaction of Amines with Carbon Monoxide (pages 547–548)

      Nobuaki Kambe, Dr. Kiyoshi Kondo, Hideo Ishii, Prof. Dr. Shinji Murai and Prof. Dr. Noboru Sonoda

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.197905471

      Tellurium catalyze the formation of urea from amines and carbon monoxide. This is the first example of activation of CO by Te and also of the formation of equimolar amounts of ureas and H2.

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    19. Reactions of Molybdate(VI) with Hydroxylamine and N-Methylhydroxylamine (pages 548–549)

      Prof. Dr. Karl Wieghardt, Dipl.-Chem. Wolfgang Holzbach, Prof. Dr. Johannes Weiss, Dr. Bernhard Nuber and Dipl.-Chem. Boris Prikner

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.197905481

      Two remarkable molybdenum complexes have been isolated on recation of aqueous solutions of MoVI oxo anions with H2NOH or MeHNOH: the yellow NO complex (1) and the colorless NO-free neutral complex (2). This shows that many yellow Mo complexes characterized only in solution pribably contain NO ligands.

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    20. Synthesis of a Hydroxylamido(2−)-O,N-(nitrosyl)molybdenum Complex (page 549)

      Prof. Dr. Karl Wieghardt and Dipl.-Chem. Wolfgang Holzbach

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.197905491

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      The first complex to contain the bidentate ligand [H N O]2− has been isolated and characterized. MoVI oxo anions react with hydroxylamine and terpyridine (tpy)to give a yellow cation (1) which can be isolated as the perchlorate. The red neutral complex (2) is formed reversibly from (1) and cyanide.

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    21. Simple Route to Li- or Zn-Metalated η5-Cyclopentadienyliron-Olefin Complexes (pages 549–550)

      Dr. Klaus Jonas and Dr. Ludwig Schieferstein

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.197905492

      Some new reactions of ferrocene with lithium and olefins involve only replacement of a C5H5 ligand. The product, e.g.(1). DME and (1). TMEDA, can be metalated with ZnCl2 or CdCl2 and transformed into trinuclear complexes with olefinic ligands bonded to iron, such as(2). Reaction of (1) and trityl chloride produces the monomeric radical CpFe(COD)•.

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    22. Tetrakis(ethylene)irondilithium and Bis(η4-1,5-cy-clooctadiene)irondilithium (pages 550–551)

      Dr. Klaus Jonas, Dr. Ludwig Schieferstein, Priv.-Doz. Dr. Carl Krüger and Dr. Yi-Hung Tsay

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.197905501

      New FeLi2-olefin complexes, e.g.(1), have been obtained from ferrocene by directed replacement of both C5H5 ligands. (1) reacts with COD to give (COD)2FeLi2(2) [isolated as (2)·2 DME or (2)·2TMEDA]. which completes the series (COD)2Ni…(COD)2CoLi…(COD)2FeLi2

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    23. Structure and Reactivity of the Orthocarbonic and Orthosilicic Acid Esters of Pyrocatechol (pages 551–553)

      Dr. Heinrich Meyer and Dr. Günter Nagorsen

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.197905511

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      The first compound found to contain planar tetracoordinated silicon is the orthosilicic ester (2). In contrast, the bondilg geometry of the central atom of the analogous orthocarbonic ester deviates only slightly from a tetrahedron. Quantum mechanical studies [e.g. on the model compound (3)] showed that planar tetracoordination is easier for silicon than for carbon. The ability of silicon to engage in sixfold coordination [type(4)] even makes such planar structures easier to achieve than the tertahedral structure.

    24. Planar Tetracoordinate Silicon (pages 553–554)

      Dr. Ernst-Ulrich Würthwein and Prof. Dr. Paul von Ragué Schleyer

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.197905531

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      The first compound found to contain planar tetracoordinated silicon is the orthosilicic ester (2). In contrast, the bondilg geometry of the central atom of the analogous orthocarbonic ester deviates only slightly from a tetrahedron. Quantum mechanical studies [e.g. on the model compound (3)] showed that planar tetracoordination is easier for silicon than for carbon. The ability of silicon to engage in sixfold coordination [type(4)] even makes such planar structures easier to achieve than the tertahedral structure.

    25. Electronic Structure of μ-Methylene-Transition Metal Complexes (pages 554–556)

      Priv.-Doz. Dr. Peter Hofmann

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.197905541

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      Dinuclear metal complexs containing a methylene bridge, e.g.(1), assume a position intermediate between carbene complexes and alkyl complexes, and also warrant interest as members of the series cyclopropanes (C3)…metal-olefin complexes (MC2)…μ-methylene complexes (MC2)…trinuclear metal clusters (M3). MO calculations on (1) provide an insight into their electronic structure.

    26. Spectroscopic Identification of Polymethyl-Substituted 2,4-Cyclohexadienones (pages 556–557)

      Prof. Dr. Gerhard Quinkert, Dr. Gerd Dürner, Dr. Erna Kleiner, Dipl.-Chem. Erhard Haupt and Prof. Dr. Dieter Leibfritz

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.197905561

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      Contrary to a widely held view, it is possible to distinguish by UV spectroscopy betwwen methyl-substituted 2,4-cyclohexadienones of the type showln. A notable relationship exists between the UV maximum of the relatively intense π*,π region and the number and position of additional methyl groups.

    27. The Question of π*,n- and π*,π Selective Photochemistry of 2,4-Cyclohexadienones (pages 557–558)

      Prof. Dr. Gerhard Quinkert, Dr. Franz Cech, Dr. Erna Kleiner and Prof. Dr. Dieter Rehm

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.197905571

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      It is generally accepted that electronically isomeric 2,4-cyclohexadienones (1) having predominatly π*,n and π*,π charcter respectively give the constitutionally isomeric dienylketenes (2) and bicyclohexenones (3). This concept does not stand up to experimental scrutiny: the bicyclic compounds (3) are also products of π*,n photochemistry; they aries from (2).

  3. Book Reviews

    1. Top of page
    2. Reviews
    3. Communications
    4. Book Reviews
    1. Book Review: Inorganic polymers. By N. H. Ray (pages 559–560)

      Reinhard Schliebs

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.197905594

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