Angewandte Chemie International Edition in English

Cover image for Vol. 35 Issue 1

January 19, 1996

Volume 35, Issue 1

Pages 3–111

Currently known as: Angewandte Chemie International Edition

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

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.199600011

      Thumbnail image of graphical abstract

      The cover picture shows a space-filling model of the anionic cesocene triple-decker complex [Cp3Cs2]. The Cs centers in this strongly bent molecule are highly ionic. The chemistry of anionic metallocenes of main group elements is a rapidly growing field and such metallocenes are structurally as well as theoretically of interest. Mixing cyclopentadienyl alkali metal compounds with cyclopentadienyl anions results in degradation of the CpMCpM polymer chains into smaller units such as [Cp2M] and [Cp3M2]. A structural comparison of these alkali metallocene complexes with the isovalent neutral alkaline earth metallocenes gives additional information on the still not well-understood bonding characteristics. The picture was painted by Peter Brinkmann, Universität Konstanz, using a technique that combines pastels and watercolors. Chemetall GmbH, Frankfurt/Main (Germany), is kindly acknowledged for providing the funding for the color print. Further details on the structure of this complex are reported by S. Harder and M. H. Prosenc on p. 97 ff.

  1. Reviews

    1. Top of page
    2. Reviews
    3. Highlights
    4. Communications
    5. Book Reviews
    1. Organic Chemistry on Solid Supports (pages 17–42)

      Prof. Dr. Jörg S. Früchtel and Prof. Dr. Günther Jung

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.199600171

      The advantages of solid-phase synthesis have been recognized by organic chemists, who have adapted numerous well-known reactions for application with immobilized substrates. For example, a polymeric support may act as a protecting group for one functional group of a compound while a second functional group is derivatized. In other applications combinatorial syntheses on supports provide access to libraries of nonpeptides from collections of building blocks. This strategy is essential for supplying new compounds for modern automated screening assays used in the search and optimization of lead structures for drugs.

    2. Copper—A “Modern” Bioelement (pages 43–60)

      Prof. Dr. Wolfgang Kaim and Dipl.-Chem. Jochen Rall

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.199600431

      Mutual stimulation of ideas in biochemistry, medical practice, and inorganic chemistry has led to the discovery of many molecular details of the biological functions of copper, an essential element in nature. Copper probably became significantly bioavailable only rather late in the evolution of life. This and the unique redox and coordination properties closely link the redox pair CuII/CuI with the metabolism of O2 and with radical ligands.

  2. Highlights

    1. Top of page
    2. Reviews
    3. Highlights
    4. Communications
    5. Book Reviews
    1. “New” Reagents for the “Old” Pinacol Coupling Reaction (pages 61–63)

      Dr. Thomas Wirth

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.199600611

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      Even 130 years after its discovery, the pinacol coupling [Eq. (a)] still has plenty of new variants. New reagents have been developed that are suitable not only for the elegant synthesis of 1,2-diols but also for the formation of amino alcohols. This powerful reaction has been used in numerous natural product syntheses.

    2. Selective Catalytic Reactions at the External Surface of Zeolite Crystals (pages 63–64)

      Dr.-Ing. Stefan Ernst

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.199600631

      The arrangement of the pore openings serves as a template for the positions of the branchings in the isomerization of n-alkanes—this is the explanation proposed by Martens et al. (Angew. Chem. Int. Ed. Engl.1995, 34, 2528) to rationalize their results in the isomerization of n-heptadecane on the zeolite ZSM-22. This reaction would thereby be the first example of key–lock catalysis on the external surface of a zeolite.

  3. Communications

    1. Top of page
    2. Reviews
    3. Highlights
    4. Communications
    5. Book Reviews
    1. Tetrasupersilyldiindium(In–In) and Tetrasupersilyldithallium(Tl[BOND]Tl): (tBu3Si)2M[BOND]M(SitBu3)2 (M = In, Tl) (pages 65–67)

      Prof. Dr. Nils Wiberg, Dipl.-Chem. Kerstin Amelunxen, Prof. Dr. Heinrich Nöth, Dr. Martin Schmidt and Dipl.-Chem. Holger Schwenk

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.199600651

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      Deep violet (tBu3Si)4In2 (1) and black-green (tBu3Si)4Tl2 (2) are formed from MBr and tBu3SiNa in THF at −78 °C [Eq. (a)]. The M atoms of 1 (decomp. 125 °C) and 2 (decomp. 52 °C) are each coordinated by two Si atoms and one M atom in a trigonal-planar fashion, and the two Si2MM planes are orthogonal.

    2. Synthesis and Structure of Seven-Coordinate Bismuth(V) Complexes with Benzenoid and Non-Benzenoid Arene Ligands: Tri(aryl)tropolonatobismuth(V) Complexes (pages 67–68)

      Dipl.-Chem. Uwe Dittes, Doz. Dr. Dr. Bernhard Klaus Keppler and Dr. Bernhard Nuber

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.199600671

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      Extremely air- and moisture-stable seven-coordinate BiV complexes 1 are obtained readily from di(acetato)tri(aryl)bismuth(v) and tropolone derivatives. The Bi atom in 1 resides in a distorted pentagonal-bipyramidal environment. Thus, stable BiV complexes are now available for biological and medicinal activity studies.

    3. Convenient New Synthesis of [7]Circulene (pages 69–70)

      Prof. Dr. Koji Yamamoto, Hiroyuki Sonobe, Dr. Hiroshi Matsubara, Dr. Masaaki Sato, Susumu Okamoto and Prof. Dr. Kazuo Kitaura

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.199600691

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      A remarkably simple synthesis of [7]circulene 1 via an ethano-bridged hexahelicene intermediate is described. Cyclic voltammetry reveals that 1 is easier to oxidize and reduce than coronene. The results of ab initio calculations for coronene, 1, and its radical ions are consistent with the experimental findings.

    4. 2-Nucleos-5′-O-yl-4H-1,3,2-benzodioxaphos-phinin-2-oxides—A New Concept for Lipophilic, Potential Prodrugs of Biologically Active Nucleoside Monophosphates (pages 70–72)

      Dr. Chris Meier

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.199600701

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      A nonenzymatic, hydrolytic tandem reaction selectively releases the 5′-phosphorylated derivatives of the antiviral active nucleoside analogues ddT and d4T from the nucleoside phosphotriesters 1 and 2. The hydrolysis of 1 and 2 can be controlled by varying the substituents X. Consequently, compounds of type 1 and 2 should, in principle, be suitable prodrugs of phosphorylated nucleosides.

    5. Chiral Recognition of α-Amino Acid Derivatives with a Homooxacalix[3]arene: Construction of a Pseudo-C2-Symmetrical Compound from a C3-Symmetrical Macrocycle (pages 72–74)

      Koji Araki, Kousuke Inada and Prof. Seiji Shinkai

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.199600721

      Thumbnail image of graphical abstract

      The shoe fits! The association constants for the complexes formed from the chiral host compound (–)-anti-1MeBu2 [shown in Eq. (a)] and chiral alkylammonium ions such as L-phenylalanine ethyl ester are up to 6.7 times greater than those with the (+) isomer of the host. anti-1MeBu2 is prepared in two steps from the homoox-acalix[3]arene 1H3 [Eq.(a)].

    6. A Convergent, Enantioselective Total Synthesis of Hapalosin: A Drug with Multidrug-Resistance Reversing Activity (pages 74–76)

      Prof. Arun K. Ghosh, Wenming Liu, Yibo Xu and Zhidong Chen

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.199600741

      Thumbnail image of graphical abstract

      Tumor cells can develop resistance towards the drugs administered in chemotherapy. Hapalosin (1, R [DOUBLE BOND] H), a cyclodepsipeptide whose total synthesis has now been achieved, can inhibit this resistance. The constitution and configuration of the compound have been confirmed by its synthesis. It should now be possible to carry out detailed structure–function studies.

    7. Proton-Induced Switching of Electron Transfer Pathways in Dendrimer-Type Tetranuclear RuOs3 Complexes (pages 76–78)

      Prof. Masa-aki Haga, Md. Meser Ali and Prof. Ryuichi Arakawa

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.199600761

      Thumbnail image of graphical abstract

      Protonation and deprotonation of Brönsted basic sites in the tetranuclear RuOs3 complex shown schematically below results in switching between two oxidation patterns A and B. In the deprotonated RuIIIOsmath image complex obtained after one-electron oxidation, electron transfer from the peripheral OsII atoms to the central RuIII site is induced by the addition of protons. bpy = 2,2′-bipyridine, — = 2,2′-bis(benz-imidazol-2-yl)-4,4′-bipyridine.

    8. [N(CH3)4][Mn(N3)3]: A Compound with a Distorted Perovskite Structure through Azido Ligands (pages 78–80)

      Dr. Franz A. Mautner, Dr. Roberto Cortés, Dr. Luis Lezama and Prof. Teófilo Rojo

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.199600781

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      Manganese(II) nitrate and tetramethylammonium azide react to give the title compound in which the azido groups function as end-to-end bridging lig-ands in all spatial directions, and whose structure can be described as corresponding to a distorted perovskite (section of the structure shown on the right). At higher temperatures the compound undergoes a reversible phase transition to a pseudo-cubic phase.

    9. Formation of a Zirconocene–Betaine System by Electrophilic Substitution with B(C6F5)3 at a Cyclopentadienyl Ligand (pages 80–82)

      Dipl.-Chem. Johannes Ruwwe, Prof. Dr. Gerhard Erker and Dr. Roland Fröhlich

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.199600801

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      A potential starting material for the development of new catalysts, the zirconocene-betaine complex 3 was obtained from the zirconocene derivative 1 by func-tionalization of a Cp ligand (via 2). Analogous reactions with metallocenes containing titanium, zirconium, or hafnium are relatively unexplored. R[DOUBLE BOND]CMe[DOUBLE BOND]CMe[BOND]CMe[DOUBLE BOND]CHMe.

    10. Heterocumulenes: Reaction of C3O2 with Ketenylidenetriphenylphosphorane; Synthesis and Structure of a Spirobis(cyclobutanedione) (pages 83–85)

      Dr. Luciano Pandolfo, Dr. Giacomo Facchin, Dr. Roberta Bertani, Dr. Paolo Ganis and Dr. Giovanni Valle

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.199600831

      Thumbnail image of graphical abstract

      Quantitatively and in one step, the heterocumulenes O[DOUBLE BOND]C[DOUBLE BOND]C[DOUBLE BOND]C[DOUBLE BOND]O and Ph3 P[DOUBLE BOND]C[DOUBLE BOND]C[DOUBLE BOND]O form spirobis(cyclobutanedione) A in a double [2 + 2]cyclo-addition. The bis(ylidic) structure was confirmed by spectroscopy and X-ray crystallography.

    11. The Organometallic Chemistry of Zirconium on an Oxo Surface Provided by p-tert-Butylcalix[4]arene (pages 85–87)

      Luca Giannini, Dr. Euro Solari, Dr. Antonio Zanotti-Gerosa, Prof. Dr. Carlo Floriani, Prof. Dr. Angiola Chiesi-Villa and Dr. Corrado Rizzoli

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.199600851

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      Distorted into an ellipse, the calix[4]arene units in novel complexes of type 1 bind the hexacoordinate Zr center. In complex 1, which is prepared in two steps by reaction of BuLi, calixarene, and ZrCl4, the ZrCl2 unit can be replaced by Zr(alkyl)2, Zr(alkyl), Zr(butadiene), and Zr(ketone) moieties. These reactions provide access to organometallic fragments bonded to a polyoxo matrix.

    12. Synthesis of Fucopeptides as Sialyl Lewisx Mimetics (pages 88–90)

      Prof. Dr. Shih-Hsiung Wu, Dr. Makoto Shimazaki, Dipl.-Chem. Chun-Cheng Lin, Dr. Lei Qiao, Dr. Wilna J. Moree, Gabriele Weitz-Schmidt and Prof. Dr. Chi-Huey Wong

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.199600881

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      The same biological activity as the antigen determinant sialyl Lewisx was shown by the fucopeptide 1 in a binding assay with E-selectin. In the design of this mimetic the type and spatial arrangement of the functional groups essential for the interaction between sialyl Lewisx and E-selectin were considered. Fucopeptide 1, which may have potential as an antiinflammatory agent, was synthesized from L-fucose. L-threonine, (2S,3R)-2-amino-3,4-dihydroxy-butyric acid, and glutarate.

    13. β,β-Dimethylcyclolanthionines, New Constrained Dipeptide Mimetics: Synthesis, Crystal Structures, and Conformational Studies (pages 90–92)

      Hui Shao, Chang-Woo Lee, Qin Zhu, Peter Gantzel and Prof. Murray Goodman

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.199600901

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      The labile disulfide bridge between cysteine residues in naturally occurring peptides can be replaced by lanthionine, as demonstrated by the synthesis of conformation-ally constrained dipeptide mimetics (see below) based on β,β-dimethylcyclolanthio-nines. Their structural features indicate that they represent a novel family of peptidomimetics.

    14. A Sequential Electron-Transfer Relay in Diporphyrin–Porphyrin–Pyromellitimide Triads Analogous to That in the Photosynthetic Reaction Center (pages 92–95)

      Prof. Atsuhiro Osuka, Dr. Satoshi Nakajima, Prof. Tadashi Okada, Seiji Taniguchi, Dr. Koichi Nozaki, Prof. Takeshi Ohno, Prof. Iwao Yamazaki, Dr. Yoshinobu Nishimura and Prof. Noboru Mataga

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.199600921

      Thumbnail image of graphical abstract

      Without a doubt, photochemically induced electron transfer in 1 proceeds stepwise. Triad 1 is one of the latest models of the photosynthetic reaction center. The rates of the individual steps in the electron transfer relay have been determined by ultra-fast laser spectroscopy.

    15. Cycloadditions of Ruthenium Alkylidyne Complexes with Carbonyl or Thiocarbonyl Compounds (pages 95–97)

      Dr. Robin B. Bedford, Dr. Anthony F. Hill, Dr. Andrew J. P. White and Dr. David J. Williams

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.199600951

      Thumbnail image of graphical abstract

      Electrophilic attack by the carbon atom of the heterocumulene at the ruthenium center characterizes the cycloadditions between the rutheni-um alkylidyne complex 1 and CO2, CS2, or MeNCS. One of the products, the thiobenzoyl complex 2. has been structurally characterized by X-ray diffraction.

    16. The Heaviest Alkali Metallocene: Structure of an Anionic Cesocene Triple-Decker (pages 97–99)

      Dr. Sjoerd Harder and Dipl.-Chem. Marc Heinrich Prosenc

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.199600971

      Thumbnail image of graphical abstract

      The strongly bent triple-decker structure shown on the right is exhibited by the anion in [Cp3Cs2][PPh4], which is obtained as a red crystalline compound by the reaction of CpCs with PPh4Cl. The coordination sphere of the Cs cation is filled by additional intermolecular interactions with neighboring [Cp3Cs2]+ ions and [PPh4] ions.

    17. On Ligand Design for Catalytic Outer Sphere Reactions: A Simple Asymmetric Synthesis of Vinylglycinol (pages 99–102)

      Prof. Barry M. Trost and Richard C. Bunt

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.199600991

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      A quantitative synthesis with an enantiomeric ratio of 99:1 has been achieved for the important building block vinylglycinol. The crucial concept lay in sculpting the chiral pocket in catalyst 1 by restricting bond rotations in its chiral-inducing ligand.

    18. O-Protonation at a Neutral Ditungsten Carbonyl Dimer to Give a Stable Hydroxycarbyne Complex (pages 102–104)

      Dr. M. Angeles Alvarez, Dr. Claudette Bois, Dr. M. Esther García, Prof. Dr. Victor Riera and Dr. Miguel A. Ruiz

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.199601021

      Thumbnail image of graphical abstract

      The reduction of a carbonyl to a methylidyne ligand in the reaction sequence below proceeds readily via the unsaturated hydroxycarbyne complex [W2(μ-COH)-(CO)2(μ-dppm)Cp2]+, the unexpected protonation product of a neutral carbonyl complex. dppm = Ph2PCH2PPh2.

    19. A New Multifunctional Heterobimetallic Asymmetric Catalyst for Michael Additions and Tandem Michael–Aldol Reactions (pages 104–106)

      Takayoshi Arai, Dr. Hiroaki Sasai, Kei-ichi Aoe, Kimio Okamura, Tadamasa Date and Prof. Dr. Masakatsu Shibasaki

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.199601041

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      Two types of metal are essential for some reactions! The first efficient catalyst for asymmetric tandem Michael – aldol reactions is the heter-obimetallic complex 1, which is easily prepared from LiAlH4 and (R)- 2,2′-dihydroxy-1,1′-binaphthyl. The cascade reaction of diethyl methylmalonate, cyclopentenone, and 3-phenylpropanal affords the three-component adduct 2 in 64% yield and 91 % ee.

    20. Enzymatic Synthesis of Peptides and Ras Lipopeptides Employing Choline Ester as a Solubilizing, Protecting, and Activating Group (pages 106–109)

      Dipl.-Chem. Michael Schelhaas, Dipl.-Chem. Simone Glomsda, Dr. Marion Hänsler, Prof. Hans-Dieter Jakubke and Prof. Herbert Waldmann

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.199601061

      Since it can be removed under extremely mild conditions and with complete selectivity by choline esterase, the solubilizing choline ester function is advantageous for high-yielding peptide syntheses. This enzyme-labile protecting group was employed in the synthesis of the S-palmitoylated and S-farnesylated C-terminal lipohexapeptide of the human N-Ras protein.

  4. Book Reviews

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