Angewandte Chemie International Edition in English

Cover image for Vol. 30 Issue 1

January 1991

Volume 30, Issue 1

Pages 1–112

Currently known as: Angewandte Chemie International Edition

    1. Cover Picture (Angew. Chem. Int. Ed. Engl. 1/1991)

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.199100011

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      The title picture shows the light blue to violet Commelina communis, a flower used in Japan for coloring paper. Its petals contain commelinin, a blue anthocyanin, whose extremely complex structure was elucidated in the 1980s by the late T. Goto and his school, In this issue, an article written by T. Goto together with T. Kondo (p. 17ff) describes in detail how the anthocyanins give rise to different colors. The flower shown on the cover is not only intended to draw attention to an excellent review article, however. It symbolizes this entire issue.

      Anniversary Flowers: This issue begins the thirtiest volume of the International Edition of Angewandte Chemie. The English edition has long helped Angewandte Chemie to attract authors and readers worldwide. This has been especially true during the last few years. The circulation of both the English and German editions continues to grow. The percentage of articles by foreign authors has increased, too, from 25% at the beginning of the 1980s to almost 50% last year. Most foreign manuscripts received in 1990 were submitted from Western Europe (45%), North America (30%), and Japan (12%). These numbers reflect the growing approval of authors and readers alike and motivate us to improve the journal still further in the future.

      Greeting Flowers: During the second half of 1990, it became apparent that the publication of the two very similar journals Angewandte Chemie and Zeitschrift für Chemie no longer made sense. The latter journal ceased publication at the end of 1990. We extend a welcoming hand to the many readers and authors of Zeitschrift, für Chemie.

      Premiere Flowers: Excellence always demands improvement. In this issue, we begin a new section called “Highlights”. The virtual flood of short communications, full research articles, and conference reports makes it increasingly difficult to avoid missing an important recent development. This is true not only for chemistry as a whole but even for a narrow field of research. The review articles in Angewandte Chemie have helped readers to obtain an overview of specific areas and trends. The new section Highlights, on the other hand, is intended to awaken the reader's awareness to new developments in statu nascendi as well as to important results from all areas of chemistry (see also Notice to Authors in this issue).

    2. Graphical Abstract (Angew. Chem. Int. Ed. Engl. 1/1991)

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.199100012

  1. Reviews

    1. Top of page
    2. Reviews
    3. Highlights
    4. Communications
    5. Book Reviews
    1. Representation in Chemistry (pages 1–16)

      Prof. Roald Hoffmann and Prof. Pierre Laszlo

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.199100013

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      Just like glass flasks, beakers, and distillation columns, chemical structures are an integral part of our profession. We are easily identified as chemists by how we draw formulas. Nonetheless, the simplicity of these formulas—whether mere sketches or glossies fit for publication—is misleading. They pose numerous questions on the ways we represent chemical structures. The picture on the right shows one way of portraying a camphor molecule.

    2. Structure and Molecular Stacking of Anthocyanins—Flower Color Variation (pages 17–33)

      Prof. Dr. Toshio Goto and Dr. Tadao Kondo

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.199100171

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      Flowers and their colors have long fascinated mankind and posed many puzzling questions. For example, how does the same anthocyanin in red roses and blue cornflowers give rise to different colors? Initially, it was thought that the color of a flower depends exclusively on the pH of the cell sap. This view no longer holds. We now know that self-association, copigmentation, the formation of metalloanthocyanins, and the sandwichlike stacking of aromatic rings are of great importance. This is exempified by a complicated anthocyanin, ternatin A, from Clitoria ternata.

    3. Polyoxometalate Chemistry: An Old Field with New Dimensions in Several Disciplines (pages 34–48)

      Prof. Michael T. Pope and Prof. Dr. Achim Müller

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.199100341

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      A huge number of anionic metal-oxygen clusters are known and new structures with often surprising reactivity are being discovered almost daily. For instance, the spherical cluster shell {V15O36} can enclose anions with differing radii; in the cluster on the right, COmath image is enclosed. Moreover, stepwise reduction of the polyoxometalates of the early transition elements V, Mo, and W changes the strength of the metal–metal bonds. This behavior makes these clusters of interest for materials science and pharmacology.

    4. Enantioselective Addition of Organometallic Reagents to Carbonyl Compounds: Chirality Transfer, Multiplication, and Amplification (pages 49–69)

      Prof. Dr. Ryoji Noyori and Dr. Masato Kitamura

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.199100491

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      Carbonyl compounds can be converted into alcohols with up to 99% ee by using dialkylzinc reagents in the presence of amino alcohols as catalysts. Based on extensive mechanistic studies, a catalytic cycle that involves monomeric and dimeric zinc complexes such as 1–3 (usually Ar = C6H5, R = CH3, C2H5) has been proposed for this catalytic asymmetric alkylation. Moreover, the nonlinearity of chirality transfer is striking—14% ee of the catalyst can give products with up to 98% ee.

  2. Highlights

    1. Top of page
    2. Reviews
    3. Highlights
    4. Communications
    5. Book Reviews
    1. The Third Allotropic Form of Carbon (pages 70–71)

      Prof. J. Fraser Stoddart

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.199100701

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      For many chemists, the molecules of the year 1990 are C60 and C70. The recent report of an efficient route of preparation—organic chemists might disagree with the word synthesis—has sparked numerous investigations into the structure, chemical reactivity, and electro- and photochemical behavior of these species. In 1991, we can expect to learn much more about this third modification of carbon (the picture on the right, which shows crystals of C70 (actually cornflower blue) was provided by F. Diederich, Los Angeles).

    2. Molecular Systems with Perfect Metal Structure (pages 72–73)

      Prof. Dr. Georg Süss-Fink

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.199100721

      The no-man's-land between typical homogeneous and heterogeneous catalysts is slowly being explored. Particularly important have been the multinuclear metal clusters synthesized and characterized in recent years. They not only serve as models for heterogeneous catalysts but also display unusual catalytic properties. The criteria governing the structures of these large clusters are revealed very clearly by the cluster dianion [Os20(CO)40]2⊖ obtained by B. F. G. Johnson and J. Lewis et al. (see also p. 107 ff.).

  3. Communications

    1. Top of page
    2. Reviews
    3. Highlights
    4. Communications
    5. Book Reviews
    1. Dynamic HPLC: A Method for Determining Rate Constants, Energy Barriers, and Equilibrium Constants of Molecular Dynamic Processes (pages 74–76)

      Dr. Jaume Veciana and Dipl.-Eng. Chem. Maria I. Crespo

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.199100741

      Kinetic and thermodynamic data for molecular transformations A ⇄ B with activation energies of 65 to 105 kJ mol−1 can be obtained by simulation of the HPLC chromatogram of mixtures of A and B. This is accomplished by using the retention times, the number of theoretical plates, the asymmetry factors, the initial molar ratios, and the relative sensitivity of the detector, together with trial parameters for the apparent rate constants of the overall forward and reverse reactions. The simulation, in turn, can be used to calculate equilibrium constants and activation energies. A precision of 8% was estimated for this method of simulation.

    2. Thermally Irreversible Photochromic Liquid Crystal Polymers (pages 76–78)

      Dr. Ivan Cabrera, Dipl.-Chem. Achim Dittrich and Prof. Helmut Ringsdorf

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.199100761

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      In the dark, both photochromic forms of co-polymer 1 (R = H, CH3; R1 = CN, OCH3) are indefinitely stable at room temperature. In combination with their mesomorphic properties, this stability makes these materials interesting for optical information storage.

    3. Selective Halogenation at Primary Positions of Cyclomaltooligosaccharides and a Synthesis of Per-3,6-anhydro Cyclomaltooligosaccharides (pages 78–80)

      Dr. Andrée Gadelle and Dr. Jacques Defaye

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.199100781

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      The cyclodextrin derivatives 2, which contain glucopyranose units in 1C4 conformation, were obtained via the 6-iodo compounds 1. The synthesis of 1 was accomplished by reaction of unsubstituted sugars with Vilsmeier-type reagents (see also following communication).

    4. Synthesis and Characterization of Per-3,6-anhydro Cyclodextrins (pages 80–81)

      Peter R. Ashton, Paul Ellwood, Ian Staton and Dr. J. Fraser Stoddart

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.199100801

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      Cyclodextrin derivatives such as 1, which contain glucopyranose units in 1C4 conformation, were synthesized from per(6-O-tosyl)-β-cyclodextrin. The pure α-cyclodextrin derivative (with six sugar units) was obtained from per(2,3-O-benzoyl-6-O-tosyl)-α-cyclodextrin. Both anhydrodextrins are potential molecular receptors in which the cavity is lined with hydroxyl groups.

    5. Aggregation of Aza Crown Ethers by Metalation: Synthesis and Crystal Structure of 1-Lithio-1,7-diaza[12]crown-4—The First Lithiated Crown Ether (pages 82–84)

      Dr. Donald Barr, Dr. David J. Berrisford, Luis Méndez, Alexandra M. Z. Slawin, Dr. Ronald Snaith, Dr. J. Fraser Stoddart, Dr. David J. Williams and Dr. Dominic S. Wright

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.199100821

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      Deprotonation of diaza[12]crown-4 with nBuLi results in dimerization. This is shown by the X-ray structure analysis, according to which the product obtained is 1. Each Li ion is five-coordinate and lies appreciably (ca. 0.94 Å) outside the plane of the crown ether. The experimentally found structural changes agree with those found for a model system by MNDO calculation. The Li ions in 1 are well saturated electronically but still accessible to reagents.

    6. Synthesis, Structure, and Rearrangement of 1,3-Dibora[5]radialenes (pages 84–85)

      Dipl.-Chem. Markus Enders, Dr. Albrecht Krämer, Dr. Hans Pritzkow and Prof. Dr. Walter Siebert

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.199100841

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      The new 1,3-bis(dimethylamino) derivative 1 is isoelectronic with decamethyl[5]radialene. The analogous 1,3-dimethyl compound 2 undergoes slow 1,5-sigmatropic H shift to give a 1,3-diborafulvene. This process is faster in the reaction with [Mo(CO)6], whereby the product is the [Mo(CO)4] complex 3.

    7. Synthesis of a Novel Macrobicyclic Cavity Possessing Six Convergent Hydroxyl Groups and Acting as a Siderophore (pages 85–86)

      Prof. Jean Louis Pierre, Prof. Paul Baret and Mrs. Giselle Gellon

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.199100851

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      Fe3⊕ is bonded more strongly to the new macrocycle 1 (R = H, Me) than to EDTA or natural siderophores, as shown by competition experiments in water at pH 11.5. Compound 1 was synthesized in high yields both by a template-controlled process and by a reaction using the dilution principle.

    8. Enzymatic Synthesis of Chiral C4 Building Blocks from meso-Tartaric Acid (pages 86–88)

      Prof. Dr. Hans Jürgen Bestmann and Dr. Ulrich Christian Philipp

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.199100861

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      The optically active C4 building blocks 1, 2, and 4 are ultimately available from maleic acid on a 10-mmol scale. Compounds 1 and 2 are obtained from the dimethyl ester of O-methylated meso-tartaric acid, 3 (R1 = R2 = CH3), by saponification of either the pro-R or pro-S ester group with porcine liver esterase (as porcine liver-acetone powder) or the lipase from Candida cylindricea, respectively. Compound 4 is obtained from a reaction product of 3 by enzymatic acylation. The chemical yields and ee values in these reactions are all greater than 90%.

    9. Molecular and Ionic Hydrogen Isocyanide (CNH) Adducts with N-H…O- and “Super-Short” N-H…N-Hydrogen Bridges: Metal-Stabilized Hydrogen Bisisocyanides (pages 88–90)

      Dr. Eberhard Bär, Prof. Dr. Joachim Fuchs, Dirk Rieger, Francisco Aguilar-Parrilla, Prof. Dr. Hans-Heinrich Limbach and Prof. Dr. Wolf P. Fehlhammer

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.199100881

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      The metal-coordinated hydrogen isocyanide in [Cr(CO)5CNH] proved to be an ideal hydrogen-bond former. Its discrete adducts with ethers and cyano complexes are surprisingly stable and some are sublimable (1, [Cr] = Cr(CO)5). According to IR, X-ray structure, and 15NMR investigations, strong N-H…O hydrogen bonds are present. The shortest bonds are found for 2 ([Fe] = FeCp(diphos)) and 3. In 3, the N-H…N bonds are symmetrical. diphos = bis(diphenylphosphino)ethane.

    10. Formation of a trans-1,2,4,5-Tetraphosphatricyclo-[, 4]hexane by [2 + 2] Cyclodimerization of a 3H-Diphosphirene (pages 90–91)

      Prof. Dr. Edgar Niecke, Dr. Rainer Streubel and Dr. Martin Nieger

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.199100901

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      Synthesis of a 3H-diphosphirene by reaction of per(trimethylsilyl)-substituted 1,2-diphospha-2-propene with hexachloroethane was the goal. Although it was not possible to isolate this unknown isomer, its formation as an intermediate was demonstrated by further reaction to give the tricyclic dimer 1 with a planar P4 unit.

    11. Metal Carbonyl Complexes of Sapphyrins (pages 91–93)

      Dr. Anthony K. Burrell, Prof. Jonathan L. Sessler, Michael J. Cyr, Ellen McGhee and Prof. James A. Ibers

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.199100911

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      Mono- and binuclear Rh and Ir complexes are easily obtained by reaction of sapphyrins with [{RhCl(CO)2}2] and/or [IrCl(CO)2(py)]. In these binuclear complexes (e.g., 1), the two [M(CO)2] fragments are no different sides of the ruffled 22 π-electron ligands. Complex 1 catayzes the hydrogenation of cyclohexenes.

    12. Unsaturated Tin Compounds: Generation and Reactivity of Me2Sn = C(SiMe3)2 and Me2Sn = N(SitBu2Me) (pages 93–95)

      Prof. Dr. Nils Wiberg and Prof. Dr. Sham-Kumar Vasisht

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.199100931

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      Stannaethene 1, which is hardly stabilized electronically, was obtained by salt elimination and its existence was shown by trapping reactions with 2,3-dimethylbutadiene and azido(di-tert-butyl) methylsilane. Stannanimine 2, formed from the azidosilane, can be “stored” as the cycloadduct 3.

    13. On the Differing Lewis Basicity of InI Compared with SnII in Molecular Indium-Tin and Thallium-Tin Alkoxides (pages 95–97)

      Prof. Dr. Michael Veith and Dr. Klaus Kunze

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.199100951

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      A nearly linear arrangement of the four metal atoms Cr, Sn, In, and Mo, as well as an eclipsed arrangement of the [M(CO)5] fragments, in complex 1 was shown by X-ray structure analysis. Complex 1 was formed by successive addition of [M(CO)5(thf)] to the bridgehead centers of Sn(OtBu)3 In. The two centers differ in their basicity.

    14. Efficient Stereoselective Total Synthesis of Denticulatins A and B (pages 97–99)

      Marc W. Andersen, Dr. Bernhard Hildebrandt and Prof. Dr. Reinhard W. Hoffmann

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.199100971

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      Five of the eight stereocenters of the denticulatin 1 were formed by stereoselective aldehyde allylboration. This approach allows an efficient synthesis of even complex molecules. Naturally occurring denticulatin is produced by Siphonaria, which are native to the tidal zones of the Indian Ocean and the Caribbean.

    15. Catalytic and Stoichiometric Enantioselective Addition of Diethylzinc to Aldehydes Using a Novel Chiral Spirotitanate (pages 99–101)

      Dipl.-Chem. Beat Schmidt and Prof. Dr. Dieter Seebach

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.199100991

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      Simple variation of the reaction conditions in the addition of Et2Zn to aldehydes in the presence of spirotitanate 1 can lead to a reversal in the configuration of the product. Stoichiometric amounts of the spirotitanate result in Re addition of Et2Zn to the aldehyde (up to 98% ee). In the presence of equimolar amounts of Ti(OCHMe2)4, catalytic amounts of 1 lead to Si addition of Et2Zn (up to 99% ee).

    16. Th6Br15H7—Stabilization of a Th6Br12 Cluster by Seven Hydrogen Atoms (pages 101–102)

      Prof. Dr. Arndt Simon, Dr. Fred Böttcher and Dr. Jeremy Karl Cockcroft

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.199101011

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      Vertices, edges, and faces—in other words, the whole periphery of the Th6 octahedron in the title compound—are covered with Br and H atoms. The structure is novel in that the H atoms are not bonded interstitially but rather from “outside” to the cluster core, as shown by neutron diffraction of the perdeuterated compound (see the picture on the right; equation image). If the metal–metal bonds in the cluster are described qualitatively by eight closed three-center two-electron bonds directed toward the middle of the faces of the octahedron, it is clearly seen that seven of these bonds are stabilized by the additional electrons of the H atoms at the centers of the faces.

    17. The Reduction of the NbX5/AlX3 System with Aluminum in the Presence of Aromatic Hydrocarbons: An Approach to Niobium(II), Niobium(I), and Niobium(0) Organometallics (pages 102–103)

      Prof. Fausto Calderazzo, Dr. Guido Pampaloni, Dr. Lucia Rocchi, Prof. Dr. Joachim Strähle and Dipl.-Chem. Klaus Wurst

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.199101021

      The niobium(0) compound [Nb(mes)2] (mes = 1,3,5-trimethylbenzene) was prepared not only by metal atom–ligand cocondensation, but also according to Equation (a). The chemical behavior of this compound is similar to that of the analogous complex [V(mes)2]. For example, it reacts under carbon monoxide atmosphere to give the green salt [Nb(mes)2(CO)][Nb(CO)6]. This new, simple approach to niobium(0) compounds should facilitate their study (DME = dimethoxyethane).

      • equation image
    18. Stereoselective Synthesis of Vicinal Diamines (pages 103–106)

      Prof. Dr. Manfred T. Reetz, Dipl.-Chem. Ralf Jaeger, Ralf Drewlies and Dipl.-Chem. Marcus Hübel

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.199101031

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      α-Amino aldimines such as 1, which are readily accessible from amino acids, react with alkyllithium and -cerium compounds in a chelation-controlled manner to give the vicinal diamines 2 in optical yields of up to 90%. However, if the donor strength of the aldimine nitrogen atom is weakened by the electron-withdrawing tosyl group, the chelation effect is suppressed and reaction with Grignard reagents gives preferentially the stereoisomeric adducts with opposite relative configuration. Bn = benzyl.

    19. 2,4,6-Triaryl-1,3,5λ3-diazaphosphinines (pages 106–107)

      Prof. Dr. Gottfried Märkl and Dipl.-Chem. Christian Dörges

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.199101061

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      The first 1,3,5λ3-diazaphosphinines 2 were synthesized from 3,5-diazapyrylium tetrafluoroborates 1 by O/P exchange with tris(trimethylsilyl)phosphane. Compounds 2 react with alkyne dienophiles in a reaction cascade to give the highly functionalized λ3-phosphinines 3 (Aryl1, Aryl2 = C6H5, 4-C6H4CH3, 4-C6H4Cl; R1, R2 = H, C6H5, SiMe3, CO2Et).

    20. (nBu4P)2[Os20(CO)40], a Thermolytically Generated High-Nuclearity Cluster with a Tetrahedral Cubic-Close-Packed Metal Core (pages 107–109)

      Angelo J. Amoroso, Lutz H. Gade, Dr. Brian F. G. Johnson, Prof. Jack Lewis, Dr. Paul R. Raithby and Wing-Tak Wong

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.199101071

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      A fully symmetrical osmium tetrahedron consisting of twenty cubic-close-packed metal atoms constitutes the framework of dianion 1. There is no evidence for interstitial carbon or hydrogen atoms in the framework. Moreover, the Os[BOND]Os distances approach those of elemental osmium. Cyclovoltammetric measurements indicate that 1 exhibits interesting electrochemical properties (see also the Highlight on p. 72).

  4. Book Reviews

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