Angewandte Chemie International Edition in English

Cover image for Vol. 34 Issue 18

October 2, 1995

Volume 34, Issue 18

Pages 1913–2061

Currently known as: Angewandte Chemie International Edition

    1. Cover Picture (Angew. Chem. Int. Ed. Engl. 18/1995)

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199519111

      Thumbnail image of graphical abstract

      The cover picture shows a space-filling molecular model of the Ca2+ -mobilizing second messenger D-myo-inositol 1,4,5-trisphosphate superimposed on a sea urchin egg that has been injected with a [Ca2+]-dependent fluorescent indicator to depict concentrations of Ca2+ in pseudocolor. Fertilizing sperm bound to the egg at the bottom left triggered a Ca2+-concentration wave (green:[Ca2+] low–about 100nM, resting state; red: [Ca2+] high–several μM; yellow: intermediate range). The local increase of the Ca2+ concentration at the binding site propagates as a regenerative wave throughout the entire cell. Inositol 1,4,5-triphosphate is one of the intracellular messengers that orchestrate this wave. More about inositol mediated processes is reported on pp. 1933–1972 by B. V. L. Potter and D. Lampe. The authors thank Dr. A. Galione, Oxford University, for the fluorescence imaging data, and Mr. K. Smith and Dr. A. S. Thompson, University of Bath, for molecular modeling.

  1. Reviews

    1. Top of page
    2. Reviews
    3. Highlights
    4. Correspondences
    5. Communications
    6. Book Reviews
    1. Chemistry of Inositol Lipid Mediated Cellular Signaling (pages 1933–1972)

      Prof. Dr. Barry V. L. Potter and Dr. Dethard Lampe

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199519331

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      A renaissance in inositol phosphate chemistry was initiated twelve years ago by the discovery of the role of myo-inositol 1,4,5-trisphosphate (1) as a second messenger. Since then, numerous methods for the synthesis of regiospecifically protected inositols and optically active inositol phosphate regioisomers and their analogues have been established with the intent of elucidating biological roles for the some of the vast array of naturally occurring inositol phosphates. The first pharmacological and biochemical agents are already available for intervention in cellular signaling pathways mediated by the hydrolysis of polyphosphoinositide lipids.

    2. C[BOND]H and C[BOND]C Bond Activation by Bare Transition-Metal Oxide Cations in the Gas Phase (pages 1973–1995)

      Dr. Detlef Schröder and Prof. Dr. Helmut Schwarz

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199519731

      With modern mass spectrometric techniques much information about reactions (pattern of reactivity, selectivity, intermediate) is accessible for the gas phase. Even if the results of, for instance, oxidations with MO+ ions (isolated, charaged molecules without counterions in a highly dilute atmosphere, undergoing strictly bimolecular reactions) are not directly applicable to the analogous reactions in condensed phase, a knowledge of the elementary steps obtained thus is needed for the rational design of such catalysts.

  2. Highlights

    1. Top of page
    2. Reviews
    3. Highlights
    4. Correspondences
    5. Communications
    6. Book Reviews
    1. Terminal E1 Ligands from Elements of Group 15 (pages 1997–1999)

      Priv.-Doz. Dr. Manfred Scheer

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199519971

      From objects of speculation to manipulable compounds: Two research groups have achieved the synthesis of the long sought metal complexes with terminal phosphido (P3−) ligands by independent routes, and both papers can be found in this issue of Angewandle Chemie. Cummins et al. report on the synthesis of 1 on p. 2042ff, Schrock et al. on the synthesis of 2 on p. 2044ff. Together with phosphaalkynes RC[TRIPLE BOND]P these are the first compounds with a singly coordinated phosphorus and will be of interest to theoreticians and preparative chemists alike. R = C(CD3)2CH3; Ar = 3,5-C6H3Me2; N3N = (Me3SiNCH2CH2)3N; M = Mo, W.

      • equation image
    2. Endotoxin Antagonists: Possible Candidates for the Treatment of Gram-Negative Sepsis (pages 2000–2002)

      Priv.-Doz. Dr. Otto Holst

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199520001

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      The acylation and phosphorylation pattern determines the effectiveness of disaccharide antagonists of lipid A (lipid A from Escherichia coli is shown on the right), the toxic principle of sepsis-inducing endotoxins from Gram-negative bacteria. These antgonists, which have not shown toxic activity for humans, have now been synthesized.

  3. Correspondences

    1. Top of page
    2. Reviews
    3. Highlights
    4. Correspondences
    5. Communications
    6. Book Reviews
    1. The Metallic Bond—Dead or Alive? A Comment and a Reply (page 2003)

      Prof. Leland C. Allen and Prof. Jeremy K. Burdett

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199520031

      What's in a name?! The letters discuss the usefulness of assigning qualitative concepts to the results of rigorous mathematical calculations. Exact definitions of the terms do not solve the dilemma, but pitfalls can be avoided with a knowledge of the assumption behind the calculations.

    2. The Metallic Bond—Dead or Alive? A Comment and a Reply (page 2004)

      Dr. J. Christian Schön

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199520041

      What's in a name?! The letters discuss the usefulness of assigning qualitative concepts to the results of rigorous mathematical calculations. Exact definitions of the terms do not solve the dilemma, but pitfalls can be avoided with a knowledge of the assumption behind the calculations.

  4. Communications

    1. Top of page
    2. Reviews
    3. Highlights
    4. Correspondences
    5. Communications
    6. Book Reviews
    1. Chiral Titanium Alkoxides as Catalysts for the Enantioselective Reduction of Ketones with Boranes (pages 2005–2006)

      Dipl.-Chem. Guido Giffels, Dr. Claus Dreisbach, Dr. Udo Kragl, Dipl.-Chem. Michael Weigerding, Prof. Dr. Herbert Waldmann and Prof. Dr. Christian Wandrey

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199520051

      Thumbnail image of graphical abstract

      A new application of chiral titanates such as 1 is the catalysis of the asymmetric addition of boranes to a ketocarbonyl group. Chiral alcohols are obtained in this reaction in good enantiomeric excesses ((S):(R) lies between 65:35 and 92:8).

    2. Diastereoselective Cathodic Cyclization of 1-(4- and 1-(3-Oxoalkyl)pyridinium Salts to Quinolizidine and Indolizidine Derivatives (pages 2007–2009)

      Dr. Rüdiger Gorny, Prof. Hans J. Schäfer and Dr. Roland Fröhlich

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199520071

      Thumbnail image of graphical abstract

      Diastereoselective electrochemical reduction—a very promising route to heterobicycles 2. The cathodic cyclization of oxoalkylpyridinium salts 1, n = 2, in aqueous sulfuric acid leads to the quinolizidines 2a,b (58% yield), whereas 1, n = 1, reacts selectively to give the indolizidine 2a in 55% yield. Pyridoazepines 2a,b, n = 3, are also accessible.

    3. Automerizations and Isomerizations in Propynylidene (HCCCH), Propadienylidene (H2CCC), and Cyclopropenylidene (c-C3H2) (pages 2009–2012)

      Randal A. Seburg and Prof. Dr. Robert J. McMahon

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199520091

      Thumbnail image of graphical abstract

      Two previously undetected automerization processes occur among C3H2 isomers. On irradiation at λ = 313 nm, compounds 1a,b equilibrate via 3a,b; irradiation of compounds 2a,b at longer wavelengths (λ>444 nm) also leads to their interconversion, perhaps via a cyclopropyne intermediate or transition state.

    4. Synthesis of Chiral γ,δ-Unsaturated Amino Acids by Asymmetric Ester Enolate Claisen Rearrangement (pages 2012–2014)

      Dr. Uli Kazmaier and Dipl.-Chem. Achim Krebs

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199520121

      Thumbnail image of graphical abstract

      Ester enolate Claisen rearrangement of the N-protected amino acid allylic esters 1 affords the corresponding chiral α-allylic amino acids 2 in excellent yields and selectivities. The quinine used for the induction can be almost completely recovered in the workup. Recrystallization with 1-phenylethylamine gives enantiomerically pure 2. R = alkyl, phenyl.

    5. Synthesis of Hexagonally Packed Mesoporous TiO2 by a Modified Sol–Gel Method (pages 2014–2017)

      David M. Antonelli and Prof. Jackie Y. Ying

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199520141

      Stable to surfactant removal by calcination, Ti-TMS1 is the first hexagonally packed, mesoporous transition metal oxide. The synthesis of this new material was achieved by a modified sol–gel technique from titanium alkoxides and phosphate surfactants. The large internal surface area, narrow and controllable pore size, thermal stability, and variable oxidation states of the metal give this new material great potential as a catalyst and sorbent.

    6. A Facile Access to 1λ5, 3λ5-Benzodiphospholes (pages 2017–2020)

      Prof. Dr. Hans Jürgen Bestmann, Dr. Helmut Paul Oechsner, Dr. Lothar Kisielowski, Dipl.-Chem. Claudia Egerer-Sieber and Dr. Frank Hampel

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199520171

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      The first PV–CR = PV species with a five-coordinate and a four-coordinate phosphorus atom, the title compound 1 in which R is CH3 or PhC = CHPh, for example, were synthesized from 1,3-diphosphaallyl cations and sodium hexamethyldisilazanide. Its “central” C atom has ylidic character. On heating the benzodiphospholes 1, a phosphorane–phosphane rearrangement takes place.

    7. Octathioporphyrazine Crown Ethers: An Octanuclear AgI Complex with Coordination in the meso Pocket (pages 2020–2022)

      Dr. John W. Sibert, Steven J. Lange, Charlotte L. Stern, Prof. Dr. A. G. M. Barrett and Prof. Dr. Brian M. Hoffman

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199520201

      Thumbnail image of graphical abstract

      Two distinct types of peripheral binding site coordinate the eight Ag1 ions in the complex cation 1. The four crown ether units each coordinate one Ag1 atom. Each of the other four Ag1 ions binds in a meso pocket that is formed by a meso N atom and two S atoms attached to the adjacent Cβ positions.

    8. Routes to Dendritic Networks: Bis-Dendrimers by Coupling of Cascade Macromolecules through Metal Centers (pages 2023–2026)

      Prof. George R. Newkome, Dr. Ralf Güther, Dr. Charles N. Moorefield, Francesca Cardullo, Prof. Luis Echegoyen, Eduardo Pérez-Cordero and Dr. Heinrich Luftmann

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199520231

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      The specific linking of two dendrimers is achieved by incorporating terpyridine moieties at precise locations in cascade molecules. Metal complex formation then enables nonrandom attachment of one dendritic assembly to another (see picture). The electronic properties of the metal depend on the dendritic environment.

    9. Stereoselective Syntheses of Retro-Isomers of N-Glucoasparagine (pages 2026–2028)

      Dipl.-Chem. Oliver Frey, Dipl.-Chem. Matthias Hoffmann and Prof. Dr. Horst Kessler

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199520261

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      A new type of linkage between the anomeric center of a pyranose and an amino acid is represented by the C-glycosidic amide bond (shown on the right). It was formed by coupling heptonic acids with a β-aminoalanine derivative. Both the α and the β anomers were prepared selectively.

    10. Unexpected Course of the Darzens Reaction of Phenyl Esters of α-Chlorocarboxylic Acids with Carbonyl Compounds–A Novel One-Step Synthesis of α-Chloro-β-lactones (pages 2028–2029)

      Dr. Christine Wedler, Dr. Annamarie Kunath and Prof. Dr. Hans Schick

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199520281

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      The use of phenyl esters in lieu of alkyl esters drastically changes the course of the Darzens reaction of α-chlorocarboxylates with carbonyl compounds. Instead of the usual glycidic esters, α-chloro-β-lactones 1 are formed in good yields. These lactones are useful synthetic building blocks. R1 = Me, Et, tBu, Ph, PhCH2CH2; R2 = H, Me, Et; R1/R2 = (CH2)4, (CH2)5.

    11. Fluxionality Induced by High Pressure: [9-D]9-Homocubyl Triflate, a Pressure-Sensing Molecule (page 2030)

      Dr. Urs. P. Spitz and Prof. Philip E. Eaton

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199520301

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      Much better than high temperature, which causes decomposition, high pressure accelerates the automerization (resembling a “molecular gear”) of homocubyl triflate 1 [Eq. (a)] as lebeling studies with [9-D]-1 showed.

    12. Catalytic Photoinduced Charge-Transfer Osmylation: A Novel Pathway from Arenes to Cyclitol Derivatives (pages 2031–2033)

      Prof. William B. Motherwell and Alvin S. Williams

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199520311

      Thumbnail image of graphical abstract

      A catalytic, highly stereoselective one-pot synthesis of inositol and conduritol derivatives (2 and 3, respectively) from benzene (1) and other simple arenes has been achieved by excitation of the charge-transfer band of the complex between the arene and osmium tetraoxide in the presence of chlorate or bromate anions as oxygen transfer reagents. DMAP = 4-dimethylaminopyridine.

    13. Tantalum-Mediated Coupling of Methane and Carbon Dioxide in the Gas Phase (pages 2033–2035)

      Dipl.-Chem. Ralf Wesendrup and Prof. Dr. Helmut Schwarz

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199520331

      The simultaneous activation of CO2 and CH4 by Ta+ ions in the gas phase was studied by means of FT-ICR mass spectrometry. The cationic oxides TaO+ and TaOmath image can be obtained by reduction of CO2, but they are inert toward CH4. In contrast, the coupling of CO2 and CH4 is achieved by the complex [TaCH2O]+ and yields TaOmath image and C2H2O, which is probably a ketene.

    14. [Pb18I44]8−–An Iodoplumbate with an Unusual Structure (pages 2035–2037)

      Dr. Harald Krautscheid and Frieder Vielsack

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199520351

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      The synthesis is simple, the structure very unusual. The [Pb18I44]8− ion (shown on the right), as a fraction of the NaCl structure type, is the largest iodoplumbate with discrete anions reported to date. The anion is obtained in the reaction of PbI2 with NaI in acetone as the tetrabutylammonium salt in the form of highly refractive, yellow octahedral crystals.

    15. Low-Temperature Tandem Enyne Allene Radical Cyclizations: Efficient Synthesis of 2,3-Dihydroindenes from Simple Enediynes (pages 2037–2039)

      Prof. Dr. Janet W. Grissom and Dahai Huang

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199520371

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      At physiological temperatures (37°C) the nonaromatic enyne allenes 2 cyclize to provide the 2,3-dihydroindenes 3. The high temperatures required for enediyne cyclizations (170-230°C) can be avoided, and a variety of functional groups should be able to survive the mild reaction conditions. Enediynes 1, which are accessible by a short synthetic sequence, are converted into compounds 3 with overall yields of 52 to 70%. R1 = H, Me; R2 = H, Me, CO2Me; R3 = Me, OMe, CO2Me, CH2OAc; CHD = cyclohexadiene.

    16. A Series of Well-Defined Metathesis Catalysts–Synthesis of [RuCl2([DOUBLE BOND]CHR′)(PR3)2] and Its Reactions (pages 2039–2041)

      Dr. Peter Schwab, Prof. Dr. Marcia B. France, Dr. Joseph W. Ziller and Prof. Dr. Robert H. Grubbs

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199520391

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      Substantially better initiators and therefore considerably more reactive than complexes of type A, the novel metathesis catalysts B are easily prepared by the reaction of [RuCl2(PPh3)3] with the appropriate diazoalkanes and subsequent phosphane exchange. While the PPh3 derivatives are excellent catalysts for living ROMP of norbornene, the complex with R = Cy, R′ = Ph is also a very efficient catalyst for the metathesis of acyclic alkenes.

    17. A Molybdenum–Phosphorus Triple Bond: Synthesis, Structure, and Reactivity of the Terminal Phosphido (P3−) Complex [Mo(P)(NRAr)3] (pages 2042–2044)

      Catalina E. Laplaza, Dr. William M. Davis and Prof. Dr. Christopher C. Cummins

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199520421

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      Molybdenum complex 1 and white phosphorus react smoothly at 28°C to give 2 with a terminal phosphido (P3−) ligand. The crystal structure of 2 reveals a monomer with a Mo–P triple bond (2.119(4) Å). Treatment of 2 with mesityl azide gives a complex with a terminal iminophosphenium (PNR+) ligand; treatment with elemental sulfur leads to a phosphorus monosulfide (PS) complex, R = C(CD3)2CH3, Ar = 3,5-C6H3Me2.

    18. Monomeric Molybdenum and Tungsten Complexes That Contain a Metal–Phosphorus Triple Bond (pages 2044–2046)

      Dr. Nadia C. Zanetti, Prof. Dr. Richard R. Schrock and Dr. William M. Davis

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199520441

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      The chloro complex [(N3N)WCl] and the phosphanide LiPPhH react to give the complex [(N3N)W[TRIPLE BOND]P] with a terminal phosphido (P3−) ligand (shown on the right). The W[BOND]P bond length in monomeric [(N3N)W[TRIPLE BOND]P] is 2.162(4) Å, virtually the same as the Ta–P bond length (2.145(7) Å) in [(N3N)Ta = P(cyclohexyl)]. N3N = (Me3SiNCH2CH2)3N.

    19. Cerium(III) Chloride Promoted Nucleophilic Addition of Organolithium Reagents to α-Alkyl-β-Ketophosphine Oxides: A New Protocol for the Synthesis of Stereochemically Defined Trisubstituted Olefins (pages 2046–2048)

      Prof. Dr. Giuseppe Bartoli, Dr. Enrico Marcantoni, Dr. Letizia Sambri and Dr. Monica Tamburini

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199520461

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      Horner key intermediates 2 for the synthesis of trisbustituted stereochemically defined olefins 3 can be obtained easily be stereoselective alkylation of α-alkyl-β-ketophosphine oxides 1 with RLi·CeCl3 complexes in THF at −78°C. Decomposition with KH gives trisubstituted alkenes with excellent diastereoselectivity.

    20. An Alkylperoxoiron(III) Intermediate and Its Role in the Oxidation of Aliphatic C[BOND]H Bonds (pages 2048–2051)

      Jinheung Kim, Dr. Edmund Larka, Elizabeth C. Wilkinson and Prof. Lawrence Que Jr

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199520481

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      Based on EPR, Raman, and mass spectral evidence, the formula 1 best describes the transient intermediate which forms upon treatment of 2 with tert-butyl hydroperoxide in the presence of alcohol. Kinetic evidence suggests that its decomposition by oxidation of the bound alcohol proceeds via the transition state 3. tpa = tris(2-pyridylmethyl)amine.

      • equation image
    21. Novel Binuclear Cobalt Dioxygen Complex—A Step on the Path to Dioxygen Activation (pages 2051–2052)

      Dr. Olivia M. Reinaud, Dr. Glenn P. A. Yap, Prof. Dr. Arnold L. Rheingold and Prof. Dr. Klaus H. Theopold

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199520511

      Thumbnail image of graphical abstract

      A six-membered Co2O4 ring in a chair conformation is featured in the diamagnetic dimer 2, which is in equilibrium with its CoII monomer 1H = -14.5(5) kcalmol−1 and ΔS = -60(3) cal (K−1 mol−1). The dimerization of 1 and loss of O2 from 2 are steps en route to dioxygen activation. Tp′ = hydrotris(3-isopropyl-5-methylpyrazolyl)borate).

    22. Gas-Phase Micelles (pages 2053–2055)

      Dr. Gary Siuzdak and Brian Bothner

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199520531

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      Stripped from the solvent that effected their aggregation, micelles (shown on the right, for example, for the cholic acid derivative CHAPS) were found intact in the gas phase. Mass spectrometric analysis provided physical evidence to verify micelle formation.

    23. Incorporation of Membrane Proteins in Solid-Supported Lipid Layers (pages 2056–2058)

      Dr. Renate Naumann, Dr. Alfred Jonczyk, Ralf Kopp, Dr. Jan van Esch, Prof. Helmut Ringsdorf, Prof. Wolfgang Knoll and Prof. Peter Gräber

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199520561

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      Monomolecular lipid mono- and bilayers having peptide spacer groups are prepared in situ on gold substrates. By fusion with liposomes containing ATPase, they spontaneously form lipid bilayers. Surface plasmon resonance spectroscopy and electrochemical measurements indicate that the enzyme is incorporated into the lipid layer (depicted schematically on the right). The activity of the enzyme, in this case the translocation of protons across the lipid layer, is detected by the current due to the discharge of protons at the gold electrode.

  5. Book Reviews

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

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