Angewandte Chemie International Edition in English

Cover image for Vol. 33 Issue 23‐24

January 3, 1995

Volume 33, Issue 23-24

Pages 2353–2543

Currently known as: Angewandte Chemie International Edition

    1. Cover Picture (Angew. Chem. Int. Ed. Engl. 23/24/1994)

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.199423511

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      The cover picture shows Emil Fischer in his Berlin laboratory around 1910 and points to the unifying theme of several articles in this issue—the 100th anniversary of Fischer's lock-and-key principle. To mark this occasion a symposium took place in Mainz, Germany, last August with the title “Supramolecular Chemistry: 100 Years Schloss-Schlüssel-Prinzip”. A. Eschenmoser's introductory remarks from this conference, F. W. Lichtenthaler's tribute to Emil Fischer, and D. E. Koshland's lecture on the extension of Fischer's principle to the theory of induced fit are presented here.

  1. Reviews

    1. Top of page
    2. Reviews
    3. Highlights
    4. Communications
    5. New Books
    6. Author Index
    7. Subject Index
    1. One Hundred Years Lock-and-Key Principle (page 2363)

      Prof. Dr. Albert Eschenmoser

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.199423631

      Emil Fischer and supramolecular chemistry: The link between the discoverer of the lock-and-key concept and major aspects of this new branch of chemistry is tracked down by A. Eschenmoser in his introductory comments at a symposium in Mainz, Germany, in August 1994. He also comments on the two fundamental selection types—postsynthesis selection and presynthesis selection, or in other words, discovery and design.

    2. 100 Years “Schlüssel-Schloss-Prinzip”: What Made Emil Fischer Use this Analogy? (pages 2364–2374)

      Prof. Dr. Frieder W. Lichtenthaler

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.199423641

      “To use a picture I would like to say that enzyme and glucoside have to fit together like lock and key in order to exert a chemical effect on each other.” These words were used in 1894 to describe what has become one of the most fertile concepts not only in organic chemistry, but also in biology and medicine. To commemorate the hundredth anniversary F. W. Lichtenthaler gives an account of how Emil Fischer was led to this analogy and how avidly it was adopted by others, yet how cautiously it was applied by its initiator.

    3. The Key–Lock Theory and the Induced Fit Theory (pages 2375–2378)

      Prof. Dr. Daniel E. Koshland Jr.

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.199423751

      As a glove changes shape when a hand slips into it, so an enzyme changes its conformation on binding a ligand. This theory of induced fit extends the lock-and-key principle that Emil Fischer proposed exactly 100 years ago. The new theory proposed by D. E. Koshland, Jr. in 1958 allows one to explain regulation and cooperative effects, and adds some new specificity principles as well.

    4. Fine Feathers Make Fine Birds: The Heck Reaction in Modern Garb (pages 2379–2411)

      Prof. Dr. Armin de Meijere and Dr. Frank E. Meyer

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.199423791

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      An almost forgotten method has turned into a creative answer to new questions in synthesis. In the past few years the palladium-catalyzed coupling of aryl and alkenyl halides with alkenes, known as the Heck reaction, and a series of related C[BOND]C bond forming reactions have gained a secure position in the organic chemist's arsenal of methods. These reactions can be conducted with chemo-, regio-, diastereo-, and even enantioselectivity, and are pivotal components of modern cascade reactions. Open-chain precursors such as 1 may thus be used to prepare impressively complex oligo-cycles like 2. R = CO2Me.

  2. Highlights

    1. Top of page
    2. Reviews
    3. Highlights
    4. Communications
    5. New Books
    6. Author Index
    7. Subject Index
    1. Dendrimers: From Generations and Functional Groups to Functions (pages 2413–2420)

      Dipl.-Chem. Jörg Issberner, Dr. Rolf Moors and Prof. Dr. Fritz Vögtle

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.199424131

      Not just the size but also the multiplication of functions possible through branching is at the forefront of dendrimer chemistry. Owing to the numerous recent key publications by Newkome, Fréchet, Moore, Majoral, Meijer, and others, this Highlight has the dimensions of a minireview.

  3. Communications

    1. Top of page
    2. Reviews
    3. Highlights
    4. Communications
    5. New Books
    6. Author Index
    7. Subject Index
    1. Palladacycles as Intermediates for Selective Dialkylation of Arenes and Subsequent Fragmentation (pages 2421–2422)

      Prof. Marta Catellani and Dr. Maria Chiara Fagnola

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.199424211

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      Palladacycles like 1 undergo spontaneous rupture of the C–C bond between the aliphatic and aromatic parts of the norbornyl-phenyl ligand after selective meta-dialkylation of the arene ring through PdIV intermediates like 2. This reaction proceeds smoothly without β-H elimination with alkyl and benzyl halides RX.

    2. Diastereomerically Pure Mannich Bases from the Addition of Enamines to Ternary Iminium Salts (pages 2422–2423)

      Prof. Dr. Nikolaus Risch and Dipl.-Chem. Michael Arend

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.199424221

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      Very high yields and diastereoselectivities, mild reaction conditions, a straightforward experimental procedure, and cheap starting materials—these are the advantages offered by the reaction of (E)-enamines 1 with iminium salts 2 to give the Mannich bases 3. Since Mannich bases are important synthetic building blocks for Pharmaceuticals and natural products, this reaction will surely prove to be extremely useful.

    3. Ladder Polymers with a Heteroacene Skeleton (pages 2424–2426)

      Dipl.-Chem. Torsten Freund, Dr. Ullrich Scherf and Prof. Dr. Klaus Müllen

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.199424241

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      High molecular mass, uniform structure, and complete solubility characterize the novel ladder polymers 1. The formation of dication 2 from a model analogue of 1 by oxidation with 2,3-dichloro-5,6-dicyanobenzoquinone (DDQ) and subsequent dehydration with trifluoromethanesulfonic acid reveals that 1 is a potent precursor for the preparation of heteroanalogous, ionic poly[n]acenes. R1 = p-C6H4-n-C10H21, R2 = p-C6H4rBu; counterion CF3SOmath image.

    4. Thermally Induced Ring Cleavage of a 2H-1,2-Azaphosphirene Tungsten Complex (pages 2427–2428)

      Dr. Rainer Streubel, Dipl.-Chem. Annette Kusenberg, Dipl.-Chem. Jörg Jeske and Prof. Dr. Peter G. Jones

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.199424271

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      Surprisingly low thermal stability in solution is displayed by the 2H-1,2-azaphosphirene tungsten complex 1; acetylene derivatives and benzaldehyde were used to trap an intermediate phosphanediyl tungsten complex formed from 1. The reaction of 1 with benzaldehyde provides a new, diastereoselective route to oxaphosphirane tungsten complexes.

    5. Porphyrin–Quinone Cyclophanes with Gradually Varied Donor–Acceptor Distances (pages 2428–2431)

      Prof. Dr. Heinz A. Staab, Dr. Ralf Hauck and Dr. Achim Feurer

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.199424281

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      How does the rate of electron transfer between the quinone and porphyrin units in cyclophanes of type 1 vary with distance? H. A. Staab et al. report here on the synthesis and properties of cyclophanes with benzene, naphthalene (1), and anthracene spacers, which were examined by spectroscopy, X-ray structure analysis, and molecular dynamics calculations.

    6. Excited-State Carbon Acids: Theoretical Studies of Suberene and Cycloheptatriene (pages 2431–2433)

      Dipl.-Chem. Hans-Martin Steuhl and Prof. Dr. Martin Klessinger

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.199424311

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      Hydrogen shift and ring closure instead of deprotonation: Cycloheptatriene (2) does not show the photoreactivity expected from MO considerations, in contrast with the dibenzo derivative 1. Semiempirical calculations trace this difference to the crossing of states on relaxation of the excited state of 2.

    7. “Free” [Fe(tpp)]+ Cation: A New Concept in the Search for the Least Coordinating Anion (pages 2433–2434)

      Dr. Zuowei Xie, Prof. Robert Bau and Prof. Christopher A. Reed

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.199424331

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      Ligand or solvate? This question is raised by the arrangement of the cation and two p-xylene solvent molecules in the crystal structure of 1 (shown on the right). Complex 1, which provides the first example of a [Fe(tpp)]+ cation not coordinated by the anion, shows that this question cannot be answered definitively, and introduces a new strategy for preparing weakly coordinating anions. tpp = tetraphenylporphyrinate.

      • equation image
    8. [(Cp**CoH)2-μ-{η22-cis-μ-[(C2H5)2Al–CH = CH–Al(C2H5)2]}] and [{Cp*2-C2H4)CoAl(C2H5)}2]: Synthesis and Structure of Unusual Co–Al Cluster Compounds (pages 2435–2437)

      Priv.-Doz. Dr. Jörg J. Schneider, Prof. Dr. Carl Krüger, Dr. Matthias Nolte, Dipl.-Chem. Ingo Abraham, Dr. Teja S. Ertel and Prof. Dr. Helmut Bertagnolli

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.199424351

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      How many metal atoms can coordinate to a C[DOUBLE BOND]C unit? The answer for Co–Al clusters 1 (R = Me) and 2 (R = Et), the first η-η22-bridged dialumin-ioethene clusters, is “four”. The complexes are formed in about 30% yield on treatment of [Cp+2-ethene)2Co] (Cp+ = C5Me5, C5Me4Et) with AlEt2H.

    9. Antenna Effect in Multichromophoric Cyclodextrins (pages 2438–2439)

      Prof. Dr. Bernard Valeur, Dr. Elisabeth Bardez, Prof. Dr. Jean-Marie Lehn, Dr. Ludovic Jullien and Dr. Josette Canceill

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.199424381

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      A water-soluble β-cyclodextrin bearing seven naphthoate chromophores forms a very stable 1:1 inclusion complex (shown right) with a merocyanine dye, which mimics the antenna effect in photosynthetic units. The energy transfer from the naphthoate chromophores to the merocyanine is shown to take place with 100 % efficiency.

    10. Platinum–Iron Silylene Complexes and Metal-Promoted Substituent Exchange between Si(NMe2)3 and P(OEt)3 Ligands (pages 2440–2442)

      Dr. Ulf Bodensieck, Dr. Pierre Braunstein, Thierry Faure, Dr. Michael Knorr, Christine Stern and Dr. Werner Deck

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.199424401

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      The silylene complexes 1 are stabilized by the electron-deficient metal fragment PtL2 rather than by a more usual electron-donating group. The base-stabilized silylene complex 2 is formed in the reaction of [Fe(CO)4{P(OEt)3}] with HSi(NMe2)3 as a result of an unprecedented exchange of OEt and NMe2 ligand substituents.

    11. The Crystal Structures of Base-Free, Monomeric Arylcopper(I) and Arylsilver(I) Compounds; Two Cases of Mistaken Identity? (pages 2443–2445)

      Prof. Arne Haaland, Dr. Kristin Rypdal, Hans Peter Verne, Dipl.-Chem. Wolfgang Scherer and Dr. Werner Richard Thiel

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.199424431

      New evidence suggests that the monomeric aryl metal compounds 2,4,6-Ph3C6H2M (M = Cu, Ag) may be mixtures of 2,4,6-Ph3C6H2M and 2,4,6-Ph3C6H2Br or merely the aryl bromide. Although the aryl metal compounds appeared to be well characterized in 1988 by spectroscopic and X-ray crystallographic methods, doubts arising from theoretical considerations—in particular C[BOND]Cu and C[BOND]Ag distances of presumably the same length—led to reexamination of the X-ray data.

    12. Synthesis of Oxa- and Azapalladacycles from Organostannanes (pages 2445–2447)

      Diego J. Cárdenas, Cristina Mateo and Prof. Antonio M. Echavarren

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.199424451

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      An intramolecular Pd–C coupling reaction yields the oxapalladacycle 1. This is the first time that the transmetalation intermediate in the Stille coupling reaction has been isolated. Complexes of type 1 react readily with alkyl, allyl, benzyl, and acyl halides to form aryl-carbon bonds. This reaction can be extended to the preparation of substituted derivatives of 1 and the aza analogue 2.

    13. A Regioselective Palladium-Catalyzed Reduction of 3,3-Heterobimetalated Allylic Acetates— Synthesis and Reactivity of Allylic Bimetallic Compounds (pages 2448–2450)

      Prof. Mark Lautens and Patrick H. M. Delanghe

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.199424481

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      Selective reaction of one of two C[BOND]Si bonds in 1 with octanal yields 2. The disilyl compound 1 and also silylstannyl compounds, useful reagents in organic synthesis, could be prepared regioselectively (>99:1) by hydride reduction of allylic acetates.

    14. Doubly Lithiated Oligosilanes: Synthesis and Structure of the First Vicinal Dilithiodisilane (pages 2450–2452)

      Dr. Johannes Belzner, Dipl.-Chem. Uwe Dehnert and Priv.-Doz. Dr. Dietmar Stalke

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.199424501

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      Reaction of cyclotrisilane 1 with lithium yields, depending on the reaction conditions, either the trisilane 2 lithiated at the terminal positions or the vicinal dilithiodisilane 3. These silanes are the first examples of this class of compounds and the first to be characterized by X-ray structure analysis. Ar = 2-(Me2NCH2)C6H4.

    15. A Chiral Lewis Acid with Two “Metal” Centers: Cooperative Binding of Two Amine Molecules to a Chiral Diboronic Ester (pages 2452–2454)

      Dr. Kyoko Nozaki, Masanori Yoshida and Prof. Dr. Hidemasa Takaya

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.199424521

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      Lewis acid/Lewis base interactions and hydrogen bonds account for the cooperative binding of two molecules of benzylamine to the chiral diboronate 1. Exclusive formation of the 1:2 complex of the Lewis acid 1 and benzylamine is evident in the NMR spectrum, which implies that the binding of the first molecule provides a suitable binding site for the second amine molecule.

    16. A Short Route to [3-15N]-3′-Azido-3′-deoxythymidine (N3-Labeled AZT) via 3-Nitro-AZT (pages 2454–2455)

      Xavier Ariza, Dr. Valentí Bou, Prof. Jaume Vilarrasa, Dr. Valya Tereshko and Dr. J. L. Campos

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.199424541

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      Nucleosides with appropriate isotopic labels are crucial for studies of nucleic acid structures, drug-binding phenomena, and related molecular recognition processes. A mild and general approach for the introduction of 15N at the 3-position of pyrimidine nucleosides is illustrated by the conversion of AZT to [3-15N]-AZT 1 (* = isotopically labeled).

    17. A Water-Soluble “Bear Trap” Exhibiting Strong Anion Complexation Properties (pages 2456–2457)

      Dr. Jonathan W. Steed, Dr. Ravindra K. Juneja and Prof. Dr. Jerry L. Atwood

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.199424561

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      Complexation with (arene)ruthenium(II) units converts calix-arenes into suitable host compounds for anions. The hexacat-ion composed of calixarene 1 with four (p-cymene)Ru fragments bound to the phenyl groups can complex a BFmath image ion, as demonstrated by X-ray structure analysis. The BFmath image ion is found deep within the host cavity.

    18. Expeditious Synthesis of a Novel C3-Symmetric Receptor that Binds Peptides Sequence-Selectively (pages 2458–2460)

      Seung Soo Yoon and Prof. W. Clark Still

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.199424581

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      Over 50 000 tripeptides in one go were tested for their binding properties towards receptor 1 (R = CO(CH2)2CO2Dye). The tripeptide library was synthesized on polystyrene beads (one compound per bead). These were then mixed with the colored receptor. The few beads that changed color were selected for characterization. Considering its remarkably high sequence selectivity and straightforward synthesis, 1 might well prove to be most useful in the areas of separation and analysis.

    19. Single-Step Six-Electron Transfer in a Heptanuclear Complex: Isolation of Both Redox Forms (pages 2460–2462)

      Dr. Jean-Luc Fillaut, Prof. Didier Astruc and Dr. Jorge Linares

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.199424601

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      The cationic heptanuclear hexaferrocenyl compound 1 can be synthesized efficiently (as the orange-red PF6 salt) by the FeCp+-induced hexaferrocenylalkylation of the hexamethylbenzene ligand of [FeCp(C6Me6)]PF6. The 6e oxidation of 1 to the heptacation and the 1 e reduction to the neutral compound are supported by cyclic voltammetry and Mössbauer spectroscopy.

    20. Fullerene–Oligonucleotide Conjugates: Photoinduced Sequence-Specific DNA Cleavage (pages 2462–2465)

      Dr. Alexandre S. Boutorine, Dr. Masashi Takasugi, Prof. Claude Hélène, Dr. Hidetoshi Tokuyama, Hiroyuki Isobe and Prof. Eiichi Nakamura

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.199424621

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      The guanine-specific cleavage of oligonucleotides is achieved with the conjugate 1, which contains a fullerene tethered to a tetradecadeoxyribonucleotide Nu(pNu)n. This conjugate was able to form a duplex with a complementary oligonucleotide, and triplexes with appropriate double-stranded oligonucleotides. Irradiation of the complexes leads to site-specfic cleavage of the target sequences—probably through the action of singlet oxygen.

    21. Bis(pentamethylcyclopentadienyl)(η3-trimethylenemethane)zirconium: A New Mode of Bonding for the Trimethylenemethane Ligand (pages 2465–2466)

      Prof. Dr. Gerhard E. Herberich, Dr. Carsten Kreuder and Dr. Ulli Englert

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.199424651

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      A bent metallocene with a side-on η3-bound trimethylenemethane (tmm) ligand is observed in the crystal structure of the title compound 1 (shown on the right). The Zr[BOND]Cl and Zr[BOND]C2 bond lengths indicate that two strong σ bonds link Zr to the terminal C atoms of the tmm ligand. The distance between Zr and the central atom C 3 is typical for a weak σ bond. Reactions of 1 with reagents that contain polar double bonds, for example methyl formate and tert-butyl isocyanate, yield insertion products with six-membered rings.

    22. Total Synthesis of Soraphen A (pages 2466–2468)

      Dr. Stephan Abel, Dominik Faber, Dr. Ottmar Hüter and Prof. Dr. Bernd Giese

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.199424661

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      From the simple building block D-glucose, soraphen 1 a (R [DOUBLE BOND] CH3) and the derivative 1 b (R [DOUBLE BOND] H) have been prepared. Compound la is the parent compound of a new class of eighteen-membered macrolides with interesting biological properties. One of the key steps of the total synthesis was the selective methylation of 1 b yielding 1 a.

    23. Novel Bimetallic Model System for Cytochrome P450: Effect of Membrane Environment on the Catalytic Oxidation (pages 2468–2470)

      Dipl.-Chem. Albertus P. H. J. Schenning, Dominicus H. W. Hubert, Dr. Jan H. van Esch, Dr. Martinus C. Feiters and Prof. Dr. Roeland J. M. Nolte

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.199424681

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      A novel membrane-bound cytochrome P450 mimic (shown schematically below, 1: a RhIII complex, 2: a manganoporphyrin) catalyzes the epoxidation of alkenes with dioxygen. The turnover numbers achieved with this catalyst are in the same range as those obtained with the natural enzyme.

    24. 1,4-Didehydrobutadiene: The Intermediate in a New Class of Thermally Induced Intramolecular Alkyne Couplings (pages 2470–2472)

      Prof. Dr. Rolf Gleiter and Dipl.-Chem. Joachim Ritter

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.199424701

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      Nonconjugated diynes can also form diradicals by cyclization. Thermolysis of 1 (R = iPr) initially yields 1,4-didehydrobutadiene 2, which reacts with a hydrogen donor R'H (e.g. solvent) to give the trapping products 3 and 4. The reactivity of 1 is explained by the electronic activation of the alkyne units by the N atoms, a sufficiently small separation of the C atoms to be linked, and a gain in energy upon formation of the σ and π bonds.

    25. Novel RhI Piano-Stool Complexes with New Hemilabile Ligands Ligating through Phosphane and Arene Groups: Synthesis, Characterization, and Reactivity (pages 2473–2475)

      Elizabeth T. Singewald, Prof. Chad A. Mirkin, Allison D. Levy and Charlotte L. Stern

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.199424731

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      Which arene ligand coordinates? An intramolecular exchange previously unknown for RhI complexes in which the phenyl ether moieties bind alternately in an η6 fashion to the Rh1 center (in 1 and 1' on the right) is observed by two-dimensional 1HNMR exchange spectroscopy. This exchange of the aryl ether-phosphane ligands probably proceeds via intermediate 2 and therefore cannot be detected when the O atoms are exchanged for CH2 groups.

    26. Homogeneous Catalytic Oxidation of Arenes and a New Synthesis of Vitamin K3 (pages 2475–2477)

      Prof. Dr. Waldemar Adam, Dr. Jianhua Lin, Dr. Chantu R. Saha-Möller, Prof. Dr. Wolfgang A. Herrmann, Dr. Richard W. Fischer and João D. G. Correia

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.199424751

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      Methyltrioxorhenium(VII)-catalyzed oxidation of 2-methylnaphthalene (1) with hydrogen peroxide leads to vitamin K3 (2) in good yield and high regioselectivity. The currently employed industrial synthesis of 2 with chromic acid produces 18 kg of chromium-containing waste per kg of product.

    27. Enediyne Quinone Imines: Truncated, Biologically Active Dynemicin Congeners (pages 2477–2479)

      Matthew D. Shair, Prof. Samuel J. Danishefsky, Taeyoung Yoon and Ting-Chao Chou

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.199424771

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      An intermediate in the total synthesis of dynemicin A, quinone imine 1 can be used as a dienophile. But 1 is also a potent cytotoxic agent against human cancer cell lines since it is able to cleave DNA. In vitro and in vivo studies showed that 1 is more effective than two frequently applied antitumor drugs. Quinone imine 1 was synthesized by the rapid oxidation of a fleeting hydroisoquinone intermediate.

    28. Sugar Calixarenes: Preparation of Calix[4]arenes Substituted at the Lower and Upper Rims with O-Glycosyl Groups (pages 2479–2481)

      Dr. Alberto Marra, Dr. Marie-Christine Scherrmann, Prof. Alessandro Dondoni, Prof. Rocco Ungaro, Dr. Alessandro Casnati and Dr. Patrizia Minari

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.199424791

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      A chiral hydrophilic environment is created at either rim of calix[4]arene by the synthesis of glycosyl derivatives such as the water-soluble tetragalactosyl calixarene 1. This derivative is potentially an attractive synthetic receptor for chiral recognition of polar organic molecules.

    29. [(CpNi)2(Cp*Al)2]: Cp*Al as a Bridging Two-Electron Ligand (pages 2482–2483)

      Dr. Carsten Dohmeier, Dr. Harald Krautscheid and Prof. Dr. Hansgeorg Schnöckel

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.199424821

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      A butterfly-shaped framework is observed for the Ni2Al2 unit in the title compound, which is synthesized from [(Cp*Al)4] and [Cp2Ni]. The planes of the Cp* ligands are nearly perpendicular to the planes of the Ni2Al triangles. The NiAl complex is diamagnetic, only slightly air- and moisture-sensitive, and remarkably stable.

    30. Mesoscopic Sheets of a Cyano-Bridged Cu[BOND]Ni Coordination Complex: Template Synthesis at the Interlayers of Cast Multibilayer Films (pages 2483–2485)

      Nobuo Kimizuka, Toyokazu Handa, Izumi Ichinose and Prof. Dr. Toyoki Kunitake

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.199424831

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      The integration of two different metals in a two-dimensional mesoscopic aggregate is possible by dipping a multibilayer film first in a solution of [Ni(CN)4]2− and then in a solution of Cu2+. The resulting aggregate, shown in an idealized structure on the right, displays anisotropic orientation similar to that of single crystals.

    31. Sterically Strained Porphyrins—Influence of Core Protonation and Peripheral Substitution on the Conformation of Tetra-meso-, Octa-β-, and Dodeca-Substituted Porphyrin Dications (pages 2485–2487)

      Dr. Mathias O. Senge, Timothy P. Forsyth, Liem T. Nguyen and Prof. Dr. Kevin M. Smith

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.199424851

      The saddle-shaped porphyrin with the largest deviation from planarity observed to date is found in the crystal structure of [H4obrtpp][CF3COO]2 · 0.5 CHCl3 (H2obrtpp = octabromotetraphenylporphyrin). The pyrrole rings in the porphyrin are twisted by 62° with respect to each other, and the β-pyrrole C atoms are displaced by over 1.5 Å from the mean plane of the porphyrin ring. This extreme distortion is caused by the bulky peripheral substituents on the porphyrin ring and the four protons at the core of the structure.

    32. Alternating Ferro- and Antiferromagnetic Interactions in a MnII Chain with Alternating End-On and End-to-End Bridging Azido Ligands (pages 2488–2489)

      Dr. Roberto Cortés, Dr. Luis Lezama, Prof. Teófilo Rojo, Prof. M. Isabel Arriortua, Dr. J. Luis Pizarro and Prof. Xavier Solans

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.199424881

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      Mn(ClO4)2 ·6H2O, 2,2'-bipyridine, and NaN3 were used to synthesize [Mn(N3)2-(bpy)]χ, the crystal structure of which (shown below) is characterized by alternating end-on and end-to-end bridging azido ligands. The existence of alternating ferro-and antiferromagnetic interactions between the S = 5/2 ions, as found previously only in copper(II) complexes, is suggested.

    33. Supramolecular Activation of para-Benzoquinone (pages 2489–2491)

      Paula A. Brooksby, Dr. A. James McQuillan, Duncan H. Purvis, Dr. Alan E. Rowan, Dr. Russell Walsh, Dr. Christopher A. Hunter and Richard J Shannon

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.199424891

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      Tetraamide hosts not only complex para-benzoquinone to form 1, they also activate the guest towards electrochemical reduction. The structure and redox properties of this system bear close similarity to those of the quinone binding domains of photosynthetic reaction centers.

    34. (H3N(CH2)6NH3)4 [W18P2O62] · 3H2O, a Microporous Solid from Dawson Anions and 1,6-Diaminohexane (pages 2491–2493)

      Dipl.-Chem. Markus Hölscher, Dr. Bodo Zibrowius, Prof. Wolfgang F. Hölderich and Dr. Ulli Englert

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.199424911

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      Almost rectangular cavities can be seen in the structure of the title compound (part of the crystal structure shown on the right), the first heteropolyoxo-tungstate with defined micropores. The compound was prepared in a hydrothermal reaction with W, WO3, H3PO4, H2O, and hexamethylenediamine. Potential applications of this compound in catalytic oxidations or as a support in shape-selective reactions must still be proven.

  4. New Books

    1. Top of page
    2. Reviews
    3. Highlights
    4. Communications
    5. New Books
    6. Author Index
    7. Subject Index
    1. New Books (Angew. Chem. Int. Ed. Engl. 23/24/1994) (page 2494)

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.199424941

  5. Author Index

    1. Top of page
    2. Reviews
    3. Highlights
    4. Communications
    5. New Books
    6. Author Index
    7. Subject Index
    1. Author Index [Angew. Chem. Int. Ed. Engl. 1994, 331] (pages 2503–2513)

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.199425031

  6. Subject Index

    1. Top of page
    2. Reviews
    3. Highlights
    4. Communications
    5. New Books
    6. Author Index
    7. Subject Index
    1. Subject Index [Angew. Chem. Int. Ed. Engl. 1994, 33] (pages 2515–2543)

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.199425151

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