Angewandte Chemie International Edition in English

Cover image for Vol. 26 Issue 1

January 1987

Volume 26, Issue 1

Pages 1–92

Currently known as: Angewandte Chemie International Edition

    1. Cover Picture (Angew. Chem. Int. Ed. Engl. 1/1987)

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198700011

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      The cover picture shows the interference pattern obtained with a laser interferometer with a synchronoulsy superposed image of a “dancing flame”. Laser light was used to reproduce very rapidly changing structures in a flame continuously. The special properties of laser light (high coherence and monochromism), however, are not only of importance for such investigations but can also be used, e.g., for the excitation of moleucled of only one definite orientation or isotopic composition. More details on the use of the use of lasers in chemistry, materials research and medicine are reported in an article by J. Wolfrum and K. Kleinermanns on page 38 ff. (Photograph: A. Schönbucher, Stuttgart (FRG)).

  1. Reviews

    1. Top of page
    2. Reviews
    3. Communications
    4. Book Reviews
    1. Unsaturated Molecules Containing Main Group Metals (pages 1–14)

      Prof. Dr. Michael Veith

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198700013

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      Unusually reactive compounds with a kind of “double bonding”- are formed when an electrophilic center and a nucleophilic center are bound directly to each other. An oligomerization can be counteracted only by bulky ligands on the main-group metal atom or on the nonmetal atom. The four-membered ring Me2Si(NtBu)2Sn is named as example; it adds H-X with formation of 1.

    2. Totally Synthetic Routes to the Higher Monosaccharides (pages 15–23)

      Prof. Samuel J. Danishefsky and Michael P. DeNinno

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198700151

      Monosaccharides with seven to eleven carbon atoms occur in a group of natural products of broadly varied biological function. A successful strategy for the synthesis of these monosaccharides has been made possible by three developments: (1) high regioselectivity and diastereofacial selectivity in the synthesis of pyranoid systems by hetero-Diels-Alder reactions; (2) stereoselective reactions for the functionalization of the pyranoid system; (3) stereoselective reactions for the transfer of chiral information from the pyranoid system to newly formed chirality centers in the side chain.

    3. Stereoselective Aldol Reactions with α-Unsubstituted Chiral Enolates (pages 24–37)

      Prof. Dr. Manfred Braun

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198700241

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      Stereoselective CC coupling can nowadays also be accomplished in Aldol reactions of the most simple enolates. Upon reaction with aldehydes, enolates of type 1 (X* is a chiral auxiliary group) can afford the desired β-hydroxy-carbonyl compounds 2. One of the diastereomers 2a or 2b dominates by far over the other. Reactions of this kind are of interest, e.g., for the synthesis of polyether and macrolide antibiotics.

    4. Laser Chemistry–What is Its Current Status? (pages 38–58)

      Dr. Karl Kleinermanns and Prof. Dr. Jürgen Wolfrum

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198700381

      Some 25 years after its discovery, the laser is irreplaceable in many areas of basic chemical research. In physical chemistry it is used, inter alia, for the nonintrusive observation of rapidly changing chemical processes, while in organic chemistry it is being exploited more and more in photochemical syntheses, and in macromolecular chemistry it is used in the preparation of monomers (vinyl chloride) and polymers (polyethylene). The separation of isotopes, the preparation of catalysts, and surface treatment by the deposition and ablation of material are further examples of successful applications in chemical and materials research.

  2. Communications

    1. Top of page
    2. Reviews
    3. Communications
    4. Book Reviews
    1. [(η-5-P5)Fe(η5-C5Me5)], a Pentaphosphaferrocene Derivative (page 59)

      Prof. Dr. Otto J. Scherer and Dipl.-Chem. Thomas Brück

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198700591

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      cyclo-Pmath image, like C5Hmath image, can function as a 6π-electron-donor in sandwich complexes: Reaction of [(η5-C5Me5)Fe(CO)2]2 and P4 affords 1, which has been characterized by NMR and mass spectroscopy. It is possible that cyclo-Pmath image is formed from Pmath image and P2.

    2. (Me3Si)2N[BOND]P[DOUBLE BOND]NSiMe3 as Educt for Electron-Rich Phoshorus-Nitrogen Ligands (pages 59–61)

      Prof. Dr. Otto J. Scherer, Dipl.-Chem. Karin Göbel and Dr. Jürgen Kaub

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198700592

      Three unusual P-N compounds stabilized in di- or trinuclear clusters are formed upon cothermolysis of [Fe3(CO)12] and 1: the 6e-donor ligand 2, the phosphanediyl 3, and the substituted hydroxy(imiuo)phosphane 4 (R = Si Me3).

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    3. Total Synthesis of the Pseudoguaianolide (+)-Confertin (pages 61–62)

      Prof. Dr. Gerhard Quinkert, Dr. Hans-Günther Schmalz, Dipl.-Chem. Egon -Walzer, Dr. Teresa Kowalczyk-Przewloka, Dr. Gerd Düner and Dr. Jan W. Bats

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198700611

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      The potential of the methyl derivative 1b as a chiral building block has been examined following the demonstrated usefulness of the compounds 1a and ent-1a.. 1b is equipped with the correct sense of chirality and the necessary functionality for stereoselective expansion of the three-membered ring and condensation of the seven-membered ring to give ( + )-confertin 2. The total synthesis of 2 is the first of an enantiomerically pure pseudoguaianolide.

    4. Control of the Molecular Weight of Polyethene in Syntheses with Bis(ylide)nickel Catalysts (pages 63–64)

      Dr. K. Alexander Ostoja Starzewski and Dr. Josef Witte

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198700631

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      Polyethenes in almost all molecular weight ranges —from polyethene waxes and hard waxes through high-density polyethene to ultrahigh molecular weight polyethene -are accessible with the aid of novel, very active bis(ylide)nickel(0) catalysts. The catalysts are prepared from bis(cyclooctadiene)nickel(0), the carbonyl-stabilized ylide ligands 1-3, and a non-stabilized ylide.

    5. Biomimetic Synthesis of a Twofold N,N′-Bridged Porphyrinogen (pages 64–65)

      Dipl.-Chem. Ralf Timmermann, Prof. Dr. Rainer Mattes and Prof. Dr. Burchard Franck

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198700641

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      A cage-like structure and a strong deformation of the tetrapyrrole system characterize the title compound 1, which was synthesized by dimerizing alkylation of 3,4-di-ethyl-2-formylpyrrole with 1,3-dibromopro-pane, reduction of the resulting dialdehyde to the dialcohol and in situ cyclocondensation.

    6. Nickel Complexes with a Propellane Structure (pages 65–67)

      Dr. Harald Schwager, Prof. Dr. Carl Krüger, Prof. Dr. Richard Neidlein and Prof. Dr. Günther Wilke

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198700651

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      Addition of nickel(0) complexes to the three-membered ring double bond of 1 leads with preservation of the three-membered ring and removal of aromaticity to the formation of compounds of type 2.

    7. Reactions of (η3-Allyl)(η5-cyclopentadienyl)palladium with Cyclopropabenzenes (pages 67–68)

      Dr. Harald Schwager, Dr. Reinhard Benn and Prof. Dr. Günther Wilke

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198700671

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      That the substituents of an educt determine the skeletal structure of the product has been found in the case of the title reactions. Cy-clopropabenzene, difluorocyclopropaben-zene and bis(trimethylsilyl)cyclopropaben-zene react with 1 and PMe3 to give three different types of palladium complexes: the η1-benzyl complex 2, a palladatricyclooctadiene, and a palladacyclobutabenzene, respectively.

    8. A Triple Decker Sandwich Structure by Reaction of Cyclopentadienylbis(ethylene)cobalt with Carbodiimides: an Unusual Cyclopentadienylcobalt Oligomer (pages 68–70)

      Sergio Stella, Prof. Dr. Carlo Floriani, Dr. Angiola Chiesi-Villa and Dr. Carlo Guastini

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198700681

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      The formation of the triple-decker 1 from [CpCo(C2H4)2] and dicyclohexylcarbodiimide was not anticipated. The Co4-compound 1 forms red crystals. The double bonds in the middle ring, drawn localized here, could also be partially delocalized (R = cyclohexyl).

    9. A New Class of Organozirconium(IV) Compounds: Alkyl Derivatives of Tetramethyltetraazadibenzo[14]annulenatozirconium(IV) (pages 70–72)

      Prof. Dr. Carlo Floriani, Stefano Ciurli, Dr. Angiola Chiesi-Villa and Dr. Carlo Guastini

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198700701

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      Macrocycles have unusually favorable promise as auxiliary ligands in compounds of the early transition metals. One example is compound 1, which is formed on reaction of the ZrCl2-complex of the same macrocyclic ligand with benzylmagnesium chloride.

    10. Unusual 1,6-Addition of a Carbenoid (pages 72–73)

      Dipl.-Chem. Michael Birkhahn, Prof. Dr. Eckehard V. Dehmlow and Dr. Hartmut Bögge

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198700721

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      Steric factors hinder intramolecular 1,2- or 1,4-addition in the RhII-catalyzed decomposition of 1, such that 2 is isolated as product of the 1,6-addition. 1 is accessible in five steps from cyclooctatetraene.

    11. First Four-Membered Metallacycles of Rhenium (pages 73–74)

      Dr. Henricus J. R. de Boer, Dr. Bartholomeus J. J. van de Heisteeg, Martina Flöel, Prof. Dr. Wolfgang A. Herrmann, Dr. Otto S. Akkerman and Prof. Dr. Friedrich Bickelhaupt

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198700731

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      The rhenacyclobutanes 2 and 3, obtained from the oxorhenium(v) complex 1, have model character for the intermediates of olefin metathesis. Both compounds are thermally stable, and, in the 1H-NMR spectrum, give a characteristic AX pattern for the geminal methylene protons.

    12. [CH3C6H5BiCl2][AlCl4] and [(CH3)6C6BiCl2] [AlCl4]–Compounds containing η6-Arene-Complexed BiClmath image Units (pages 74–75)

      Dr. Walter Frank, Jürgen Weber and Elisabeth Fuchs

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198700741

      The ability of AlCl3 to abstract chloride ions from BiCl3 makes it possible to synthesize the title compounds in the presence of toluene and hexamethyl benzene, respectively. 1, the hexamethylbenzene complex, is an arene-stabilized, dimeric dichlorobismuth(III) tetrachloroaluminate. The coordination of bismuth can be described as strongly distorted octahedral; five Cl ligands (two shorter, three longer Bi–Cl distances), one arene ligand.

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    13. High-Pressure LiGe with Layers Containing Two- and Four-Coordinate Germanium Atoms (pages 76–78)

      Dr. habil Jürgen Evers, Gilbert Oehlinger, Dipl.-Chem. Gerhard Sextl and Dr. Hans-Otto Becker

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198700761

      The preparation, from a Zintl-phase with a semimetal, of a high-pressure phase in which the coordination in the semimetal partial structure is no longer reconcilable with the Zintl-Klemm concept has been accomplished for the first time with LiGe. At normal pressure LiGe can still be classed under the Zintl phases, whereas LiSn can no longer be so classified. The LiGe high-pressure phase crystallizes in a novel structure type, which is made up of layers containing two- and four-coordinate germanium and which shows close relationships to the structures in LiSn and LiPb.

    14. Crystal Structure of [α-Nitrobenzyllithium · Ethanol]n; A Lithium Nitronate-Ethanol Interaction (pages 78–79)

      Dr. Gerhard Klebe, Karl Heinz Böhn, Michael Marsch and Prof. Dr. Gernot Boche

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198700781

      The title compound 2 is a lithium nitronate which crystallizes out with ethanol. Ethanol crystallizes during the preparation of 2 from 1 and lithium ethoxide outlined below, but is also present as solvent. Remarkable features of crystalline 2 are, in particular, the bonding of Li to nitronate and ethanol O-atoms and the O[BOND]H ⃛O bridges from ethanol to a nitronate O-atom.

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    15. Synthesis of Nitriles via the Ylide Anion of Sodium Cyanotriphenylphosphoranylidenemethanide (pages 79–81)

      Prof. Dr. Hans Jüryen Bestmann and Dipl.-Chem. Martin Schmidt

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198700791

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      A convenient access to nitriles having a variety of extremely different structures is provided by the ylide anion 1, which is isolable as the sodium salt. By reaction with alkyl halides RX, 1 can be converted into cyclic α,β-unsatu-rated nitriles such as 2; the “dienyl cyanides” 3 and alkynyl cyanides R[BOND]C[TRIPLE BOND]C[BOND]CN are obtainable from 1 by reaction with aldehydes RCHO and esters RCOOR', respectively.

    16. Magnesium Phosphides–Synthesis and Structure of [Mg(PHPh)2(tmeda)] (pages 81–82)

      Dr. Evamarie Hey, Dr. Lutz M. Engelhardt, Dr. Colin L. Raston and Dr. Allan H. White

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198700811

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      Application as PRmath image transfer reagents is for-seen for the new inorganic magnesium reagents [Mg(PHPh)2] and the crystalline, monomeric title compound 1. The latter was prepared in high yield by monometalation of PhPH2 with the versatile reagent nBusBuMg and addition of TMEDA. In 1 the Mg[BOND]P distances are equal but the Mg[BOND]P[BOND]C angles are not.

    17. As4S5N10–A Diaminosulfane Derivative with Two Bicyclic Arsino Sulfur Diimides (pages 82–83)

      Prof. Dr. Max Herberhold, Dr. Karlheinz Guldner, Prof. Dr. Alfred Gieren, Dipl.-Phys. Catalina Ruiz-Pérez and Dr. Thomas Hübner

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198700821

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      An unexpected redox reaction ensues in the reaction of K2SN2 with AsX3. When X = Br, moderately air-stable, red crystals of 1 are obtained in about 40% yield instead of the expected compound As2(NSN)3

    18. Imino-, Phosphoranylidene-, and Sulfuranylidenephosphanes by 1,3-Silyl Migration (pages 83–84)

      Dipl.-Chem. Frank Zurmühlen and Prof. Dr. Manfred Regitz

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198700831

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      Compounds with λ3-phosphorus of coordination number two are currently attracting a great deal of attention. The title compounds 1, X = N, SR″, PR″R′″, are obtainable via the route outlined below. The stable sulfur derivatives are the first of their kind.

    19. Isomerization Reactions in the System Dewar-Phosphinine/Phosphaprismane/Phosphabenzvalene/Phosphinine (pages 85–86)

      Dipl.-Chem. Karsten Blatter, Dipl.-Chem. Wolfgang Rösch, Dipl.-Chem. Uwe-Josef Vogelbacher, Dr. Jürgen Fink and Prof. Dr. Manfred Regitz

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198700851

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      Instead of many words, just some structural formulas: All compound types except 2 and 6 (R [DOUBLE BOND] CO2Me) are new!

    20. New AuPt2 A-Frame Cluster Complexes (pages 86–87)

      Dr. Gilles J. Arsenault, Dr. Ljubica Manojlović-Muir, Dr. Kenneth W. Muir, Dr. Richard J. Puddephatt and Dr. Ilse Treurnicht

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198700861

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      Electrophilic gold reagents add to the Pt[BOND]Pt bond of 1 to give trinuclear cluster compounds. From the crystal structure a 3c2e bonding can be concluded for the Pt2-Au group in 2. In analogous reactions with silver or copper electrophiles, the ligand sphere is attacked, and not the Pt-Pt bond.

    21. Mixed-Metal Cluster Formation Carbonylmetalate-Induced Pt-P Bond Cleavage in [PtCl2(Ph2PCH2PPh2)] (pages 88–89)

      Dr. Pierre Braunstein, Nicolas Guarino, Dr. Claude de Méric de Bellefon and Jean-Luc Richert

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198700881

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      Ph2PCH2PPh2 bridges the metal centers in the heterometal clusters that are formed via partial ligand migration upon reaction of the title compound with carbonylmetalates such as [Mn(CO)5]. Reaction with [Na2Fe(CO)8] leads, inter alia, to the formation of the cluster 1. The reactions confirm that the lability of the Pt[BOND]P bond suffices for the synthesis of clusters

  3. Book Reviews

    1. Top of page
    2. Reviews
    3. Communications
    4. Book Reviews
    1. Book Review: Plasma Polymerization. By H. Yasuda (page 91)

      Ernst-Günther Schlosser

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198700911