Angewandte Chemie International Edition in English

Cover image for Vol. 36 Issue 1‐2

February 3, 1997

Volume 36, Issue 1-2

Pages 3–171

Currently known as: Angewandte Chemie International Edition

    1. Cover Picture (Angew. Chem. Int. Ed. Engl. 1/2/1997)

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199700011

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      The cover picture shows the formula of globo H-KLH in the center, which show the strongest immunological activity in the presence of the immununological adjuvant QS-21. Globo H-KLH is a conjugate of the hexasaccharide globo H and hemocyanin from Megathura crenulata. Antibodies against globo H-KLH—the syringe reminds us that their formation is induced in mice—recognize the globo H epitope on the surface of breast cancer cells and activate the complement system to initiate lysis of the tumor cells. The sugar epitope of globo H was synthesized from glycal units (shown schematically at the top of the picture) and linked with KLH. The transfer of the immunization strategy to humans is the next step in the project that Danishefsky, Livingston, et al. report on page 125 ff (graphics: G. Schulz, Fussgönheim, Germany).

  1. Editorial

    1. Top of page
    2. Editorial
    3. Reviews
    4. Highlights
    5. Communications
    6. Book Reviews
    1. You have free access to this content
      Editorial (pages 3–4)

      Peter Gölitz

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199700031

  2. Reviews

    1. Top of page
    2. Editorial
    3. Reviews
    4. Highlights
    5. Communications
    6. Book Reviews
    1. Transport and Detoxication: Principles, Approaches, and Perspectives for Research on the Blood – Brain Barrier (pages 24–41)

      Dr. Achim Aigner, Dr. Sabine Wolf and Prof. Dr. Hans Günter Gassen

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199700241

      Minding the gates! Lipophilic xenobiotic compounds are potentially dangerous substances for the central nervous system. But the blood–brain barrier, which is an anatomical constraint with special morphological features, specific proteins, and transport systems, blocks passage of certain neurotoxic substances and serves as a site of active detoxication.

  3. Highlights

    1. Top of page
    2. Editorial
    3. Reviews
    4. Highlights
    5. Communications
    6. Book Reviews
    1. Fluorotitanium Compounds—Novel Catalysts for the Addition of Nucleophiles to Aldehydes (pages 43–45)

      Dr. Rudolf O. Duthaler and Dr. Andreas Hafner

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199700431

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      A breakthrough in enantioselective catalytic addition of allylsilanes to aldehyes was made by Gauthier and Carreira with a fluorotitanium catalyst (1) prepared in situ from TiF4 and binaphthol. Only 10% of 1 gives 94% ee for the addition of allyltrimethylsilane to, for example, tert-butylcarbaldehyde! The extreme polarity of the Ti–F bond is responsible for the special properties of catalyst 1.

    2. Electron Crystallography—Now a Handy Method (pages 46–47)

      Dr. Wilhelm Mertin

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199700461

      Multiple scattering of electrons in a crystal and the resulting interference problems make electron crystallography of inorganic substances a problematic undertaking. A recent publication by T. E. Weirich et al. now shows that electron crystallography could be the method of choice, for example, to determine the structure of small crystals. Providing that one has access to a high-resolution electron microscope, the other requirements of this method are relatively small.

    3. Overlong C[BOND]C Single Bonds (pages 48–49)

      Prof. Dr. Gerd Kaupp and Dipl.-Chem. Jürgen Boy

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199700481

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      What is the maximum length of a single bond between carbon atoms? Certainly, this question cannot be answered by quantum mechanical calculations alone—reliably interpreted physical measurements on real molecules are crucial. The longest unequivocally determined C[BOND]C single bonds (1.72 Å) have recently been found in tetraphenyldihydrocyclobutarenes 1 and 2.

  4. Communications

    1. Top of page
    2. Editorial
    3. Reviews
    4. Highlights
    5. Communications
    6. Book Reviews
    1. Organometallic Chemistry of [W2(OCH2tBu)8] (pages 52–54)

      Prof. Malcolm H. Chisholm, Dr. Kirsten Folting, Matthew A. Lynn, Dr. William E. Streib and Darin B. Tiedtke

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199700521

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      An unusual orientation of the bond is shown by the bridging ethyne ligand in complex 1, which is prepared from [W2(OCH2tBu)8] and ethyne: the crystal structure analysis of 1 revealed that the C[BOND]C bond of this ligand is neither parallel nor perpendicular to the W[BOND]W bond, but at an angle of 67° to it. Furthermore, the reactivity studies of [W2(OCH2tBu)8] with CO, ethene, allene, benzophenone, and thiobenzophenone have provided several tungsten complexes with remarkable structures.

    2. Molecular Self-Assembly to Give the Antiferromagnetic Cage Compound [{CpFe(CO)2(Mes)PO2}4{MesPO3Fe2(OH)Cl}2] (pages 55–56)

      Prof. Dr. Ingo-Peter Lorenz, Dr. Wolfgang Pohl and Prof. Dr. Heinrich Nöth

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199700551

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      Aerial oxidation with drastic consequences: The dinuclear building block [Fp2(Mes)PH]Cl (Fp = CpFe(CO)2, Mes = mesityl) is converted into the polynuclear, antiferromagnetic cage compound 1. In addition to retention and elimination of the Fp units at the phosphorus atoms, four iron(III) centers, four μ2-phosphinato, and two μ3-phosphonato ligands are formed, which are connected through O bridges.

    3. Linear Pentanuclear Complexes Containing a Chain of Metal Atoms: [Comath image5-tpda)4(NCS)2] und [Nimath image5-tpda)4Cl2] (pages 56–59)

      Dr. Shen-Jye Shieh, Chin-Cheng Chou, Gene-Hsiang Lee, Dr. Chih-Chieh Wang and Prof. Shie-Ming Peng

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199700561

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      Both anti–anti–anti–anti and syn–syn–syn–syn conformations of the bound metal ions are possible with the new ligand N,N′-bis(α-pyridyl)-2,6-diaminopyridine (H2tpda). Pentanuclear CoII and NiII complexes are accessible with this ligand (see sketch on the right). The metal chain is helically wrapped by four all-syn tpda ligands.

    4. An Interwoven Supramolecular Cage (pages 59–62)

      Peter R. Ashton, Dr. Andrew N. Collins, Matthew C. T. Fyfe, Dr. Peter T. Glink, Dr. Stephan Menzer, Prof. J. Fraser Stoddart and Prof. David J. Williams

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199700591

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      Hydrogen bonds and π[BOND]π stacking stabilize a supramolecular cage (depicted schematically on the right) constructed from five components, namely two trifurcated trisammonium cations and three ditopic crown ether molecules. This molecule is a remarkable example of a programmed supramolecular system: the information essential for the cage's assembly is stored in the covalent frameworks of the two building blocks.

    5. In4S[C(SiMe3)3]4: An Organoindium Compound with an In4S Core Isovalence Electronic to Pentahydro-closo-pentaborate(2–) (pages 62–64)

      Prof. Dr. Werner Uhl, Rene Graupner, Prof. Dr. Wolfgang Hiller and Markus Neumayer

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199700621

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      A trigonal-bipyramidal In4S central framework, which in terms of its electron count resembles a closo-cluster, is present in the title compound (structure on the right; C(SiMe3)3 substituents on the In atoms are omitted). This was prepared by treatment of In4[C(SiMe3)3]4 with the sulfur donor propylene sulfide and is the first organoindium analog of the closo-borates.

    6. TlI[C(SiMe3)3]—An Alkylthallium(I) Compound with a Distorted Tetrahedron of Tl Atoms in the Solid State (pages 64–65)

      Prof. Dr. Werner Uhl, Sven Uwe Keimling, Dr. Karl Wilhelm Klinkhammer and Dr. Wolfgang Schwarz

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199700641

      Weak thallium–thallium interactions are present in the thallium tetrahedron of the crystalline alkylthallium(I) compound Tl[C(SiMe3)3], which is easily accessible from cyclopentadienylthallium(I) and tris(trimethylsilyl)methyllithium. In solution, however, only the monomer of the extremely thermally sensitive compound can be detected.

    7. “Redox-Switch” Catalysis of C[BOND]C Bond Formation with H2: One-Electron Reduction of the Trityl Cation (pages 65–67)

      Prof. Robert T. Hembre and J. Scott McQueen

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199700651

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      Different products are formed from the electron transfer reaction between the ruthenium hydride 1 and the trityl cation when 1 is employed as a “redoxswitch” catalyst or as stoichiometric reducing agent. In the first case 1 converts H2 into a one-electron reducing agent for C[BOND]C bond formation, thus yielding the product known as Gomberg's dimer. In contrast, only triphenylmethane is produced in the stoichiometric reactions, by an electron-transfer/hydride-transfer mechanism.

    8. New Cage Compounds: Preparation and Characterization of Chiral C3-Symmetric Macrobicyclic Tris(phosphazides) (pages 67–70)

      Dr. Mateo Alajarín, Prof. Pedro Molina, Antonia López-Lázaro and Dr. Concepción Foces-Foces

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199700671

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      Highly unusual! Both the Z configuration of the intracyclic N[BOND]N bond and the conformation of the triphos group in 1 are novel. This chiral macrocycle, which is formed from the appropriate tripodal tris(azide) and triphos by self-assembly, has propellerlike, C3 symmetry according to its X-ray crystal structure. triphos = CH3C(CH2PPh2)3.

    9. [(η5-C5Me5)Al[BOND]Fe(CO)4]—Synthesis, Structure, and Bonding (pages 70–72)

      Dipl.-Chem. Jurij Weiss, Dana Stetzkamp, Dr. Bernhard Nuber, Prof. Dr. Roland A. Fischer, Dipl.-Chem. Christian Boehme and Prof. Dr. Gernot Frenking

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199700701

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      The bonding in the unprecedented complex [Cp*Al[BOND]Fe(CO)4] (depicted on the right) was investigated by quantum theoretical methods by using the model compound [CpAl[BOND]Fe(CO)4]. The strength of Al [RIGHTWARDS ARROW] Fe donor – acceptor bond, which is characteristic for this complex, is estimated to be about 50 kcal mol−1.

    10. Relative Configuration and Synthesis of a New C-4 Branched Sugar, a Component of the Lipooligosaccharide LOS-III from Mycobacterium gastri (pages 72–75)

      Jacques Longépé, Dr. Jacques Prandi and Prof. Jean-Marie Beau

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199700721

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      The total synthesis of four diastereomeric glycosides was necessary to determine the relative configuration of the epitope of a highly antigenic lipooligosaccharide isolated from Mycobacterium gastri. The correct diastereomer is shown below.

    11. The First 2-Carba-nido-pentaborane(8) Derivative; Structure of Sodium Hexaethyl-2, 4-Dicarba-nido-hexaborate(1 −) (pages 75–77)

      Prof. Dr. Bernd Wrackmeyer, Dipl.-Chem. Hans-Jörg Schanz and Dr. Wolfgang Milius

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199700751

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      Integration of a carbon atom in the carborane cage is the key feature of the deprotonation of 1 with Na[Et3BH] to give the sodium salt 2. The process is reversible: treatment of 2 with methanol leads to the reformation of 1.

    12. Myrmicarin 663: A New Decacylic Alkaloid from Ants (pages 77–80)

      Frank Schröder, Dr. Volker Sinnwell, Horst Baumann, Dr. Manfred Kaib and Prof. Dr. Wittko Francke

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199700771

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      Chemical warfare in insects: Ants have a vast arsenal of chemical weapons for defense or to catch prey. Here the isolation and identification of a highly sensitive alkaloid, myrmicarin 663, which has an entirely novel carbon skeleton, is reported.

    13. Microporous Magnesium Aluminophosphate STA-1: Synthesis with a Rationally Designed Template and Structure Elucidation by Microcrystal Diffraction (pages 81–83)

      Graham W. Noble, Dr. Paul A. Wright, Dr. Philip Lightfoot, Dr. Russell E. Morris, Kelly J. Hudson, Prof. Åke Kvick and Dr. Heinz Graafsma

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199700811

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      The design of inorganic solids and state-of-the-art microcrystallography at Europe's newest synchrotron facility go hand-in-hand in the synthesis and structure elucidation of STA-1, a low-density member (projection shown on the right) of the family of large-pore aluminophosphates.

    14. Probing Gaseous Ion–Molecule Complexes with Chiral Agents: The Reaction of Arenium Ions with (R)-([BOND])-s-Butyl Chloride (pages 83–85)

      Dr. Massimiliano Aschi, Prof. Dr. Fulvio Cacace and Dr. Anna Troiani

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199700831

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      Enantiomerically pure, gaseous reagents can be used to probe the chemical identity and the spatial arrangement of reaction partners confined within ion–molecule complexes (schematically represented on the right). The addition of gaseous arenium ions to (R)-([BOND])-s-C4H9Cl affords complexes within which aromatic alkylation proceeds with complete racemization. This suggests that the components of the complex undergo mutual rotation and that the s-butyl cation is the electrophile.

    15. On the Mobility of Trivalent Ions: Pr3+ in Pr3+-β″-Al2O3 (pages 85–87)

      Dr. Joachim Köhler and Prof. Dr. Werner Urland

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199700851

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      Mobile trivalent cations in solids? The results of temperature-dependent, single-crystal X-ray structure investigations of a Pr3+ -β″-Al2O3 crystal (see structure on the right, Pr3+ as black sphere) indicate just such an unusual ionic current transport mechanism.

    16. Atom-Bridged Intermediates in N- and P-Atom Transfer Reactions (pages 87–91)

      Marc J. A. Johnson, P. Mae Lee, Aaron L. Odom, Dr. William M. Davis and Prof. Christopher C. Cummins

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199700871

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      Formal N-atom insertion into the metal–-metal triple bond of the diamagnetic compound 1, which has been known for over twenty years, results in the paramagnetic, nitrido-bridged molecule 2. The characterization of three such N- and P-atom bridged species is described, and their role as intermediates in three-electron atom transfer reactions is highlighted.

    17. Insertion of Functional Groups into Square-Planar Units: A New Construction Principle for Open Microporous Framework Structures (pages 91–93)

      Michael Schindler and Prof. Dr. Werner H. Baur

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199700911

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      Large pores and reactive centers characterize the novel, more open vanadium phosphates. The three-dimensional nets on which they are based differ from those of classical microporous materials such as aluminosilicate zeolites; however, they have interesting topological relationships to some of them (see, for example, the framework of the sodalite type depicted on the right). Based on these relationships, microporous materials can be envisaged that contain arbitrary functional groups.

    18. New Nickel-Catalyzed Carbozincation of Alkynes: A Short Synthesis of (Z)-Tamoxifen (pages 93–95)

      Dipl.-Chem. Thomas Stüdemann and Prof. Dr. Paul Knochel

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199700931

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      A new highlight in the repertoire of carbometalation reactions is the highly stereo- and regioselective nickel-catalyzed carbozincation of internal alkynes. This is exemplified by a short and effective synthesis of the anti-breast-cancer drug (Z)-tamoxifen (see below; Z : E > 99 : 1; acac = acetylacetone, dba = dibenzylideneacetone). This reaction also allows the stereoselective synthesis of various tri- and tetrasubstituted olefins in good yield.

    19. Hydroxyamines as a New Motif for the Molecular Recognition of Phosphodiesters: Implications for Aminogloycoside–RNA Interactions (pages 95–98)

      Martin Hendrix, Phil B. Alper, Dr. E. Scott Priestley and Prof. Dr. Chi-Huey Wong

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199700951

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      Particularly stable complexes with bidentate binding are formed between 1,3-hydroxyamines and dimethylphosphate, which serve as models of the complexes formed by aminoglycoside antibiotics such as neomycin B (1) and RNA phosphodiesters. This recognition motif involving a hydrogen bond with the hydroxyl group is also found in the complexation of anions by simple aminoglycosides in aqueous solution.

    20. A Straightforward Access to α-Functional Phospholide Ions (pages 98–100)

      Dr. Serge Holand, Muriel Jeanjean and Prof. Dr. François Mathey

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199700981

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      The synthesis of porphyrin-like arrays based on the phosphole ring has moved a step closer with simple and general route to α-functional phospholide ions presented here [Eq. (a)]. py = 2-pyridyl.

    21. The First Large-Pore Vanadosilicate Framework Containing Hexacoordinated Vanadium (pages 100–102)

      Dr. João Rocha, Paula Brandão, Zhi Lin, Dr. Michael W. Anderson, Dr. Viveka Alfredsson and Dr. Osamu Terasaki

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199701001

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      A structure similar to that of microporous titanosilicate ETS-10 is reported for the first large-pore vanadosilicate framework containing stoichiometric amounts of hexacoordinated vanadium. A section of the high-resolution electron micrograph of the vanadosilicate is shown on the right.

    22. The Simultaneous Use of H-Bonding and Coulomb Interactions for the Self-Assembly of Fumaric Acid and Cyclic Bisamidine into One- and Two-Dimensional Molecular Networks (pages 102–104)

      Olivier Félix, Prof. Dr. Mir Wais Hosseini, Dr. André De Cian and Prof. Jean Fischer

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199701021

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      Fourfold hydrogen donors or acceptors for hydrogen bonding, the diprotonated bisamidine 1-2H2+ and the deprotonated fumaric acid 22−, cocrystallize to form one-dimensional α-networks when the ratio of 1-2H+ to 22− is 1 : 1 and two-dimensional β-networks when the ratio is 1 : 2.

    23. Preparation of Enantiomerically Pure 5-Palladatricyclo[4.1.0.02, 4]heptanes and Conversion into Enantiomerically Pure Complexes with Helical Chirality at Palladium (pages 104–106)

      Dr. A. Stephen K. Hashmi, Dipl.-Ing. Frank Naumann, Dipl.-Chem. Ralf Probst and Dr. Jan W. Bats

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199701041

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      A dramatic deviation from square-planar coordination for PdII complexes: the C[BOND]Pd[BOND]C and P[BOND]Pd[BOND]Planes in the helical chiral complexes 2 (∪ = 1,1′-ferrocenediyl) are unexpectedly tipped toward each other by as much as 30°. These complexes are prepared from the appropriate bidentate phosphane ligands and the bishomopalladole 1, which is remarkably stable and availalbe in enantiomerically pure form in good yields. E = CO2Me.

    24. Geometry-Tunable Lewis Acidity of Amidinium Cations and Its Relevance to Redox Reactions of the Thauer Metal-Free Hydrogenase: A Theoretical Study (pages 107–109)

      Prof. Jerzy Cioslowski and Prof. Dr. Gernot Boche

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199701071

      What are the thermodynamic prerequisites of the Berkessel–Thauer mechanism of action of the first metal-free hydrogenase? Model reactions of planar and bent amidinium ions with H2 in the absence and presence of H2O and NH3 as bases demonstrate the significance of a proton acceptor in these reactions; the bending of the amidinium ion provides the necessary fine-tuning.

    25. Enantioselective Synthesis of Homoallylamines by Nucleophilic Addition of Chirally Modified Allylboron Reagents to Imines (pages 109–110)

      Prof. Dr. Shinichi Itsuno, Katsuhiro Watanabe, Prof. Dr. Koichi Ito, Ashraf A. El-Shehawy and Prof. Dr. Ali A. Sarhan

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199701091

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      N-silylated imines are well-suited for reaction with chirally modified allylboron reagents to give enantiomerically enriched primary homoallylamines in high yields [Eq. (a)]. The chiral ligand, here N-tosyl-(–)-norephedrin, can be recovered after the reaction and used again to generate the chiral allylboron reagent. Ts = p-toluenesulfonyl.

    26. Assembly of Novel DNA Cycles with Rigid Tetrahedral Linkers (pages 111–113)

      Jufang Shi and Prof. Donald E. Bergstrom

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199701111

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      Rigid vertices are essential for the formation of supramolecular rings with DNA sequences. Two p-(2-hydroxyethyl)phenylethynylphenyl spacers attached to a central sp3 C atom are extended with oligonucleotide chains (single-stranded DNA). The conjugates that form (see below) self-assemble into a series of cyclic homologues, which can be separated by gel electrophoresis.

    27. [Me(PhMe2Si)2SiLi] and [Ph(Me3Si)2SiLi]: Preparation, Characterization, and Evidence for an Intramolecular Li[BOND]Ph Interaction (pages 113–115)

      Prof. Dr. Akira Sekiguchi, Dipl.-Chem. Masato Nanjo, Dr. Chizuko Kabuto and Prof. Dr. Hideki Sakurai

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199701131

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      Lithium–mercury exchange of the appropriate precursors in toluene yielded the first unsolvated, dimeric lithiosilanes 1. X-ray crystallographic data and NMR spectra of both compounds provide evidence of intramolecular lithium–phenyl interactions.

    28. Thermal Decomposition of [(η5-C5Me5)TiMe3]: Synthesis and Structure of the Methylidyne Cubane [{(η5-C5Me5)Ti}43-CH)4] (pages 115–117)

      Dr. Román Andrés, Dr. Pilar Gómez-Sal, Dr. Ernesto de Jesús, Dr. Avelino Martín, Dr. Miguel Mena and Dr. Carlos Yélamos

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199701151

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      An almost perfect Ti4C4 cube is present in compound 1, which is formed by methane elimination from [Cp*TiMe3] at 95°C. Compound 1 is a dark brown crystalline solid that is stable in solution in toluene at 200°C for several days. Cp* = C5Me5.

    29. An Al4(OH)4 Eight-Membered Ring in a Molecular Aluminopolysiloxane and Its Behavior with Bases (pages 117–119)

      Prof. Michael Veith, Maria Jarczyk and Dr. Volker Huch

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199701171

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      Only three of the four diethyl ether molecules are coordinated to the OH groups in the crystal structure of the aluminopolysiloxane 1. Compound 1 is obtained from tert-butoxyaluminum dihydride and diphenylsilanediol in Et2O. The fourth coordination site is sterically shielded by two oppositely placed OSi(Ph2)OSi(Ph2)O bridges. Replacement of Et2O with Et3N results in twofold deprotonation of the polycycle; now only two donor molecules can coordinate to the central eight-membered ring.

    30. A Complex Catalytic Cycle Leading to a Regioselective Synthesis of o,o′-Disubstituted Vinylarenes (pages 119–122)

      Prof. Marta Catellani, Dr. Franco Frignani and Armando Rangoni

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199701191

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      Palladium(0), (II), and (IV) complexes are intermediates in the unusual palladium catalyzed synthesis of 2,6-dialkyl-substituted vinylarenes. Since these complexes discriminate between alkyl and aryl iodides and between strained and terminal olefins at certain stages of the process, this provides both a highly chemoselective and a regioselective access to 1,2,3-trisubstituted arenes (see, for example, Eq. (a)).

    31. Unconventional Amphiphilic Polymers Based on Chiral Polyethylene Oxides (pages 122–125)

      Henk M. Janssen, Emiel Peeters, Marga F. van Zundert, Dr. Marcel H. P. van Genderen and Prof. Dr. E. W. Meijer

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199701221

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      Regular repeats of polar (P) and apolar units (A) in the main chain of polyethylene oxides earmark a new class of amphiphilic polymers. This primary structure was designed in analogy to peptides that form coiled-coil structures. In aqueous solution these macromolecules undergo a transition from random coil to helical conformations prior to phase separation.

    32. Immunization of Mice with a Fully Synthetic Globo H Antigen Results in Antibodies against Human Cancer Cells: A Combined Chemical—Immunological Approach to the Fashioning of an Anticancer Vaccine (pages 125–128)

      Dr. Govindaswami Ragupathi, Dr. Tae Kyo Park, Dr. Shengle Zhang, Dr. In Jong Kim, Linda Graber, Sucharita Adluri, Prof. Kenneth O. Lloyd, Prof. Samuel J. Danishefsky and Prof. Philip O. Livingston

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199701251

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      Of mice and men: A vaccine composed of the fully synthetic globo H human breast tumor antigen 1 and a carrier protein elicits the formation of IgM antibodies in mice. These antibodies bind to MCF-7 breast cancer cells and trigger effective complement-mediated cell lysis. These promising results from the immune system of the mouse prompts a strategy to foster active immunity in humans.

    33. Detection and Characterization of a Pre-Reactive Complex in a Mixture of Water and Fluorine: Rotational Spectrum of H2O…F2 (pages 129–130)

      Stephen A. Cooke, Dr. Gina Cotti, Prof. John H. Holloway and Prof. Anthony C. Legon

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199701291

      A planar (C2v) or effectively planar (Cs) geometry is exhibited by the pre-reactive intermediate H2O…F2, which has been identified in gaseous mixtures of H2O and F2. The rotational spectrum of this intermediate, which was obtained by using a Fourier-transform microwave spectrometer equipped with a fast-mixing nozzle, reveals that H2O…F2 has an O…F distance of 2.719(4) Å and is very weakly bound.

    34. Tuning the Structure and Reactivity of the [Cu2(μ-O)2]2+ Core: Characterization of a New Bis(μ-oxo)dicopper Complex Stabilized by a Sterically Hindered Dinucleating Bis(triazacylononane) Ligand (pages 130–133)

      Dr. Samiran Mahapatra, Dr. Victor G. Young Jr., Susan Kaderli, Prof. Andreas D. Zuberbühler and Prof. William B. Tolman

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199701301

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      Ligand-induced perturbation of structure and function of a copper–dioxygen complex is revealed by structural characterization and reactivity studies of the complex shown on the right. In addition to preventing formation of a (μ-peroxo)dicopper isomer, notable effects arising from the ethylene linker between the capping ligands include discernible puckering of the [Cu2(μ-O)2]2+ unit, lengthened Cu[BOND]O distances, and slowed intramolecular monooxygenase reactivity compared to planar analogs lacking the tether.

    35. Synthesis and Structure of the First Molecular Thulium(II) Complex: [TmI2(MeOCH2CH2OMe)3] (pages 133–135)

      Prof. Dr. Mikhail N. Bochkarev, Dr. Igor L. Fedushkin, Anatoly A. Fagin, Tatyana V. Petrovskaya, Dr. Joseph W. Ziller, Randy N. R. Broomhall-Dillard and Prof. Dr. William J. Evans

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199701331

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      Divalent 4f element chemistry can now be expanded from Eu, Yb, and Sm to include Tm since a synthetic route to the first crystallographically characterizable molecular complex to TmII has been found. The intense green title complex was isolated from the reaction of TmI3 and Tm in dimethoxyethane. The photosensitive complex has the pentagonal-bipyramidal structure shown on the right.

    36. meso, meso-Linked Porphyrin Arrays (pages 135–137)

      Prof. Atsuhiro Osuka and Hitoshi Shimidzu

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199701351

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      The perpendicular arrangement of porphyrin units in dimer 1 is reflected in a large excitonic coupling that leads to splitting of the Soret bands and only modest spectral changes in the Q-bands. Compound 1 and the analogous trimer and tetramer are prepared by oxidative coupling of the corresponding 5,15-diarylporphyrin and are the first examples of compounds having direct meso, meso-linked porphyrin chromophores. Ar = 3,5-tBu2C6H3.

    37. X-ray Structure of [Ru(bpy)3]0: An Expanded Atom or a New Electride? (pages 137–140)

      Eduardo E. Pérez-Cordero, Dr. Charles Campana and Prof. Luis Echegoyen

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199701371

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      No counteranions or solvent molecules are found in single crystals of [Ru(bpy)3]0, an air-sensitive but thermally stable new material. Analysis of the X-ray structural data reveals a relatively undistorted C3-symmetric system with empty lattice spaces, which are represented by empty circles in the picture on the right. This packing structure is reminiscent of those in electrides.

    38. Synthesis, Structure, High-Resolution Spectroscopy, and Laser Chemistry of Fluorooxirane and 2,2-[2H2]-Fluorooxirane (pages 140–143)

      Dr. Hans Hollenstein, Dr. David Luckhaus, Dipl.-Chem. Jörg Pochert, Prof. Dr. Martin Quack and Dr. Georg Seyfang

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199701401

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      Formation of a CO double bond by elimination of HF is the reaction undergone by the newly prepared fluorooxiranes (show below for the deuterated compound) on multiphoton excitation with a CO2 laser: the difference in the CO bond lengths [pm] suggests ketene formation. The structural characterization was performed by high-resolution FTIR spectroscopy.

    39. Ene Reactions of Alkynes for the Stereoselective Synthesis of Allylamines (pages 143–145)

      Dipl.-Ing. Armin R. Ofial and Prof. Herbert Mayr

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199701431

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      Counterion in control! When complex anions with low nucleophilicity are used, a previously unkown ene reaction of iminium ions and alkynes occurs [Eq. (a)], which provides straightforward stereo- and regioselective access to substituted allylamines.

    40. Synthesis and Isolatin of a Homodimer of Cadmium Selenide Nanocrystals (pages 145–147)

      Dr. Xiaogang Peng, Troy E. Wilson, Prof. Dr. A. Paul Alivisatos and Prof. Dr. Peter G. Schultz

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199701451

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      By size-selective precipitation homodimeric CdSe nanocrystals could be isolated from a mixture of oligomers formed when monodisperse CdSe nanocrystals (see right) were linked by the bifunctional organic ligand, bis(acyl hydrazide). TEM images revealed a reproducible separation between CdSe particles of approximately a quarter of the particle diameter. This distance is consistent with the physical dimensions of the linker.

    41. Formation of Supramolecular Donor–Acceptor Complexes between Bis(pyridiniomethyl)azobenzenes and Eosin in Solutions and at Solid Interfaces: Transduction into Optical and Microgravimetric Signals (pages 147–150)

      Dr. Koodali T. Ranjit, Sharon Marx-Tibbon, Iddo Ben-Dov and Prof. Itamar Willner

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199701471

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      The formation and dissociation of complexes between eosin derivatives and the photoisomerizable azobenzene derivatives (E)-1 and (Z)-1 is reversibly switched light. An eosin monolayer assembled onto a quartz crystal is an active interface for the transduction of the photochemically induced formation of the complex with (E)-1 and the dissociation of the complex upon photoisomerization to the Z isomer. Thus optical signals can be transduced into electronic signals.

    42. Low-Melting, Liquid-Crystalline Metalloporphyrins (pages 150–152)

      Dr. Qing Min Wang and Prof. Dr. Duncan W. Bruce

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199701501

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      The type of mesophase can be controlled by the addition of side chains to porphyrins bearing several long terminal chains (see, for instance, 1). Either columnar phases or those characteristic of rodlike molecules are formed, whose transition temperatures are lower than those found in the parent systems.

    43. Valence-Delocalized and Valence-Trapped FeIIFeIII Complexes: Drastic Influence of the Ligands (pages 152–155)

      Sujit K. Dutta, Dr. Jürgen Ensling, Dipl.-Chem. Rüdiger Werner, Dr. Ulrich Flörke, Prof. Dr. Wolfgang Haase, Prof. Dr. Philipp Gütlich and Prof. Dr. Kamalaksha Nag

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199701521

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      The two macrocyclic ligands H2L1 and H2L2 are not very different, but their FeIIFeIII complexes are remarkably so. [L1Fe2(μ-OAc)2](ClO4) is valence-delocalized on the Mössbauer time scale over the range 1.8–364 K, whereas [L2Fe2(μ-OAc)(OAc)(H2O)](ClO4)·2H2O is valence-trapped even at room temperature. The difference in properties of these complexes is also reflected in their electronic spectra, in their electrochemical and magnetic behavior, and in their structures.

    44. Biomimetic Synthesis of Lamellarin G. Trimethyl Ether (pages 155–156)

      Dipl.-Chem. Alexander Heim, Dipl.-Chem. Andreas Terpin and Prof. Dr. Wolfgang Steglich

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199701551

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      Three steps to lamellarins—these marine alkaloids such as 1, which show cytotoxic and immunomodulatory activity, are formed from two arylpyruvic acids and one (phenylethyl)amine building block. The key step in this reaction sequence is a Heck cyclization.

    45. Synthesis and Coordination Chemistry of Fluorine-Containing Cages (pages 156–158)

      Priv.-Doz. Dr. Herbert Plenio, Dipl.-Chem. Ralph Diodone and Dirk Badura

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199701561

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      Covalently bound fluorine atoms are effective donors! This is demonstrated by the F4O3N1 coordination of the Cs+ ion in the complex with the macropolycyclic ligand 1. Three of the four shortest bonds to the metal ion are Cs+[BOND]F bonds, and one of these is extremely short (284.2(3)pm).

    46. A Stable Hetero-trans-cyclopentene (pages 159–160)

      Prof. Dr. Adolf Krebs, Dr. Karl-Ingo Pforr, Dipl.-Chem. Walter Raffay, Dipl.-Chem. Bernd Thölke, Prof. Dr. W. A. König, Dr. Ingo Hardt and Prof. Dr. Roland Boese

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199701591

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      A strongly deformed C[BOND]C double bond is present in the chiral trans-cycloheptene derivative 1. Nonetheless it is thermally quite stable and can be separated into enantiomers. Two effects are responsible for this: four methyl groups in the α-positions increase the barriers for the trans–cis isomerization and the dimerization, and the introduction of Si(CH3)2 in the place of CH2 in the trans-cycloheptene reduces the ring strain.

    47. Aggregation and Redox-Disproportionation in Tripodal Indium and Thallium Amides: First Characterization of Mixed-Valent MI/MII Compounds (M = In, Tl) (pages 160–163)

      Konrad W. Hellmann, Priv.-Doz. Dr. Lutz H. Gade, Dr. Alexander Steiner, Prof. Dr. Dietmar Stalke and Frank Möller

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199701601

      Thumbnail image of graphical abstract

      Aggregation through weak metal–metal contacts as well as redox disproportionations are the chemical characteristics of the metal exchange products of the tripodal tris(lithium amide)s [H3CC{CH2N(Li)SiMe3}3(L)3] (L=dioxane, THF) with MCl (M = In, Tl). These reactions yield the first examples of mixed-valent MI/MII compounds like [H3CC(CH2NSiMe3)3Tl2]2 (see structure on the right).

    48. Laser Chemistry in Suspensions: New Products and Unique Reaction Conditions for the Carbon–Steam Reaction (pages 163–166)

      Huxiong Chen, Thomas McGrath and Prof. Dr. Gerald J. Diebold

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199701631

      Irradiation of aqueous suspensions of carbon black with a pulsed laser heats the carbon particles to high temperatures, initiating chemical reactions. In addition to H2, CO, and CO2, the usual products in the carbon–steam and shift reactions, CH4, C2H2, C2H4, and C2H6 are also produced as the carbon is consumed.

    49. Total Synthesis of Epothilone A: The Olefin Metathesis Approach (pages 166–168)

      Dr. Zhen Yang, Yun He, Dr. Dionisios Vourloumis, Dr. Hans Vallberg and Prof. Dr. K. C. Nicolaou

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199701661

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      A flexible alterative route to the total synthesis of the antitumor agent epothilone A (1, see below) has been achieved by a highly convergent strategy involving olefin metathesis as a key step. The strategy may allow the chemical synthesis of a library of designed epothilones for biological screening.

  5. Book Reviews

    1. Top of page
    2. Editorial
    3. Reviews
    4. Highlights
    5. Communications
    6. Book Reviews
    1. Book Review: Qu'est-ce que l'alchimie? By P. Laszlo (pages 169–170)

      Christoph Meinel

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199701692

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