Angewandte Chemie International Edition in English

Cover image for Vol. 31 Issue 10

October 1992

Volume 31, Issue 10

Pages 1265–1398

Currently known as: Angewandte Chemie International Edition

    1. Cover Picture (Angew. Chem. Int. Ed. Engl. 10/1992)

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199212651

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      The cover picture shows a portrait of August Wilhelm von Hofmann painted in 1890 by Heinrich von Angeli. The painting was commissioned by the German paint manufacturers for the National Gallery, and was presented by Heinrich Caro on July 7, 1890. The honor of such a commission was almost equal to that of the award of a title and required the Kaiser's blessing. The Viennese artist, who was one of the most popular portrait painters of the royal courts in Vienna, London, St. Petersburg, and Berlin because of his mastery in composition and harmonious costuming, rejected the usual attributes of learning (the lectern and books) that characterize the majority of the paintings of Berlin scientists commissioned for the National Gallery and indeed can be seen in Angeli's initial study for Hofmann's portrait (formerly in the possession of the Deutsche Chemische Gesellschaft; see the picture in Ber. Dtsch. Chem. Ges.1942, 75 A, facing p. 147). Instead he favored a monumental, even high-priestly representation.

  1. Reviews

    1. Top of page
    2. Reviews
    3. Highlights
    4. Communications
    5. Corrigenda
    6. Book Reviews
    1. August Wilhelm Hofmann—“Reigning Chemist-in-Chief” (pages 1265–1282)

      Prof. Christoph Meinel

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199212653

      The German Chemical Society of Berlin held its inaugural meeting 125 years ago, on November 11, 1867. The main purpose of the Society was to unite pure and applied chemistry and foster cooperation between academic research and the chemical industry. And, indeed, it soon became the major forum for German and even European chemistry. Its program clearly bears the hallmark of a single individual: August Wilhelm Hofmann, the Society's first president, who died 100 years ago. The life and times of this legendary chemist, who can rightfully be considered the father of synthetic chemistry, are captured here.

    2. The Chemistry of GALLEX—Measurement of Solar Neutrinos with a Radiochemical Gallium Detector (pages 1283–1297)

      Dr. Edmund Henrich and Prof. Dr. Klaus H. Ebert

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199212831

      How does one identify 1.18 71Ge atoms in the presence of 1.037 × 102971Ga atoms? This question must be answered during development of GALLEX, an experiment designed to detect low-energy solar neutrinos, for in the 30.3 tons of natural gallium employed in the GALLEX experiment 1.1871Ga atoms are converted into 1.1871Ge atoms per day by the trapping of solar neutrinos. The 71Ge atoms in turn decay with a half-life of 11.4 days. This means that approximately sixteen 71Ge atoms are produced after four weeks and must be separated quantitatively if possible, concentrated, and fed into a counting tube. This review outlines the experimental steps for achieving this goal and the results obtained so far on the solar neutrino flux and neutrino mass.

    3. Scanning Tunneling Microscopy and Atomic Force Microscopy in Organic Chemistry (pages 1298–1328)

      Dr. Jane Frommer

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199212981

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      The scanning of objects with an intimacy not previously known to provide images of surfaces with atomic and molecular resolution is possible with scanning tunneling microscopy and atomic force microscopy. As a result these techniques are entering many fields of physics, chemistry, and biology. Apart from the observation and characterization of surfaces, designed modifications such as depicted on the right in an image of circular hydrocarbon domains on a fluorocarbon monolayer can be made—which opens up further applications. The enigmatic faces were created by localized manipulation with the AFM probe.

  2. Highlights

    1. Top of page
    2. Reviews
    3. Highlights
    4. Communications
    5. Corrigenda
    6. Book Reviews
    1. Compounds with Three-Membered Rings Containing Boron (pages 1329–1331)

      Priv.-Doz. Dr. Hansjörg Grützmacher

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199213291

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      Three-membered ring systems containing heavier main group elements and almost every combination of elements can now be prepared. The isolobal analogy between C+ and B makes three-membered rings containing boron especially interesting for both theoreticians and synthetic chemists. With the synthesis of oxadiborirane 1 by Paetzold et al. (Angew. Chem. Int. Ed. Engl.1992, 31, 1040) and boriranes 2 by Berndt et al. (see communication on p. 1384) the synthesis of a diborirane, namely a B2C three-membered ring, appears within reach. The carbon atom in such a molecule is postulated to have a planar bonding geometry. R = tBu and 2,3,5,6-Me4C6H, X = N(SiMe3)2, Cl, Me.

    2. Cascade Cyclizations (pages 1332–1334)

      Prof. H. Martin R. Hoffmann

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199213321

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      The one-step construction of complex polycyclic frameworks from monocyclic precursors, that is, the initiation and controlled termination of entire reaction cascades, is also possible in radical reactions. The selective formation of C[BOND]C bonds with radicals has become a useful synthetic method as is shown in the syntheses of 1 (hirsutene) and 2(the framework of cedrane). In each case, the cyclization was triggered by Bu3SnH/azobis(isobutyronitrile). Hanessian et al. have extended this method with a variation in which dienes and trienes are cyclized with Me3SnH generated in situ, and the C[BOND]Sn bond formed is then subjected to oxidative cleavage (3 [RIGHTWARDS ARROW] 4).

  3. Communications

    1. Top of page
    2. Reviews
    3. Highlights
    4. Communications
    5. Corrigenda
    6. Book Reviews
    1. Intermolecular Additions and Cycloisomerizations by a Pd-Catalyzed Sequence of an Intramolecular Redox Reaction and an Addition (pages 1335–1336)

      Prof. Dr. Barry M. Trost, Walter Brieden and Karl H. Baringhaus

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199213351

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      Unusual chemoselectivity is found in the novel reaction sequence catalyzed by the palladium complex 3 by which propargyl acetates 1 are smoothly converted into synthetically interesting geminal diacetates 2. Even when the R group contains double bonds, hydroxyl, or carbonyl groups, 2 is formed exclusively in excellent yields. Macrolides can also be prepared by this method, dba = Dibenzylidenacetone.

    2. Chemoenzymatic Syntheses of the Optically Active Hydroperoxides of Phosphatidylglycerol and Phosphatidylethanolamine with Lipase, Lipoxygenase, and Phospholipase D (pages 1336–1338)

      Kenji Yoneda, Keiji Sasakura, Shoichi Tahara, Prof. Dr. Junkichi Iwasa, Prof. Dr. Naomichi Baba, Dr. Takao Kaneko and Dr. Mitsuyoshi Matsuo

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199213361

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      The enantioselective, lipase-catalyzed stearoylation of 2-O-benzylglycerol is the first step in one of the two synthetic routes to phosphatidylethanolaminehydroperoxide 1. Compound 1 and the phosphatidylglycerolhydroperoxide 2, prepared in a similar fashion, were both purified by thin-layer chromatography, and their structures determined by NMR spectroscopy and mass spectrometry. Lipidhydroperoxides are important for medical research, since their formation in vivo may trigger diseases such as cancer and arteriosclerosis.

    3. Azidoiodoiodine(1+) Hexafluoroantimonate: The First Binary Nitrogen–Iodine Cation (pages 1338–1339)

      Dr. Inis C. Tornieporth-Oetting, Dipl.-Chem. Peter Buzek, Prof. Dr. Paul von Ragué Schleyer and Priv.-Doz. Dr. Thomas M. Klapötke

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199213381

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      A nonplanar, chainlike structure for the cation I2Nmath image is suggested by the findings of Raman spectroscopy and the results of ab initio calculations (depicted here). This unprecedented binary I-N cation can be prepared by the reaction of IN3 with I2/SbF5 or of AgN3 with I3SbF6. (Caution: explosive!)

    4. Control of the Reaction of n-Butyllithium with Benzo[b]tellurophene by the Solvent—Either Metalation or Tellurium–Lithium Exchange To Give an Interesting Lithiostyryllithium (pages 1339–1341)

      Prof. Dr. Adalbert Maercker, Ing.-grad. Heinrich Bodenstedt and Prof. Dr. Lambert Brandsma

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199213391

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      A drastic solvent dependence is observed for the reaction of benzo[b]tellurophene (2) with nBuLi: whereas in THF exclusively α-metalation occurs with the formation of 1, in hexane the interesting dilithiated styrene 3 is formed.

    5. “[Cp*Co[DOUBLE BOND]CoCp*]” is a Hydride (pages 1341–1343)

      Jörg L. Kersten, Prof. Arnold L. Rheingold, Prof. Klaus H. Theopold, Prof. Charles P. Casey, Ross A. Widenhoefer and Dr. Cornelis E. C. A. Hop

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199213411

      The supposed synthesis of the cobalt complex [Cp*Co[DOUBLE BOND]CoCp*] was in the spotlight at the end of last year (Angew. Chem. Int. Ed. Engl. 1991, 30, 1124). But the compound described at that time is actually the mixed-valent cobalt hydride 2. The reaction of the dinuclear complex 1 with LiAlH4 yields two paramagnetic cobalt complexes (2 and 3), which have been fully characterized by X-ray crystallography and spectroscopic methods, as well as by protonation and carbonylation. See also the Corrigendum on p. 1392.

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    6. Tetrakis(η1-phosphabenzene)nickel (pages 1343–1345)

      Prof. Dr. Christoph Elschenbroich, Dipl.-Chem. Mathias Nowotny, Dipl.-Chem. Andreas Behrendt, Prof. Dr. Werner Massa and Sigrid Wocadlo

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199213431

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      The first homoleptic η1-heteroarene nickel(0) complex is compound 1. Apparently, this tetrahedral phosphabenzene complex represents a stability niche because neither pyridine nor arsabenzene complexes are accessible by analogous methods. It is also surprising that despite the small steric bulk of the C5H5P ligand and the short Ni-P bond, a dissociation equilibrium NiL4⇌NiL3 + L is established.

    7. Catalytic Oxidation of Partially and Fully Fluorinated Olefins with Osmium Tetroxide (pages 1345–1347)

      Prof. Wolfgang A. Herrmann, Dr. Stefan J. Eder and Wolfgang Scherer

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199213451

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      A commonly held conception must be revised.The OsO4-catalyzed cis-hydroxylation of olefins was never tested with fluorinated olefins, because it was assumed that electron-poor olefins would not react with OsO4. But under the standard reaction conditions even perfluorinated olefins can be converted into osmate esters such as 1 quickly and quantitatively. Their subsequent hydrolysis provides cis-diols, ketones, or 1,2-diketones.

    8. High Molecular Weight Polypropylene through Specifically DesigneZirconocene Catalysts (pages 1347–1350)

      Dr. Walter Spaleck, Dr. Martin Antberg, Dr. Jürgen Rohrmann, Dr. Andreas Winter, Dr. Bernd Bachmann, Dr. Paul Kiprof, Dr. Joachim Behm and Prof. Dr. Wolfgang A. Herrmann

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199213471

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      A breakthrough for the technical application of zirconium catalysts in isotactic propylene polymerization has been achieved with complexes 1. The highest molecular mass of polypropylene, the best isotacticity, and the highest activity of all catalysts are provided by 1, R1 = R3 = CH3, R2 = i-C3,H7. Hydrogenation of the six-membered ring drastically lowers the activity and the molecular mass obtained.

    9. Phosphorus(V) Selenides with Phosphorus in a Trigonal-Planar Environment (pages 1350–1352)

      Prof. Dr. Alfred Schmidpeter, Dipl.-Chem. Georg Jochem, Dr. Konstantin Karaghiosoff and Priv.-Doz. Dr. Christian Robl

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199213501

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      Phosphorus ylide substituents Ph3PCR (for example, R = Me, Ph) can stabilize a phosphorus(V) center with trigonal-planar coordination: dithioxo- 1 and diseleno-λ5-phosphanes 2 remain monomeric, and the chloride and bromide salts of the selenoxophosphonium ion 3 do not rearrange to the covalent phos-phinoyl halides. The central, positively charged phosphorus atom is electronically stabilized by the ylide substituent.

    10. The Structure of the [1.1]Ruthenocenophane Dication: Metal–Metal Bond Formation and the Consequences of Proximity (pages 1352–1354)

      Prof. Dr. Ulrich T. Mueller-Westerhoff, Prof. Dr. Arnold L. Rheingold and Dr. Gerhard F. Swiegers

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199213521

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      Nonbonding Ru-Ru interactions in [1.1]-ruthenocenophane (1) that can be attributed to the proximity of the metal centers and the formation of a Ru-Ru single bond in the dication (12+) are the reason for the low oxidation potential of 1 and for the stability of 12+. As the X-ray structure analysis of the BFmath image salt of 12+ shows (structure here viewed down the Ru-Ru bond), the two ruthenocene halves are distinctly twisted to accommodate the CH2 bridges.

    11. Octakis(1,1,2-trimethylpropyl)octasilacubane: Synthesis, Molecular Structure, and Unusual Properties (pages 1354–1356)

      Prof. Dr. Hideyuki Matsumoto, Koichi Higuchi, Dr. Soichiro Kyushin and Dr. Midori Goto

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199213541

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      The thermodynamically and kinetically stable peralkyloctasilacubane1 is formed in the reaction of SiCl3 (R = CMe2CHMe2) with Na. The orange-red compound is soluble in hydrocarbons and was characterized by spectroscopy and X-ray crystallography. Both its long-wavelength electronic transition in the UV/VIS spectrum at λ ≈ 500 nm and its low oxidation potential found by cyclic voltammetry at 0.43 V—unusual values for cy-clopolysilanes—are traced back to the highly strained Si8 framework.

    12. Structure of a Product of Double Addition to C70: [C70{Ir(CO)Cl(PPhMe2)2}2]·3C6H6 (pages 1356–1358)

      Prof. Alan L. Balch, Joong W. Lee and Dr. Marilyn M. Olmstead

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199213561

      The addition occurs at opposite poles of C70 when two Ir complexes each coordinate in a dihapto fashion to a 6-6 ring junction to form the title compound. Although the splitting of the 31P NMR signals of this complex at low temperatures implies that an isomeric mixture is present, X-ray studies on the products of different batches reveal only one isomer in the solid state.

    13. Synthesis of the Species-Specific Mycobacterium avium Trisaccharide (Serovar 21) for the Preparation of a Neoglycoprotein for Immunological Studies (pages 1358–1360)

      Dr. Thomas Ziegler

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199213581

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      A blockwise construction strategy was used to synthesize the complex pyruvylated oligosaccharide 1. The oligosaccharide can be easily attached to a carrier protein (R = (CH2)5-NH-BSA, BSA = bovine serum albumin) and might thus be used directly as a neoantigen for diagnostic purposes or for the preparation of specific antibodies. This is crucial for the early specific diagnosis of infections in AIDS patients, which was formerly possible only by time-consuming cultivation of isolated bacteria.

    14. Novel Strategies for the Synthesis and Crystallization of Electrophilic Dinuclear Cations: Solution and Solid-State Properties of [Re2(NCCH3)10][Mo6O19]2 (pages 1360–1362)

      Stacey N. Bernstein and Prof. Kim R. Dunbar

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199213601

      An attractive route to mixed-valent metal oxides has been developed from the observation that on slow heating 1 completely loses its acetonitrile ligands at temperatures below 350 °C and is transformed into an oxide containing MoVI and Re in two oxidation states. Salt 1 is prepared surprisingly simply according to Equation (a) and shows unexpected electron-acceptor properties, which makes it a potential source of a naked Remath image ion. The structural parameters of the cation of 1 point to a Re[BOND]Re triple bond, although no strong α or π donors stabilize the system.

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    15. [Ga(C5H5)]: Synthesis, Identification, and Ab Initio Investigations (pages 1362–1364)

      Dipl.-Chem. Dagmar Loos, Prof. Dr. Hansgeorg Schnöckel, Dr. Jürgen Gauss and Dipl.-Chem. Uwe Schneider

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199213621

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      [GaCpl] is monomeric and has C5v symmetry. This last cyclopentadienyl compound of an element in the third main group in the oxidation state I was obtained from GaCl and [MgCp2]. The structure was examined by spectroscopy and detailed ab initio calculations (structure shown here).

    16. [Ga4{C(SiMe3)3}4] with a Tetrahedral Ga4 Skeleton (pages 1364–1366)

      Dr. Werner Uhl, Prof. Dr. Wolfgang Hiller, Dr. Marcus Layh and Dr. Wolfgang Schwarz

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199213641

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      The unusual oxidation state i and M4tetrahedral in the solid-state characterize tris(tri-methylsilyl)methylgallium, the disproportionation product of the reaction of Ga2Br4 · 2dioxane with solvent-free LiC-(SiMe3)3. Although only the monomeric unit is detected by mass spectrometry, tetramers (X-ray structure shown here) are found in the solid state.

    17. [V(SNC9H6)3] and [V(SNH2C6H4)2(SNHC6H4)], Homoleptic Vanadium(III) Complexes with Sulfur–Nitrogen Donor Ligands, and [V(SNC5H4)3], the First Thiolatovanadium(II) Complex (pages 1366–1368)

      Prof. Gerald Henkel, Prof. Bernt Krebs and Dr. Wilfried Schmidt

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199213661

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      The sulfur and nitrogen atoms of the pyridinethiolato ligands coordinate to the central atom in the vanadium(II) complex [V(SNC5H4)03](1) to form a distorted octahedral geometry. In each set of neighboring ligands one S atom and one N atom are trans to each other; the chelate rings are planar. Such complexes with bifunctional ligands are important as models for vanadium centers in biomolecules.

    18. Novel Metal Thiolates: [Co2(SC3H7)5], the First Complex with Face-Sharing MS4 Tetrahedra (pages 1368–1369)

      Prof. Gerald Henkel and Dipl.-Chem. Stefan Weissgräber

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199213681

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      A trigonal bipyramid made up of sulfur atoms with two cobalt atoms in the cavity, or two face-sharing CoS4 tetrahedral—both are apt descriptions of the structure of the title anion 1. The Co[BOND]Co distance is remarkably short (2.491(1) Å), and the isopropyl groups of the three bridging thiolato ligands have a paddle-wheel-type arrangement about a C3 axis. Complex 1 is obtained from cobalt(II) nitrate and sodium propane-2-thiolate and can be isolated as the ammonium salt.

    19. On the Mechanism of Coherent Dihydrogen Tunneling in Transition Metal Trihydrides (pages 1369–1372)

      Prof. Dr. Hans-Heinrich Limbach, Dr. Gerd Scherer, Marcus Maurer and Dr. Bruno Chaudret

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199213691

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      The large, temperature-dependent scalar coupling constants between the metal-bonded hydrogen atoms in trihydrido complexes are caused by a mutual quantum exchange between the two identical forms, that is, by a coherent tunneling process. In this report the experimental findings are explained by the reaction pathway sketched below, in which a metastable dihydrogen complex is formed.

    20. Diastereoselective Addition of Allylsilanes to Aldehydes: Synthesis of Enantiomerically Pure Homoallylic Alcohols (pages 1372–1373)

      Prof. Lutz F. Tietze, Dr. Angelika Dölle and Dipl.-Chem. Kai Schiemann

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199213721

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      Very high selectivities (de > 99%) are achieved in the preparation of homoallyl ethers 2 by treatment of aliphatic aldehydes with allylsilane and 1, the trimethylsilyl ether of N-trifluoroacetylnorpseudoephedrine (chiral inductor). The reductive cleavage of ether 2 with Na in liquid NH3 provides interesting synthetic building blocks, the homoallyl alcohols 3, in enantiomerically pure form. When aromatic aldehydes or ethers of other aminoalcohols are used, the selectivities and yields are dramatically reduced.

    21. 5′-P-Borane-Substituted Thymidine Monophosphate and Triphosphate (pages 1373–1375)

      Dr. Jeno Tomasz, Dr. Barbara Ramsay Shaw, Dr. Ken Porter, Dr. Bernard F. Spielvogel and Dr. Anup Sood

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199213731

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      The attachment of the BH3 group to the phosphorus atom is the crucial step in the synthesis of boranophosphate 1 and -triphosphate 2. These compounds could be as useful in biochemical and molecular biological investigations as the related thiophosphates because of the prochiral (in 1) and chiral (in 2) phosphorus centers and the similar charge distribution to the thiophosphates.

    22. Cationic Metallocene Polymerization Catalysts. Synthesis and Properities of the First Base-Free Zirconocene Hydride (pages 1375–1377)

      Dr. Xinmim Yang, Charlotte L. Stern and Prof. Tobin J. Marks

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199213751

      High electrophilicity and polymerization activity as well as ion-pairing effects not based on the bridging hydrogen atoms are the most notable characteristics of the cation in 2, a model compound for Ziegler-Natta catalysts. This hydrido complex is accessible by hydrogenolysis of 1 or by hydride abstraction from 3.

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    23. The Formation of cyclo-P4 Ligands with Maximum Electron Donor Ability (pages 1377–1379)

      Dr. Manfred Scheer, Christa Troitzsch and Prof. Dr. Peter G. Jones

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199213771

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      The opening of a P[BOND]P edge in the P4 tetrahedron by a Rh complex fragment is the first reaction step in the three-component reaction between [RhCp′(CO)2], P4, and [Cr-(CO)5(thf)]. The tetraphosphabicyclobutane ligand thus formed may then use the lone pairs of all the phosphorus atoms for the coordination of Cr(CO)5 units to give 1. Loss of CO and cleavage of a P[BOND]P bond leads to a complex in which the cyclo-P4 ligand acts as a 12-valence-electron donor. Cp′ = η5 − C5H4tBu, equation image.

    24. Synthesis and Biological Activity of D-3-Deoxy-3-Fluorophosphatidylinositol—A New Direction in the Design of non-DNA Targeted Anticancer Agents (pages 1379–1381)

      Prof. Dr. Alan P. Kozikowski, Dr. Werner Tückmantel and Dr. Garth Powis

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199213791

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      myo-Inositol causes no disruption in the growth-inhibiting effect of the phos-phatidylinositol (Ptdlns) derivative 1. This first synthetic Ptdlns analogue with a myo-inositol configuration may point the way to new anti-cancer agents based on the interruption of Pdtlns signaling, which do not inhibit cell growth by interaction with DNA.

    25. Synthesis and Complexation Properties of a Cyclodextrin-Derived Siderophore Analogue (pages 1381–1383)

      Dr. Anthony W. Coleman, Dr. Chang-Chun Ling and Prof. Marcel Miocque

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199213811

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      Simultaneous complexation of metal ions and inclusion of organic molecules is possible with the α-cyclodextrin derivative 6A,6C,6E-triamino-N,N′,N″-tris(2,3-dihydroxybenzoyl)-pentadeca-O-methyl-α-cyclodextrin (1) shown schematically here. The NMR spectra of 1, 1 + Fe3+, 1 + A13+, and 1 + A13+ + p-nitro-phenolate support this thesis.

    26. Boriranes: Structures and Thermal Ring Openings (pages 1384–1386)

      Dr. Peter Willerhausen, Dr. Günter Schmidt-Lukasch, Claudia Kybart, Dr. Jürgen Allwohn, Prof. Dr. Werner Massa, Prof. Michael L. McKee, Prof. Paul von Ragué Schleyer and Prof. Armin Berndt

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199213841

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      Any of the three bonds in the C2B ring of C-borylated boriranes can be cleaved thermally with formation of C-borylmethyleneboranes 1, diboratetrahydronaphthalenes, or (after reaction of the appropriate boriranes with ethyl vinyl ether) dihydroboroles depending on the substituents. The electrocyclic exothermic ring-opening known for the transformation of cyclopropenylium ions into allyl cations has not been observed previously for the isoelectronic boriranes; according to calculations the ring-opening is endothermic. R = SiMe3.

    27. Stereoselective Synthesis of Phosphate-Modified Building Blocks of DNA (pages 1386–1388)

      Dipl.-Chem. Wendelin Samstag and Prof. Dr. Joachim W. Engels

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199213861

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      The directed synthesis of one phosphonate diastereomer and therefore control of the stereochemistry at the P atom was achieved for the first time in the preparation of the 3′, 5′-linked phosphonates 1 through careful choice of substituents at the P atom. Also 3′,3′- and 5′,5′-linked phosphonates were obtained easily on successive treatment of two protected nucleosides with the phosphonylation reagent RPCl2, and subsequent oxidation with t BuOOH. R = iPr, benzyl, (S)-( + )-methylbutyl; T = thymidyl, Tr = trityl.

    28. Fullerene Sugars: Preparation of Enantiomerically Pure, Spiro-Linked C-Glycosides of C60 (pages 1388–1390)

      Prof. Andrea Vasella, Peter Uhlmann, Christian A. A. Waldraff, Prof. François Diederich and Dr. Carlo Thilgen

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199213881

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      “Sweetened buckyballs” are prepared in good yields. The C-glycosylated, uniform, enantiomerically pure C60 monoaddition products 1 (R = benzyl, pivaloyl) are differentiated not only by their chi-roptical properties, but also by the conformation of the glycosyl residue, which is dependent on its substituents.

    29. Configuratively Stable Dipeptide Aldehydes from D-Glucosamine Hydrochloride (pages 1391–1392)

      Dipl.-Chem. Thomas Kolter, Annegret Klein and Priv.-Doz. Dr. Athanassios Giannis

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199213911

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      Chiral N-benzyloxycarbonyl-protected amino acids and D-glucosamine hydrochloride are the starting materials for the two-step synthesis of configuratively stable dipeptide aldehydes 1 and their subsequent products, peptide Michael acceptors 2. These compounds may serve as synthetic building blocks and as potential protease inhibitors. Z = CO2CH2Ph; representative R and R′ groups are iPr and OtBu, respectively.

  4. Corrigenda

    1. Top of page
    2. Reviews
    3. Highlights
    4. Communications
    5. Corrigenda
    6. Book Reviews
    1. You have free access to this content
      On the Reaction of Pentamethylcyclopentadiene with Cobalt Atoms: A Reexamination (page 1392)

      Dr. Jörg J. Schneider

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199213921

      [Cpmath imageCo2] is still unknown. The compound reported a year ago as [Cpmath image Co2] (Angew. Chem. Int. Ed. Engl.1991, 103, 1124) is, in fact, [Cpmath imageCo2H3]. [Cpmath imageCo3H4], the major component of the eluate of the chromatography after removal of a mononuclear sandwich complex, was not identified at that time.

  5. Book Reviews

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