Angewandte Chemie International Edition in English

Cover image for Vol. 35 Issue 13‐14

July 1996

Volume 35, Issue 13-14

Pages 1359–1579

Currently known as: Angewandte Chemie International Edition

    1. Cover Picture (Angew. Chem. Int. Ed. Engl. 13/14/1996)

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199613581

      Thumbnail image of graphical abstract

      The cover picture shows a ribbon model of a hairpin pyrrole/imidazole polyamide–oligonucleotide simultaneously binding the major and minor grooves of DNA (red circles: N-methylimidazole; blue circles: N-methylimidazole; blue circles: N-methylpyrrole rings; diamond: β-alanine). The structural formulas on the right depict the molecular interactions responsible for sequence-specific recognition: T · AT and C + GC base triplets are formed by Hoogstein hydrogen bonding of T to a Watson–Crick AT base pair and protonated MeC to a Watson–Crick GC base pair. On the left is the complex of the polyamide ImPyPy-γ-ImPyPy-β with the site 5′-TGACA-3′ (circles with dots: lone pairs on N3 of purines and O2 of pyrimidines; circles containing an H: N2 hydrogen on guanine; dashed lines: putative hydrogen bonds). The energetics and specificity of the complex is reported by Szewczyk et. al. on pages 1487 ff. The picture was generated with MacDraw Pro software.

  1. Reviews

    1. Top of page
    2. Reviews
    3. Highlights
    4. Communications
    5. Book Reviews
    1. Glycals in Organic Synthesis: The Evolution of Comprehensive Strategies for the Assembly of Oligosaccharides and Glycoconjugates of Biological Consequence (pages 1380–1419)

      Prof. Samuel J. Danishefsky and Dr. Mark T. Bilodeau

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199613801

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      Open-minded carbohydrate chemists are well advised to consider glycals for oligosaccharide synthesis. Glycal-based methods, which obviate many of the onerous protecting group manipulations that have dominated this field, have led to syntheses of blood group determinants and antigen recognition domains. The artificial glyco-protein at the most advanced stage of preclinical development is the protein conjugate 1 of the human globo H breast tumor antigen.

    2. Recent Developments of Molecular Chemistry for Sol–Gel Processes (pages 1420–1436)

      Prof. Dr. Robert J. P. Corriu and Dr. Dominique Leclercq

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199614201

      New precursors and different gelation processes are among the most important results to have emerged from the field of sol–gel chemistry in the last few years. In particular, the use of nonhydrolytic processes and the application of organic–inorganic precursors in the preparation of gels are very promising developments. These have brought the planned synthesis of solids with specific properties a step closer.

    3. CC-1065 and the Duocarmycins: Understanding their Biological Function through Mechanistic Studies (pages 1438–1474)

      Prof. Dale L. Boger and Douglas S. Johnson

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199614381

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      A class of potent antitumor antibiotics including CC-1065 and the duocarmycins (for example 1) and their properties relevant for DNA alkylation are the topics of this review. The hypotheses on the mechanism of their function are defined with the evidence gleaned from synthetic derivatives and the ent-isomers of the natural products. The deduced fundamental relationships between structure, functional reactivity, and biological properties are described.

  2. Highlights

    1. Top of page
    2. Reviews
    3. Highlights
    4. Communications
    5. Book Reviews
    1. Planar-Chiral Ferrocenes: Synthetic Methods and Applications (pages 1475–1477)

      Prof. Dr. Antonio Togni

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199614751

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      The first industrial applications of chiral ferrocenyl lignds of the Josiphos type have recently been disclosed. Compound 1a is used in the Rh-catalyzed, asymmetric hydrogenation of 2, a precursor in a new commercial synthesis of (+)-biotin. Ligand 1b is part of the highly active Ir catalyst used for the reduction of imine 3, from which the herbicide (S)-Metolachlor is made.

    2. Design of Diradical-based Hydrogen Abstraction Agents (pages 1478–1480)

      Prof. Dr. Peter Chen

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199614781

      Why are diradicals used as hydrogen abstraction agents in the enediyne antitumor antibiotics, and what would happen if a “nonnatural” diradical were to be used? The very slow abstraction rates by arene diradicals suggest an answer to the question of the functional significance of diradicals versus monoradical abstraction agents in the natural products, and furthermore, suggest potential strategies for the rational modification of DNA-cleaving agents by alteration of the diradical “warhead”.

  3. Communications

    1. Top of page
    2. Reviews
    3. Highlights
    4. Communications
    5. Book Reviews
    1. Template Assembled Synthetic Proteins (TASP) as Functional Mimetics of Proteins (pages 1482–1485)

      Prof. Dr. Manfred Mutter, Dr. Pascal Dumy, Dr. Patrick Garrouste, Dr. Christian Lehmann, Dipl.-Chem. Marc Mathieu, Dipl.-Chem. Cristina Peggion, Dipl.-Chem. Stéphane Peluso, Dr. Alain Razaname and Dr. Gabriele Tuchscherer

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199614821

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      The bare essentials of a functional protein are all that are retained when the structural domain of a native protein is replaced by a synthetic template molecule (see picture below). New strategies for the synthesis of this novel type of template-assembled synthetic peptide (TASP) provide functional mimetics of receptors and antibodies.

    2. Synthesis, Crystal Structure, and Magnetic Properties of an Octanuclear Nickel(II) Complex with a hexahedro-Ni8 Core (pages 1485–1487)

      Prof. Dr. Juan Faus, Dr. Francisco Lloret, Prof. Dr. Miguel Julve, Juan M. Clemente-Juan, Dr. M. Carmen Muñoz, Prof. Dr. Xavier Solans and Dr. Mercedes Font-Bardía

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199614851

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      A Ni8 cube, assembled with twelve bridging μ-violurato ligands, is present in 1 (H3vi = violuric acid). The oximate groups of the ligands lie along the edges of the cube, connecting the metal ions in an unprecedented trans conformation (see picture, • [DOUBLE BOND] Ni) and mediating a strong antiferromagnetic coupling between the paramagnetic centers about 5 Å apart. Counterions: Ni2+, 4 K+.

    3. Sequence-Specific Recognition of DNA by a Major and Minor Groove Binding Ligand (pages 1487–1489)

      Jason W. Szewczyk, Eldon E. Baird and Prof. Peter B. Dervan

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199614871

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      A combination of the binding models for the simultaneous recognition of both grooves of DNA led to the design of a polyamide–oligonucleotide ligand that binds to a specific DNA sequence with an association constant of Ka > 2 × 1010M−1. The oligonucleotide portion forms a triple helix in the major groove of DNA, and the polyamide unit forms a hairpin in the minor groove (see ribbon model below).

    4. Selective Binding of the Dipeptides L-Phe-D-Pro and D-Phe-L-Pro to β-Cyclodextrin (pages 1490–1492)

      Milana Maletic, Dipl.-Chem. Helma Wennemers, Dr. D. Quentin McDonald, Prof. Ronald Breslow and Prof. W. Clark Still

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199614901

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      A combinatorial approach revealed the highly selective binding of the dipeptides L-Phe-D-Pro and D-Phe-L-Pro to β-cyclodextrin. NMR spectroscopy and molecular modeling provide a picture of the possible binding mode and an explanation of why those specific dipeptides were selected from the tripeptide library.

    5. Self-Assembly of a Two-Component Hydrogen-Bonded Network: Comparison of the Two-Dimensional Structure Observed by Scanning Tunneling Microscopy and the Three-Dimensional Crystal Lattice (pages 1492–1495)

      Dipl.-Phys. Katrin Eichhorst-Gerner, Dr. Andreas Stabel, Dipl.-Chem. Georg Moessner, Dr. Dries Declerq, Dr. Suresh Valiyaveettil, Priv.-Doz. Dr. Volker Enkelmann, Prof. Dr. Klaus Müllen and Prof. Dr. Jürgen P. Rabe

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199614921

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      Molecular recognition in monolayers on graphite: Stoichiometric (2:1) donor–acceptor complexes of 5-alkoxyisophthalic acids with bifunctional aromatic bases have been detected with scanning tunneling microscopy (STM). The 2D crystal lattice of the donor–acceptor complex from the hexadecoxy-substituted isophthalic acid and 2,5-dimethylpyrazine is shown schematically below.

    6. Poly(phenylenesulfidephenylenamine) (PPSA)—the “Compound” of Polyphenylenesulfide with Polyaniline (pages 1495–1497)

      Dr. Li Xiang Wang, Dipl.-Chem. Thomas Soczka-Guth, Dr. Edsko Havinga and Prof. Dr. Klaus Müllen

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199614951

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      Two structures, one polymer. Two important materials, polyaniline and polyphenylenesulfide, have been combined to form a single compound, poly(phenylenesulfidephenylenamine) (PPSA, 1). The new soluble polymer 1 can be obtained with well-defined structure and high molecular weight from a polysulfonium cation precursor.

    7. Synthesis and Structure of a Discrete Hexanuclear Uranium–Phosphate Complex (pages 1497–1498)

      Ladd M. Mokry, Dr. Norman S. Dean and Prof. Carl J. Carrano

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199614971

      Thumbnail image of graphical abstract

      The first high-nuclearity uranium complex contains an octahedral array of metal centers that is coordinated by twelve diphenylphosphate as well as eight oxo or hydroxo ligands. Although the degree of protonation of the capping centers could not be determined unambiguously, many of the findings point to OH ligands. The picture on the right shows the U6O8 framework of the complex.

    8. 2-Triaxanemethyl Cation and 2,10-para-[32.56]Octahedranedimethyl Dication (pages 1499–1501)

      Prof. George A. Olah, Dr. Herwig A. Buchholz, Prof. G. K. Surya Prakash, Dr. Golam Rasul, Dr. James J. Sosnowski, Prof. Roger K. Murray Jr., Doz. Dr. Mikhael A. Kusnetsov, Dr. Shelue Liang and Prof. Dr. Armin de Meijere

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199614991

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      A description as sets of nonclassical, unsymmetric, bridged bicyclobutonium ions fits the title ions 1 and 2. These are accessible by ionization of the corresponding methanol derivatives in superacidic media; the assignment of structure rests on ab initio calculations and on comparisons of experimental and calculated 13C NMR chemical shifts.

    9. Hexaborylbenzene and Tetraborylethene Derivatives (pages 1501–1503)

      Andreas Maderna, Dr. Hans Pritzkow and Prof. Dr. Walter Siebert

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199615011

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      Transition metal catalyzed reactions of the diborylacetylene 1 allow access to perborylated C[BOND]C multiply bonded systems. Cyclotrimerization of 1 results in the hexaborylbenzene 2. Diboration of 1 with the diborane 3 provides the tetraborylethene derivative 4. Compounds 2 and 4 react with LiMe and AlMe3 under cleavage of the boron–oxygen bonds. The dodecamethyl derivative C6(BMe2)6 forms the structurally characterized complex [C6(BMe2)6 · 2 Li2O2C6H4 · 8 NC5H5] with pyridine and Li2O2C6H4.

    10. Synthesis of Naturally Occurring, Conformationally Restricted Oxazole- and Thiazole-Containing Di- and Tripeptide Mimetics (pages 1503–1506)

      Dr. Georgi Videnov, Dipl.-Chem. Dietmar Kaiser, Dipl.-Chem. Christoph Kempter and Prof. Dr. Günther Jung

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199615031

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      An important step in the synthesis of heterocyclic amino acids such as 1, which can be used to modify and constrain peptide backbones, is the newly developed oxidation of dihydrooxazoles to give oxazoles with 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU)/CCl4/acetonitrile/pyridine.

    11. Synthesis of the DNA Gyrase Inhibitor Microcin B17, a 43-Peptide Antibiotic with Eight Aromatic Heterocycles in its Backbone (pages 1506–1508)

      Dr. Georgi Videnov, Dipl.-Chem. Dietmar Kaiser, Dipl.-Biol. Marc Brooks and Prof. Dr. Günther Jung

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199615061

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      One of the most unusual ribosomally synthesized and posttranslationally modified polypeptides, microcin B17, is a polypeptide antibiotic (see structure below). The total synthesis of this large molecule with oxazole and thiazole rings now enables structure–activity studies in a very important field of drug targeting.

    12. [Sb12{(2-MeO)C6H4N}18]·6 THF; A Twenty-Four Membered Imidoantimony (III) Metallacycle (pages 1508–1510)

      Dr. Michael A. Beswick, Maxwell K. Davies, Michael A. Paver, Dr. Paul R. Raithby, Dr. Alexander Steiner and Dr. Dominic S. Wright

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199615081

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      Six Sb2N2 rings linked by single imido–N bridges to give a 24-membered ring characterize the structure of the title compound (the core is shown on the right). This is the largest Group 15 metal–imido complex to be structurally characterized and the first p block metal–imido metallacycle.

    13. Metastable Reverse Globular Micelles and Giant Micellar Wires from Block Copolymers (pages 1510–1512)

      Dipl.-Phys. Joachim P. Spatz, Dipl.-Chem. Stefan Mößmer and Prof. Dr. Martin Möller

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199615101

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      Formation of reverse cylindrical micelles of a block copolymer with a long core block is kinetically controlled. The diagram shows the relative energy of the different structures.

    14. Synthesis, Structure, and Bonding of a Mixed-Valent Tetraphosphete (pages 1512–1514)

      Prof. Dr. Walter Frank, Dipl.-Chem. Volker Petry, Dipl.-Chem. Elmar Gerwalin and Dr. Guido J. Reiss

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199615121

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      The bonds are of equal length between the four P atoms, two with the coordination number 4 and two with the coordination number 2, that form the central four-membered ring of the dispirocyclic tetraphosphete 1. This ring exhibits a large rhombic distoration that is manifested by an unusually acute λ5P-λ3P-λ5P angle.

    15. A Mild General Procedure for the One-Pot Conversion of Amides to Aldehydes (pages 1515–1516)

      Dr. Shelley Bower, Dr. Kristina A. Kreutzer and Prof. Dr. Stephen L. Buchwald

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199615151

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      A wide range of amides containing different functional groups were readily converted into their corresponding aldehydes by means of a simple protocol. The reaction with [Ti(OiPr)4] and Ph2SiH2 proceeds at room temperature via an enamine intermediate, which is then hydrolyzed to afford the aldehyde [Eq (a)].

    16. Reversible Formation of Raftlike Organoimidotetrarhodium Clusters by the Migration of RhLmath image Fragments (pages 1516–1518)

      Dr. Cristina Tejel, Dr. You-Mao Shi, Dr. Miguel A. Ciriano, Dr. Andrew J. Edwards, Dr. Fernando J. Lahoz and Prof. Luis A. Oro

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199615161

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      The formation of three new metal-metal bonds results from the addition of CO to the tetranuclear complex 1. This process invovles the migration of the Rh center coordinatated to the arene ligand in 1 to the open edge of the Rh3 core to give the complex 2. The reaction is reversible, and thus the Rh center hops from one site to the other by addition or removal of a two-electron ligand

      [DOUBLE BOND] 1,5-cyclooctadiene.

    17. LiCHCl2 · 3 Pyridine, Structure of a Carbenoid with a Tetrahedral C Atom (pages 1518–1520)

      Dipl.-Chem. Achim Müller, Michael Marsch, Dr. Klaus Harms, Dr. John C. W. Lohrenz and Prof. Dr. Gernot Boche

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199615181

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      C[BOND]Cl bonds approximately 10 pm longer than those in CH2Cl2 are present in LiCHCl2 · 3 C5H5N (1). This and the sum of the bond angles around C (308° excluding the C[BOND]Li bond) confirms the increased p character of the C[BOND]Cl bonds and thus the pronounced electrophilicity of carbenoids. Calculations on the solvated and nonsolvated carbenoid and the comparison with experimental data reveal the remarkable influence of solvation on structure, stability, and 13C chemical shift, which is useful for predicting the structures of such molecules in solution.

    18. Porphyrinoid Macrocycles Based on Thiophene—The Octaethyltetrathiaporphyrin Dication (pages 1520–1524)

      Prof. Dr. Emanuel Vogel, Dr. Michael Pohl, Dr. Adalbert Herrmann, Dr. Torsten Wiss, Christoph König, Dr. Johann Lex, Prof. Dr. Maurice Gross and Dr. Jean Paul Gisselbrecht

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199615201

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      As a model compound in the thiaporphyrin series, the perchlorate of the dication 1 is ideal because of its favorable solubility properties. The key step in its synthesis is the acid-induced condensation (not biomimetic!) of 3,4-diethyl-2-hydroxymethylthiophene that affords the tetra- as well as the pentacyclocondensation product. The latter product opens a route to the 22π pentathiapentaphyrin trication 2, the sulfur analog of pentaphyrin.

    19. Template-Driven Syntheses of Polymeric Metal Cyanides: A Chiral Nanoporous Host for the nBu4N+ Ion (pages 1525–1527)

      Dr. Peter Schwarz, Dr. Stefan Eller, Dipl.-Chem. Eric Siebel, Tarek M. Soliman MSc, Prof. Dr. R. Dieter Fischer, Dr. David C. Apperley, Nicola A. Davies MSc and Prof. Dr. Robin K. Harris

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199615251

      A comfortable fit is provided for the large tetrabutylammonium ion within the wide channels of the new host–guest compound [(nBu4N)0.5(Me3Sn)3.5Fe(CN)6]. The lipophilic walls are formed by helical [Fe-CN-Sn-NC] chains involving {Fe(CNSnMe3)6} octahedra that are enantiomorphically derivatized due to cross-linking.

    20. The Effect of the Surrounding Medium on the Interaction of Nitriles with Boron Trifluoride (pages 1527–1529)

      Prof. Ian R. Beattie and Peter J. Jones

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199615271

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      The remarkable change in the B[BOND]N bond lengths of CH3CN · BF3 and HCN · BF3 between the gas phase and the condensed phase has been attributed to effects of the surrounding medium. Results herein suggest that in BF3-rich argon matrices, CH3CN · BF3 and HCN · BF3 are present in the form with a short B[BOND]N bond, as is CH3CN · BF3 in solution in benzene. The two structural alternatives for HCN · BF3 are shown schematically above.

    21. Intramolecular Movements of Lithium in Crystals (pages 1529–1533)

      Prof. Dr. Michael Veith, Dr. Michael Zimmer, Kira Fries, Dr. Jutta Böhnlein-Maus and Dr. Volker Huch

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199615291

      Rotations of the atoms around the center of gravity of the molecule characterize the cooperative intramolecular movement of the two lithium atoms in the solid amide Li2[(tBu[BOND]O[BOND]SiMe2)2N]2 just above room temperature. This movement can be stopped by cooling the sample, whereupon a phase transition occurs. A further phase transition occurs at temperatures above 100°C leading to a “plastic phase” in which whole molecules tumble around their centers of gravity.

    22. New Family of Enantiomerically Pure Liquid Crystals Containing a Chiral Biphenyl Core (pages 1533–1535)

      Prof. Dr. Guy Solladié, Philippe Hugelé, Dr. Richard Bartsch and Dr. Antoine Skoulios

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199615331

      Thumbnail image of graphical abstract

      Cholesteric mesophases are formed by compounds of type 1 with axial chirality. The key to this behavior is the rigid twisted biphenyl core; the planes of the two aryl rings form an angle of 56° (R [DOUBLE BOND] R′ [DOUBLE BOND] 4-C8H17OC6H4CO2).

    23. An Electroactive Photoisomerizable Monolayer-Electrode: A Command Surface for the Amperometric Transduction of Recorded Optical Signals (pages 1535–1537)

      Amihood Doron, Dr. Eugenii Katz, Dr. Moshe Portnoy and Prof. Itamar Willner

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199615351

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      A phenoxynaphthacenequinone forms a densely packed monolayer together with 1-tetradecanethiol on a gold electrode. The assembly can be reversibly switched to enable amperometric transduction of an optical signal. In the diagram on the right the current is switched off by irradiation with UV light.

    24. Pyranosyl-RNA: Base Pairing between Homochiral Oligonucleotide Strands of Opposite Sense of Chirality (pages 1537–1541)

      Dr. Ramanarayanan Krishnamurthy, Dr. Stefan Pitsch, Dr. Mark Minton, Dr. Christian Miculka, Dr. Norbert Windhab and Prof. Dr. Albert Eschenmoser

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199615371

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      Pyranosyl-RNA, an isomer of natural RNA (constitution and pairing conformation shown on the right), displays remarkable properties. Homochiral pyranosyl-RNA strands with opposite senses of chirality are found to pair to give quasi-racemic duplexes. Correspondingly altered pairing rules result.

    25. Chemical Double-Mutant Cycles for the Measurement of Weak Intermolecular Interactions: Edge-to-Face Aromatic Interactions (pages 1542–1544)

      Harry Adams, Fiona J. Carver, Dr. Christopher A. Hunter, Juan Carlos Morales and Dr. Eileen M. Seward

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199615421

      Thumbnail image of graphical abstract

      Quantitative descriptions of complex recognition processes rely on the measurement of the magnitude of weak intermolecular interactions such as the π-π interaction between arene units. In one approach thermodynamic cycles of compounds with structural variations (mutations) are constructed. The association energy ΔG for the edge-to-face π-π interaction in complex 1 was determined to be 1.4±0.8 kJ mol−1.

    26. μ3-Imido-Functionalized Chevrel–Sergent-Type Molecular Clusters, a New Class of Inorganic–Organic Hybrid Compounds: Preparations and Alkylation Reactions (pages 1544–1547)

      Dr. Santiago Uriel, Dr. Kamal Boubekeur, Prof. Dr. Patrick Batail and Dr. Jesús Orduna

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199615441

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      Under extremely mild conditions, [Re6Q5Cl9] ions (Q [DOUBLE BOND] S, Se) react with bis(trimethylsilyl)amine derivatives to give clusters of the type [Re6Q53-NSiMe3)Cl8]2− (shown on the right). These are isostructural and isoelectronic with the Chevrel–Sergent cluster cores [Mo6Q8]4−. The μ3-imido-functionalized clusters react with electrophiles and thus offer opportunities to extend the chemistry of genuine inorganic–organic hybrid compounds.

    27. Octakis(3,4-dimethylphenylthio)naphthalene: A Designed Spider Host of Unparalled Versatility (pages 1547–1549)

      Dr. Gary A. Downing, Dr. Christopher S. Frampton, James H. Gall and Dr. David D. MacNicol

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199615471

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      Nanoscale cavities with T symmetry capable of accommodating such diverse species as S[DOUBLE BOND]CCl2, PbEt4, and C60 are formed by the designed title compound. The adducts crystallize, uniquely for a purely organic system, in the cubic space group Pn¯3. The crystal structure of the title compound in its PbEt4 clathrate is shown on the right.

    28. Synthesis and Structure of ortho-Phenylenezinc (pages 1550–1552)

      Drs. Marcel Schreuder Goedheijt, Ing. Tom Nijbacker, Dr. Otto S. Akkerman, Prof. Dr. Friedrich Bickelhaupt, Drs. Nora Veldman and Dr. Anthony L. Spek

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199615501

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      Dimeric in the crystal and trimeric in THF solution—this remarkable phenomenon is shown by ortho-phenylenezinc, which can be obtained from the analogous mercury compound and zinc. In solution the equilibrium shown below lies well to the right. The dimer probably crystallizes due to favorable packing effects.

    29. The [Mnmath image(μ-O)(μ-PhBO2)2]2+ Unit: A New Structural Model for Manganese-Containing Metalloproteins (pages 1552–1554)

      Ursula Bossek, Dipl.-Chem. Helga Hummel, Dr. Thomas Weyhermüller, Prof. Dr. Karl Wieghardt, Dr. Stephen Russell, Lodewijk van der Wolf and Dr. Uwe Kolb

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199615521

      By employing boronato instead of carboxylato bridges in the dication [Mnmath image(μ-O)-(μ-PhBO2)2L2]2+ (L = 1,4,7-trimethyl-1,4,7-triazacyclononane), a Mnmath image unit has been stabilized for the first time. Together with the di-μ-carboxylato-μ-oxodimanganese complexes of analogous structure, there is now an “isostructural series” available containing Mnmath image, MnIIMnIII, Mnmath image, MnIIIMnIV, Mnmath image units. The Mn K-edge energy of the corresponding complexes increases linearly with increasing oxidation level. This is of importance for EXAFS investigations of metalloproteins containing manganese.

    30. Screw-Sense-Selective Polymerization of Isocyanides by Dinuclear μ-Ethynediyl Complexes (pages 1554–1556)

      Fumie Takei, Koichi Yanai, Dr. Kiyotaka Onitsuka and Prof. Dr. Shigetoshi Takahashi

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199615541

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      Single-handed helical polymers of the type 2 are the products of the screw-sense-selective polymerization of achiral isocyanides ArNC initiated by the helical oligomer complexes 1. The latter are accessible from μ-ethynediyl-bridged dinuclear Pd,Pt complexes by reaction with 3-CNC6H4CO2R* (R* = (+)- and (-)-menthyl).

    31. [2.2.2.2]Metacyclophane-1,9,17,25-tetrayne (pages 1556–1558)

      Dr. Takeshi Kawase, Noriko Ueda, Dipl.-Chem. Hossein Reza Darabi and Prof. Dr. Masaji Oda

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199615561

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      The smallest [2n]metacyclophan-n-yne known to date is the title compound 1. It was synthesized from the precursor tetraenes by bromination/dehydrobromination and is stable at room temperature. According to an X-ray structure analysis, 1 is nearly planar and the alkyne units are slightly bent (167.7–169.9°).

    32. Carbanion-Mediated Heterocyclizations: Regiospecific, General Route to Dibenzo- [b,e]phosphininones by Synthetic Anionic Equivalents of Friedel–Crafts Reactions and Remote Fries Rearrangement (pages 1558–1560)

      Dr. Matthew Gray, Brain J. Chapell, Dr. Nicholas J. Taylor and Prof. Victor Snieckus

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199615581

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      A new double anionic equivalent of the Friedel–Crafts reaction is observed upon treatment of the carbamoyltriarylphosphane oxide 1 with lithium diisopropylamide (LDA) to produce the phosphacycle 2. The scope of this and related reactions is delineated.

    33. The First Synthesis of Enantiopure (–)- and (+)-Isoterrein from Optically Inactive meso-Tartaric Acid (pages 1560–1562)

      Prof. Dr. Marian Mikołajczyk, Maciej Mikina, Dr. Michał W. Wieczorek and Dr. Jarosław Błaszczyk

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199615601

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      The complete desymmetrization of optically inactive meso-tartaric acid with (+)-camphor in the presence of trimethyl orthoformate is the key to the synthesis of both enantiomers of the cyclopentenoid isoterrein in enantiomerically pure form.

    34. Alkylation of 1-Naphthol with Alcohols over an Iron Oxide Catalyst (pages 1562–1565)

      Hanna Grabowska, Dr. Włodzimierz Miśta, Dr. Ludwik Syper, Prof. Dr. Józef Wrzyszcz and Dr. Mirosław Zawadzki

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199615621

      High yields and selectivities are achieved for the alkylation of 1-naphthol with alcohols in the presence of an iron catalyst in a continuous gas-phase process. The resulting 2-alkyl-1-naphthols can be easily separated from the product mixture. This opens up new possibilities for the synthesis of important industrial intermediates.

    35. Intermolecular Carbene–Carbene Coupling of a Nucleophilic Vinylidene and an Electrophilic 1-Methoxyethylidene Ligand (pages 1565–1567)

      Priv.-Doz. Dr. Rüdiger Beckhaus, Dipl.-Chem. Jürgen Oster, Dr. Rhett Kempe and Dr. Anke Spannenberg

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199615651

      Thumbnail image of graphical abstract

      The first example of an intermolecular carbene–carbene coupling reaction between a Fischer and a Schrock carbene ligand is achieved by coupling of the vinylidene fragment in 1 with the methoxyethylidene ligand in 2. In the resulting red titanacyclic chromium carbene complex 3 the chromium is coordinated in such a way by the methoxy substituent that the bicyclic framework is virtually planar.

    36. Epothilone A and B—Novel 16-Membered Macrolides with Cytotoxic Activity: Isolation, Crystal Structure, and Conformation in Solution (pages 1567–1569)

      Prof. Dr. Gerhard Höfle, Dr. Norbert Bedorf, Ing. Heinrich Steinmetz, Prof. Dr. Dietmar Schomburg, Dr. Klaus Gerth and Prof. Dr. Hans Reichenbach

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199615671

      Thumbnail image of graphical abstract

      How similar must a compound be to taxol in order to displace it from its binding site on microtubules? The microbial secondary metabolites epothilones A (1a) and B (1b) provide an answer to this question. These comparatively small, simply constructed, and highly cytotoxic macrolides surprisingly show no similarity to taxol, according to X-ray and NMR spectroscopic results.

    37. A Short Enantioselective Synthesis of Carbanucleosides (pages 1569–1572)

      Prof. Dr. Barry M. Trost, Dr. Robert Madsen, Dr. Simon G. Guile and Andrew E. H. Elia

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199615691

      Thumbnail image of graphical abstract

      Surprisingly, purines, unlike other nucleophiles, affect the enantioselectivity of the Pd-catalyzed desymmetrization of cis-3,5-diacyloxycyclopent-1-enes 1, even though they are formally not involved in the enantiodiscriminating step. Under suitable conditions this influence can be minimized. From 2, the alkylated adenine and analogues 3 can be obtained, and the latter can be employed in the short asymmetric syntheses of antiviral agents (–)-carbovir and (–)-aristeromycin. X [DOUBLE BOND] PhCO2; Y [DOUBLE BOND] OCONPh2, NH2, Cl; Z [DOUBLE BOND] H, NH2, NHAc; L* [DOUBLE BOND] chiral ligand.

    38. Directed Synthesis of Nonsymmetrical Bis-Steroidal Pyrazines and the First Biologically Active Cephalostatin Analogues (pages 1572–1574)

      Dipl.-Chem. Michael Drögemüller, Dipl.-Chem. Rolf Jautelat and Prof. Dr. Ekkehard Winterfeldt

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199615721

      Thumbnail image of graphical abstract

      Thermolysis of vinylazides affords azirines that can be captured in situ with enamino ketones. This reaction sequence (see below) was developed into a new general method for the preparation of nonsymmetrical pyrazines and applied to the synthesis of cephalostatin analogues with high biological activity.

  4. Book Reviews

    1. Top of page
    2. Reviews
    3. Highlights
    4. Communications
    5. Book Reviews
    1. Book Review: Les secrets de la casserole. By H. This (pages 1575–1577)

      Peter Weyerstahl

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199615751

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