Angewandte Chemie International Edition in English

Cover image for Vol. 35 Issue 2

February 2, 1996

Volume 35, Issue 2

Pages 119–223

Currently known as: Angewandte Chemie International Edition

    1. Cover Picture (Angew. Chem. Int. Ed. Engl. 2/1996)

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199601171

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      The cover picture shows a methanol molecule interacting with an acid site (AlOH) in the cage of a silicon-rich sodalite (Si = blue, O = red, Al = yellow, C = green, H = white). The spheres representing the alcohol and the acidic site have been enlarged by a factor of two for reasons of clarity, and the methanol molecule is surrounded by an isosurface of its electron density. The dynamic behavior of the alcohol at finite temperature is crucial for the understanding of many catalytic processes. These state-of-the-art computer simulations that provide new insights into the microscopic mechanism of the interaction of methanol with molecular sieves are discussed by E. Nusterer, P. E. Blöchl, and K. Schwarz on p. 175ff.

  1. Reviews

    1. Top of page
    2. Reviews
    3. Highlights
    4. Communications
    5. Corrigenda
    6. Book Reviews
    1. Aluminum(I) and Gallium(I) Compounds: Syntheses, Structures, and Reactions (pages 129–149)

      Dr. Carsten Dohmeier, Dr. Dagmar Loos and Prof. Dr. Hansgeorg Schnöckel

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199601291

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      A highlight in the rapidly developing field of AlI and GaI compounds is the synthetic work with high-temperature molecules such as AlCl and GaCl at low temperature. Halides such as [Al4Br4(NEt3)4] and [Ga5Cl7(OEt2)5], and organometallic compounds such as [GaCp*] and [Al4Cpmath image] (shown on the right) have been prepared, and their structures have been characterized unambiguously.

    2. Electronegativity and Molecular Properties (pages 150–163)

      Dr. D. Bergmann and Prof. Juergen Hinze

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199601501

      The atoms shape the properties of the molecules that are constructed from them. This assumption is the fundemantal idea behind the attempt to define electronegativities of atoms, and particularly of atomic (hybrid) orbitals, in a form that enables successful predictions of molecular properties without large theoretical effort. As examples, the comparisons between experimentally determined and theoretically predicted bond energies and force constants of bonds, amongst others, are described.

  2. Highlights

    1. Top of page
    2. Reviews
    3. Highlights
    4. Communications
    5. Corrigenda
    6. Book Reviews
    1. New, Efficient Routes to Cyclic Enediynes (pages 165–166)

      Dr. Burkhard König

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199601651

      The search for simple and pharmacologically active enediynes should be considerably facilitated by a new sequence leading to acyclic and also cyclic enediynes, which proceeds via a carbenoid intermediate. The recently reported intramolecular variant yields functionalized enediynes on a multigram scale from readily accessible starting materials in yields of up to 95%.

    2. Vitamin B12: The Haze Clears (pages 167–170)

      Prof. Dr. Bernhard Kräutler and Prof. Dr. Christoph Kratky

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199601671

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      The first X-ray analysis of a B12 protein, the B12-binding domain of the methionine synthase of Escherichia coli, led to a surprising finding: there the B12 derivative, methylcobalamin, is not bound in the “base-on” form present in solution and in the crystal. Instead a histidine residue coordinates at the cobalt center of the protein-bound cofactor in place of the nucleotide function.

  3. Communications

    1. Top of page
    2. Reviews
    3. Highlights
    4. Communications
    5. Corrigenda
    6. Book Reviews
    1. [(AsOH)3(MoO3)3(AsMo9O33)]7− and [(AsOH)6(MoO3)2(O2Mo[BOND]O[BOND]MoO2)2-(AsMo9O33)2]10−: Coupling of Highly Negatively Charged Building Blocks (pages 171–173)

      Prof. Dr. Achim Müller, Erich Krickemeyer, Dr. Stephan Dillinger, Dipl.-Chem. Jochen Meyer, Dr. Hartmut Bögge and Anja Stammler

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199601711

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      For the directed synthesis of polyoxometalates the linking of the heteropolyanion 1 (schematic representation shown on the right) to form the dimeric anion 2 is extremely significant. The formation of the corresponding potassium salts of 1 and 2 from K2MoO4 and As2O3 is controlled merely by the pH value of the solution.

      • equation image
    2. Synthesis of Chiral 1,1′-Iminodicarboxylic Acid Derivatives from α-Amino Acids, Aldehydes, Isocyanides, and Alcohols by the Diastereoselective Five-Center–Four-Component Reaction (pages 173–175)

      Dr. Anton Demharter, Dipl.-Chem. Werner Hörl, Dr. Eberhardt Herdtweck and Prof. Dr. Ivar Ugi

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199601731

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      Not only yields of up to 98% but also diastereomeric excesses of up to 84% are the advantages of this effective and versatile multicomponent reaction for the synthesis of iminodicarboxylic acid derivatives in a one-pot reaction [Eq. (a)].

    3. Structure and Dynamics of Methanol in a Zeolite (pages 175–177)

      Ernst Nusterer, Dr. Peter E. Blöchl and Prof. Dr. Karlheinz Schwarz

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199601751

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      A direct view of a single methanol molecule as it interacts at finite temperatures with the acid site of a zeolite catalyst is obtained from molecular dynamics simulations. The results agree with experimental IR spectra, change the previously held notion of mechanisms of reactions in zeolites, and explain how the silicon-to-aluminum ratio of the framework influences the mode of adsorption for methanol in zeolites. One of the structures calculated is shown schematically on the right.

    4. Single-Chain Polyprenyl Phosphates Form “Primitive” Membranes (pages 177–180)

      Dr. Gianluca Pozzi, Véronique Birault, Dr. Birgit Werner, Olivier Dannenmuller, Prof. Yoichi Nakatani, Prof. Guy Ourisson and Prof. Susumu Terakawa

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199601771

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      Good candidates for model units from which the vesicles of the most primitive “protocells” may have been made are polyprenyl phosphates like A. These phosphates have carbon chains with fifteen or more C atoms. The vesicles can be observed by optical or electron microscopy.

    5. Shape-Selective Catalysis with Microporous Amorphous Mixed Oxides (pages 180–182)

      Prof. Dr. Wilhelm F. Maier, Prof. Dr. Johan A. Martens, Dipl.-Chem. Stephan Klein, Dr. Jens Heilmann, Dr. Rudy Parton, Dr. Karen Vercruysse and Prof. Dr. Pierre A. Jacobs

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199601801

      Ti- and V-containing amorphous glasses with inner surfaces of several hundred m2g−1 and pore diameters of 0.7 nm can be prepared by a sol-gel process. Like zeolites, these amorphous microporous mixed oxides AMM-MxSi show catalytic shape-selectivites. The epoxidation of alkenes with tert-butylhydroperoxide on Ti-containing glasses is catalyzed size-selectively. In the hydrocracking test of decane, these materials show a product distribution that indicates the presence of Brønstedt centers in a shape-selective environment, as well as tubular pores, the lack of additional cavities, and an effective pore size comparable to those of 10- and 12-ring zeolites.

    6. Asymmetric Dihydroxylation Enables Rapid Construction of Chiral Dendrimers Based on 1,2-Diols (pages 182–186)

      Han-Ting Chang, Dr. Chien-Tien Chen, Dr. Teruyuki Kondo, Dr. Gary Siuzdak and Prof. K. Barry Sharpless

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199601821

      Ninety chiral centers and a molecular mass of 11354 Da are the outstanding features of the largest C3-symmetric, chiral dendrimer to date. As general approach to these chiral polyether compounds (1) styrenes or stilbenes are converted into 1,2-diols by asymmetric dihydroxylation; (2) the resulting building blocks are then linked together to form dendrons by a uniquely effective ether-forming reaction, in which the vincinal hydroxyls are alkylated with benzylic bromides by using KOH pellets in refluxing toluene; (3) the dendrons are coupled to a core unit such as 1,3,5-benzene-tricarbonyl trichloride.

    7. A Novel Lithocenophane Derivative of a Trisgermole Dianion: [Li(thf)(tmeda)][2,3,4,5-Et4-Ge,Ge-{Li(2,3,4,5-Et4C4Ge)2}C4Ge] (pages 186–188)

      Adj. Prof. Dr. Jang-Hwan Hong, Dr. Youlin Pan and Prof. Dr. Philip Boudjouk

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199601861

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      A lithium-containing intermediate 1 can be isolated in the synthesis of a trigermole from 1,1-dichloro-tetraethylgermole. NMR and X-ray diffraction studies reveal that one Li cation is part of a lithocene structure, while the second is in an environment similar to common organolithium compounds. In the solid state, the second lithium center is tetrahedrally coordinated to two nitrogen atoms of TMEDA, the oxygen atom of THF, and the Ge atom of one of the π-complexed germole rings.

    8. Patterns of Multiple Additions to Fullerene C70: Isolation and Structural Characterization of [C70{Pt(PPh3)2}4] (pages 188–190)

      Prof. Dr. Alan L. Balch, Dr. Leijun Hao and Dr. Marilyn M. Olmstead

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199601881

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      Up to four platinum centers can be bound to C70, as the synthesis of [C70{Pt(PPh3)2}4] 1 with idealized C2v symmetry has shown. The four Pt(PPh3)2 groups are bound at two types of 6-6 ring junctions. The stepwise addition of Pt(PPh3)2 groups occurs initially to the most pyramidalized C-C bonds at the poles of the fullerene with subsequent additions to the adjacent 6-6 ring junctions.

    9. Acyclic Stereocontrol in Radical Reactions: ρ-Selectivity with Oxazolidinone Auxiliories (pages 190–192)

      Prof. Mukund P. Sibi and Dr. Jianguo Ji

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199601901

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      It's the addition of Lewis acids that does it! Reaction (a) proceeds with diastereoselectivities ≥ 100:1 if the radical transfer takes place in the presence of Lewis acids such as MgI2, MgBr2, or Sc(OTf)3. The influence of the substituents at position 4 of the oxazolidinone ring on the allylation was also studied.

    10. A Sustainable Catalyst for the Partial Oxidation of Methane to Syngas: Ni/Ca1-xSrxTiO3, Prepared In Situ from Perovskite Precursors (pages 192–195)

      Dr. Takashi Hayakawa, Hideaki Harihara, Dr. Arnfinn G. Andersen, Dr. Andrew P. E. York, Dr. Kunio Suzuki, Dr. Hiroyuki Yasuda and Dr. Katsuomi Takehira

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199601921

      High activity and negligible coke formation in the course of the catalytic partial oxidation of CH4 to syngas are characteristics of the Ni/Ca4-xSrxTiO3 catalyst, which is readily accessible by the citrate method from nickel nitrate, alkaline earth metal carbonates, and tetraisopropoxidotitanium. The properties and efficiency of the catalyst are normally only associated with catalysts that contain considerably more expensive metals such as Rh, Ir, and Ru.

    11. Resolving the Puzzling Eclipsed Conformation of the Methyl Group in a Tricyclic Orthoamide Trihydrate (pages 195–197)

      Dr. Ito Chao and Jye-Chan Chen

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199601951

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      The electrostatic molecular potential and a molecular orbital analysis give evidence why the unusual eclipsed conformation is preferred for the Cmath image[BOND]CH3 bond in the crystal of 1·3 H2O. The studies conclude that three C-HċO interactions can indeed overcome the low rotational barrier of 1.

    12. Synthesis of the Nonamannan Residue of a Glycoprotein with High Mannose Content (pages 197–200)

      Dr. Peter Grice, Prof. Dr. Steven V. Ley, Dr. Jörg Pietruszka and Dr. Henning W. M. Priepke

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199601971

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      Deliberate tuning of the reactivity of the appropriate glycosyl donors enables nonamannan 1 to be prepared efficiently in a concise manner. Bound through a disaccharide linker, 1 is a major constituent of the envelope glycoprotein gp120 of the human-immunodeficiency virus (HIV). Gp120 plays an important role in the attachment to and penetration of target cells by HIV and in the antiviral response.

    13. Chiral Phosphanyldihydrooxazoles in Asymmetric Catalysis: Enantioselective Heck Reactions (pages 200–202)

      Dipl.-Chem. Olivier Loiseleur, Peter Meier and Prof. Dr. Andreas Pfaltz

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199602001

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      Enantiomeric excesses of up to 99% have been obtained in Heck reactions of cyclic olefins with (phosphanyldihydrooxazole)Pd catalysts [Eq. (a)]. In contrast to analogous (BINAP)Pd-catalyzed reactions, essentially no isomerization of the products by C[DOUBLE BOND]C bond migration is observed.

    14. Molecular Recognition of Carboxylate Ions Based on the Metal–Ligand Interaction and Signaled through Fluorescence Quenching (pages 202–204)

      Dr. Giancarlo De Santis, Prof. Dr. Luigi Fabbrizzi, Dr. Maurizio Licchelli, Prof. Dr. Antonio Poggi and Dr. Angelo Taglietti

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199602021

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      Aromatic carboxylate ions bearing an acceptor or donor substituent are recognized by the ZnII-containing receptor 1, and their binding is signaled through quenching of the fluorescence of the appended anthracene unit [Eq. (a)]. Quenching of the fluorophore is induced by an electron transfer to or from the substituent. R = aryl.

    15. [S(NtBu)3]2−—A Cap-Shaped Dianion, Isoelectronic with the Sulfite Ion and Oxidizable to a Stable Radical Anion (pages 204–206)

      Roland Fleischer, Dr. Stefanie Freitag, Dr. Frank Pauer and Priv.-Doz. Dr. Dietmar Stalke

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199602041

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      Two dianionic caps, linked by four lithium atoms, characterize the structure of the Li salt 1 of the tripodal ligand [S(NtBu)3]2−. On addition of THF to 1 one lithium atom leaves the inner region and coordinates to only two N atoms and a THF molecule. Oxidation of white 1 with O2 or iodine leads to a dark blue, stable radical monoanion.

    16. Epoxidation of Electron-Deficient Olefins by a Nucleophilic Iron(III) Peroxo Porphyrinato Complex, Peroxo(tetramesitylporphyrinato)ferrate(1−) (pages 206–208)

      Marlene F. Sisemore, Dr. Judith N. Burstyn and Dr. Joan S. Valentine

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199602061

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      Direct oxygen transfer to an olefinic bond is possible from the FeIII complex 2 if the double bond is electron-deficient as in 1 [Eq. (a)]. Complex 2 is analogous to intermediates proposed for cytochrome P450 type enzymes.

    17. Synthesis and Structure of the Bis(imido)gold Complex [Aumath image(NtBu)2(PPh3)4]+Cl·2C6H5CH3; a Higher Homologue of the Organotris-(triphenylphosphaneaurio)ammonium Ions (pages 208–209)

      Robert E. Allan, Dr. Michael A. Beswick, 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.199602081

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      A “bowtie-shaped” Au5 moiety (structure shown on the right, PPh3 ligands on the terminal Au centers have been omitted) is the characteristic structural feature of the title complex. This is formed in high yield by the reaction of [AuCl(PPh3)] with [tBuNHLi] (1:1 equiv) in toluene. The cation can be regarded as the next homologue of cations of the type [(AuPPh3)3NR]+ and is the largest structurally characterized imidogold(I) species to date.

    18. Synthesis of the First Titana[3]radialene and Its Ring Enlargement to a Titanacyclopentene (pages 210–212)

      Prof. Dr. Adalbert Maercker and Dr. Andreas Groos

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199602101

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      A whole range of titanacycles can be prepared from the dilithio compound 1 and titanocene dichloride. The initial product in the reaction, radialene 2, rearranges immediately into titanacyclopentene 3. Cyclopentenes like 4 arise from the reaction of 3 with alkynes.

    19. Model Compounds for the Homogeneous Hydrodesulfurization of Benzothiophene: Insertion of Manganese into the S[BOND]C(aryl) Bond (pages 212–214)

      Conor A. Dullaghan, Shouheng Sun, Prof. Gene B. Carpenter, Brandon Weldon and Prof. Dwight A. Sweigart

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199602121

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      A highly nonplanar metallacyclic ring with a nucleophilic sulfur atom is contained in the binuclear complex 2, which is formed by reduction of the benzothiophene complex 1 in the presence of additional ligands (L = CO, P(OMe)3, P(OEt)3). This reaction, which proceeds by the insertion of manganese into the S-C(aryl) bond, is of interest in the context of catalytic desulfurization of fossil fuels.

    20. Poly(A·A·U) Triple Helix Formation Promoted by Porphyrin Assembly (pages 215–216)

      Dr. Rosaria Lauceri, Tiziana Campagna, Dr. Annalinda Contino and Prof. Dr. Roberto Purrello

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199602151

      A multicomponent molecular recognition process leads to a self-assembled “quaternary” supramolecular complex formed from porphyrins and an “unusual” poly(A·A·U) triple helix. The formation of this superstructure is promoted by porphyrin aggregation and a number of recognition processes (Watson-Crick and Hoogsteen pairing, coulombic interactions, and stacking interactions).

    21. A General and Efficient Method for the Monohydroxylation of Alkanes (pages 217–218)

      Prof. Dr. Gregorio Asensio, Dr. Rossella Mello, Prof. Dr. María Elena González-Núñnez, Gloria Castellano and Julia Corral

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199602171

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      The initially formed alcohols do not oxidize further when primary and secondary C-H bonds are oxidized by dioxirane 1 in the presence of a large excess of trifluoroacetic anhydride. The reactions (a) proceed with excellent yields under very mild conditions. R = alkyl, aryl; R′ = H, alkyl, aryl.

    22. Preparation of 1,3-Dizinc Compounds by a Boron–Zinc Exchange (pages 218–220)

      Dipl.-Chem. Holser Eick and Prof. Dr. Paul Knochel

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199602181

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      Excellent yields of 1,5-dizincacyclooctanes 2 (R = H, Bu) are readily available from the reaction of 1,3-bis(diethylboryl)propanes 1 with diethylzinc. After transmetalation with Cu1 salts, the heterocycles 2 react with electrophiles (allylic and propargylic bromides, benzoyl chloride, etc.) in satisfactory to good yields; the reaction with 1,4-dibromo-2-butyne leads to the bis(methylene)cyclopentane 3 (R = Bu).

    23. New Catalysts and Conditions for a C[BOND]H Insertion Reaction Identified by High Throughput Catalyst Screening (pages 220–222)

      Prof. Kevin Burgess, Hee-Jong Lim, Alexander M. Porte and Prof. Gary A. Sulikowski

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199602201

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      A microtiter plate was used to set up 96 different conditions for the asymmetric C-H insertion reaction of diazo compound 1 which leads to the heterocycle 2. This high throughput catalyst screening process unearthed a superior set of conditions, and a new silver-based catalyst for the reaction. L-Men = L-Menthyl.

  4. Corrigenda

    1. Top of page
    2. Reviews
    3. Highlights
    4. Communications
    5. Corrigenda
    6. Book Reviews
    1. You have free access to this content
      Correction of “1,1-Di-, 1,2,3-Tri- and 1,1,4,4-Tetra-tert-butyl-1,3-butadiene” (page 222)

      Prof. Dr. Henning Hopf, Dipl.-Chem. Ralf Hänel, Prof. Dr. Peter G. Jones and Dipl.-Chem. Peter Bubenitschek

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199602221

  5. Book Reviews

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

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