Angewandte Chemie International Edition in English

Cover image for Vol. 35 Issue 8

May 3, 1996

Volume 35, Issue 8

Pages 795–915

Currently known as: Angewandte Chemie International Edition

    1. Cover Picture (Angew. Chem. Int. Ed. Engl. 8/1996)

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199607931

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      The cover picture shows schematically the structures of dimeric and trimeric complexes of two leucine zipper peptides (designated A and L) and the assigned peaks of the molecular ions in the ESI mass spectrum. The equilibria between the three homo- and heteromeric dimers and the four homo- and heteromeric trimers are recognizable in the spectrum. The development of ESI mass spectrometry and its perspectives for analysis of supramolecular complexes are discussed by M. Przybylski and M. O. Glocker on page 806 ff.

  1. Reviews

    1. Top of page
    2. Reviews
    3. Highlights
    4. Communications
    5. Book Reviews
    1. Electrospray Mass Spectrometry of Biomacromolecular Complexes with Noncovalent Interactions—New Analytical Perspectives for Supramolecular Chemistry and Molecular Recognition Processes (pages 806–826)

      Prof. Dr. Michael Przybylski and Dr. Michael O. Glocker

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199608061

      Soft ionization methods that yield singly and multiply charged ions of intact complexes containing noncovalent interactions enable the direct mass spectrometric analysis of biomacromolecular complexes such as protein dimers, double-stranded polynucleotides, enzyme–substrate and enzyme–cofactor complexes, and host–guest systems. The method of choice for analysis of supramolecular structures in solution is electrospray mass spectrometry, which is the focus of this review.

    2. Main Group Element Analogues of Carbenes, Olefins, and Small Rings (pages 828–856)

      Priv.-Doz. Dr. Matthias Driess and Prof. Dr. Hansjörg Grützmacher

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199608281

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      Carbon is an “exotic” element. This is the conclusion drawn following the comparison of the structures and electronic properties of olefins, cyclopropanes, and bicyclo[1.1.0]butanes with related compounds composed of the carbene-analogous elements or fragments X,Y of the heavier Group 13–15 elements (shown schematically on the right). The structures and properties of these inorganic compounds are determined by the intrinsic characteristics of the corresponding carbene analogues X:. The structural distortions in doubly bonded systems can be discussed on the basis of the Carter–Goddard–Malrieu–Trinquier (CGMT) model. Thus, rules with broad application concerning the prediction of structures and electronic character can be better derived by studying the compounds with heavy main group elements.

  2. Highlights

    1. Top of page
    2. Reviews
    3. Highlights
    4. Communications
    5. Book Reviews
    1. Separation, Characterization, and Fraction Collection in the Nanoliter Domain with Capillary Electrophoresis (pages 857–859)

      Dr. Aran Paulus

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199608571

      The smaller the better! Capillary electrophoresis aims at ever smaller amounts of analyte, as demonstrated by the latest developments described here. Recent results fuel the ultimate dream of the chemist: to find the needle in the haystack and play with it, or to separate and identify by spectroscopy a single component in a complex mixture and subsequently manipulate it, even if it is a single molecule.

    2. Superlattices, Thin Films, and Materials Design—A Mechanistic Approach (pages 859–861)

      Prof. Dr. Robert Schöllhorn

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199608591

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      Modulated thin layer precursor systems provide the basis for a novel rational synthesis strategy for the controlled preparation of complex metastable structures. By sequential deposition of the elements required and subsequent thermal treatment, specific superlattices with alternating composition can be synthesized. The picture shows, as an example, a niobium titanium selenide in which the niobium content increases from top to bottom (intra- and interlayer distances increase; one half of the unit cell of the superlattice is shown).

  3. Communications

    1. Top of page
    2. Reviews
    3. Highlights
    4. Communications
    5. Book Reviews
    1. Anions Stabilized by β-Nitro Groups: The Acidity and ortho-Metalation of Nitrocubanes—Penta- and Hexanitrocubanes (pages 864–866)

      Dr. Kirill Lukin, Dr. Jianchang Li, Dr. Richard Gilardi and Prof. Philip E. Eaton

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199608641

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      The first direct metalation of a β-C[BOND]H bond activated by nitro groups is seen in the reaction of 1,3,5,7-tetranitrocubane (1) with base (see below). Such β-nitro carbanions were used to synthesize penta- (2) and hexanitrocubanes, the first cubanes containing vicinal nitro groups.

    2. Stable Tin and Lead Derivatives of Nitrocubanes: Their Formation and Use in Multiple Functionalization (pages 866–868)

      Dr. Kirill Lukin, Dr. Jianchang Li, Dr. Richard Gilardi and Prof. Philip E. Eaton

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199608661

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      A new synthetic method—β-metalation of nitrocubanes with amides of tin or lead—was used to make a series (n = 1-4) of stable stannyl and plumbyl derivatives. Appropriate cleavages of the cubyl–lead bonds provided tetrahalotetranitro-cubanes and penta- and hexanitrocubanes (see below; R = Me, Et; R′ = Et, SiMe3; X = Br, I).

    3. Heterometallic Polymeric Cluster Compounds Derived from Tetrathiotungstate and Silver(I): Syntheses and Crystal Structures of {[AgWS4]}n [NH4]n and {[W4Ag5S16]}n[M(DMF)8]n (M = Nd and La) (pages 868–870)

      Qun Huang, Prof. Xintao Wu, Quanming Wang, Tianlu Sheng and Jiaxi Lu

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199608681

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      A one-dimensional polymeric anion chain, composed of octanuclear cyclic cluster fragments [W4Ag4S16]4− linked through Ag+ ions (see below), has been isolated from the ammonium tetrathiotungstate/silver nitrate system. Lanthanide(III) ions (Nd or La), which are coordinated by eight DMF ligands and play a crucial role in the formation of the cluster compound, are encapsulated between the chains.

    4. The First C2-Symmetric, Chiral Monomethine Dye—An Apparent Violation of the Helicity Rule for Optical Rotation (pages 870–872)

      Dr. Lutz Eggers, Prof. Volker Buss and Prof. Dr. Gerald Henkel

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199608701

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      The P-helically twisted chromophore of the chiral monomethine dye (R,R)-1 (structure shown on the right) shows a negative Cotton effect for the long-wavelength cyanine band—in apparent violation of established helicity rules. Quantum mechanical calculations and a component analysis support the experimental findings, lending surprisingly additional support for those rules. X = C(CH3)C3H7, counterion: ClOmath image.

    5. Formation of a Novel μ-Nonasulfido Ligand and Its Degradation into a μ-Disulfido Ligand at a Diiridium Center (pages 872–874)

      Masayuki Nishio, Dr. Hiroyuki Matsuzaka, Dr. Yasushi Mizobe and Prof. Masanobu Hidai

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199608721

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      Surprisingly, nine sulfur atoms are present in the bridging polysulfido ligand in the diiridium complex 1 (shown on the right), which was prepared by the reaction of 2 with S8. Upon treatment with NaBPh4, the nonasulfido ligand in 1 is converted into a bridging disulfido ligand, and this reaction is accompanied by a one-electron oxidation of the diiridium core to give the paramagnetic diiridium cation 3. Cp* = C5Me5.

      • equation image
    6. The Influence of Substituents on the Formation of Liquid Crystals Induced by Hydrogen Bonds (pages 874–876)

      Dipl.-Chem. Henry Bernhardt, Priv.-Doz. Dr. Wolfgang Weissflog and Prof. Dr. Horst Kresse

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199608741

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      Derivatives of pyridine and benzoic acid having suitable structures can associate through single hydrogen bonds to form liquid crystalline systems. The “know-how” was established by systematically varying the substituents on the benzoic acid (see below): weakly electron-withdrawing substituents are the most efficient for inducing a liquid crystalline state when the substituent on the pyridine ring is an electron donor.

    7. Carbene Complexes of Divalent Chromium (pages 876–878)

      Prof. Dr. Alexander C. Filippou, Dipl.-Chem. Dirk Wössner, Dr. Bernhard Lungwitz and Dr. Gabriele Kociok-Köhn

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199608761

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      The first carbene complexes 1 (R = H, Me; X = Cl, Br) of divalent chromium were obtained selectively by addition of hydrogen halides to the metal–carbon triple bond in [(η5-C5R5)(CO)2Cr≡CNiPr2]. These carbene complexes react with isocyanides, phosphanes, and phosphites to give cationic CrII carbene complexes.

    8. Propargylation of Carbonyl Compounds by Umpolung of Propargylpalladium Complexes with Diethylzinc (pages 878–880)

      Prof. Dr. Yoshinao Tamaru, Sachio Goto, Akihiro Tanaka, Masamichi Shimizu and Dr. Masanari Kimura

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199608781

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      The first nucleophilic additions of propargylpalladium complexes have been achieved with the reactions (a), R1 = H, Me, Ph, R2 = H, Me, Ph, SiMe3. In these reactions in addition to the homopropargyl alcohol 1, the allenyl alcohol 2 was only formed for R1 = H, R2 = Me, Ph and the ethylallene 3 for R1 = Ph, R2 = H.

    9. Chemo- and Diastereoselective Epoxidation of Chiral Allylic Alcohols with the Urea Hydrogen Peroxide Adduct, Catalyzed by Titanium Silicate 1 (pages 880–882)

      Prof. Dr. Waldemar Adam, Dr. Rajiv Kumar, Dr. T. Indrasena Reddy and Dipl.-Chem. Michael Renz

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199608801

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      The threo epoxy alcohol 2 is the major stereoisomer formed in the epoxidation reaction of the chiral allylic alcohol 1 when the zeolite titanium silicate 1 (TS-1) is employed as heterogeneous catalyst and the urea hydrogen peroxide adduct (UHP) as oxygen source. The hydroxy-directing effect is rationalized in terms of hydrogen bond formation analogous to that for the mechanism of peracid epoxidation.

    10. Silolyl Anions and Silole Dianions: Structure of [K([18]crown-6)+]2[C4Me4Si2−] (pages 882–884)

      William P. Freeman, Prof. Dr. T. Don Tilley, Glenn P. A. Yap and Prof. Dr. Arnold L. Rheingold

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199608821

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      Nearly equivalent C[BOND]C distances in the five-membered ring of the dianion C4Me4Si2−, which could be isolated in crystalline form as a potassium salt in the presence of [18]crown-6 (structure on the right), suggest a high degree of delocalization. In contrast, 29Si and 13C NMR spectroscopic investigations of the silolyl anions C4Me4SiR (R [DOUBLE BOND] SiMe3, Si(SiMe3)C4Me4) show that delocalization in these systems is minimal.

    11. N-Acyl Enamines in the Paternò–Büchi Reaction: Stereoselective Preparation of 1,2-Amino Alcohols by C[BOND]C Bond Formation (pages 884–886)

      Dr. Thorsten Bach

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199608841

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      Photochemical reversal of polarity of a carbonyl compound facilitates the construction of N-substituted, α,β-difunctional amino oxetanes 2 by C[BOND]C bond formation. The reaction with suitable alkene substrates 1 provides the products in good yields and with excellent regio- and diastereoseiectivity. R = H, alkyl; R1 = alkyl, OrBu.

    12. Polybenzoid C54 Hydrocarbons: Synthesis and Structural Characterization in Vapor-Deposited Ordered Monolayers (pages 886–888)

      Dipl.-Chem. Markus Müller, Dipl.-Phys. Jörg Petersen, Dipl.-Phys. Rainer Strohmaier, Dipl.-Phys. Christian Günther, Prof. Dr. Norbert Karl and Prof. Dr. Klaus Müllen

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199608861

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      A simple route to the title compounds is accessible by the elegant and structure-specific cycloaddition–cyclodehydrogenation sequence (1 [RIGHTWARDS ARROW][RIGHTWARDS ARROW][RIGHTWARDS ARROW] 2). Owing to the high temperature stability of the large polybenzoid C54 hydrocarbons, they can be characterized in ordered vapor-deposited monolayers by means of scanning tunneling microscopy and electron diffraction.

    13. Copper(I)-Promoted Stille Cross-Coupling of Stannyl Enol Ethers with Enol Triflates: Construction of Complex Polyether Frameworks (pages 889–891)

      Prof. Dr. K. C. Nicolaou, Mitsunobu Sato, Dr. Neil D. Miller, Janet L. Gunzner, Dr. Johanne Renaud and Dr. Edouard Untersteller

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199608891

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      A simple and efficient route to bistetrahydropyranyl systems like 1 relies on the coupling of a stannyl enol ether with an enol triflate in the presence of a catalytic amount of [Pd(PPh3)4] and excess amounts of CuCl and K2CO3. Complex polyether structures are also accessible in good yields, as the synthesis of a structural element of maitotoxin demonstrates.

    14. The “Bare” Uranyl(2+) Ion, UOmath image (pages 891–894)

      Dipl.-Chem. Hans H. Cornehl, Dr. Christoph Heinemann, Dr. Joaquim Marçalo, Dr. António Pires de Matos and Prof. Dr. Helmut Schwarz

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199608911

      Ion–molecule reactions between U2+ and oxygen donors or “charge-stripping” collisions between singly charged UOmath image ions and O2 collision partners generate uranyl(2 +) ions in the gas phase. These do not readily dissociate into singly charged fragments. The standard enthalpy of formation for UOmath image is estimated to be 371 ± 60 kcalmol−1, in accord with the results of ab initio calculations.

    15. Combination of the Fe4S4 and M[BOND]CN[BOND]Fe Redox Functions (pages 894–895)

      Nianyong Zhu, Prof. Dr. Jürgen Pebler and Prof. Dr. Heinrich Vahrenkamp

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199608941

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      The unusually low magnetic moments of octanuclear complexes containing [Fe4S4(NC[BOND]MLn)4] cluster ions (shown below) are unprecedented in the chemistry of Fe4S4 clusters and ferredoxins. The new compounds are redox-active mixed-valence complexes containing iron centers in the oxidation state +2.5 and show intense intervalence transfer absorptions.

    16. [5+2]Cycloaddition of Cyclic N-Phosphino-1-azadienes: Synthesis, Structure, and Reactivity of the First Seven-Membered Iminophosphorane (pages 896–897)

      Prof. Dr. José Barluenga, Dr. Miguel Tomás, Dr. Klaus Bieger, Santiago García-Granda and Rafael Santiago-García

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199608961

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      Unusual structure and reactivity characterize 1, an iminophosphorane, which is formed by a 1,5-dipolar cycloaddition from a diazaphosphinine and dimethyl acetylenedicarboxylate. Compound 1 rearranges into 2 in solution, and reacts with electrophiles to give 3a,b.

    17. Mixed-Metal Triple-Decker Sandwich Complexes with the Porphyrin/Phthalocyanine/Porphyrin Ligand System (pages 898–899)

      Dr. Driss Chabach, Dr. André De Cian, Prof. Dr. Jean Fischer, Prof. Dr. Raymond Weiss and Prof. Dr. Mohamed El Malouli Bibout

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199608981

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      Either a metal atom or the phthalocyanine ligand is the site of the first oxidation of the heteronuclear triple-decker complexes of type 1, depending on whether they contain an oxidizable CeIII ion or not. Now the first X-ray structure of such a heteronuclear triple-decker complex (1, M [DOUBLE BOND] Ce, M′ [DOUBLE BOND] Gd, p [DOUBLE BOND] oep) has also been achieved.

    18. Direct Observation of Enantiomorphous Monolayer Crystals from Enantiomers by Scanning Tunneling Microscopy (pages 900–901)

      Forrest Stevens, Dr. Daniel J. Dyer and Prof. David M. Walba

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199609001

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      The formation of chiral structures from achiral or racemic components is of great interest because of its implications, for example, for the origin of biological chirality. Monolayers of racemic molecules can form chiral structures, but the precise origin of these structures has been unclear. Images of both enantiomers (that of the (S) enantiomer is shown on the right) and the racemate of a liquid crystal obtained by scanning tunneling microscopy present strong evidence that the racemate forms domains of enantiomerically pure molecules.

    19. Synthesis of Thiophosphoryl Derivatives of Proline: Building Blocks for Phosphanyl-Substituted Peptides with β-Turns (pages 902–904)

      Prof. Scott R. Gilbertson and Robert V. Pawlick

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199609021

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      Amino acids containing potential ligand sites offer interesting perspectives for peptide–metal complexes. FMOC and BOC forms of a proline derivative with phosphanyl groups have been synthesized, and this amino acid was incorporated into a short peptide possessing β-turn secondary structure. The structures of both the peptide and its rhodium complex 1 were analyzed by 2D NMR spectroscopy.

    20. Studies on the Asymmetric Synthesis of Stemona Alkaloids: Total Synthesis of (−)-Stenine (pages 904–906)

      Dr. Yoshiki Morimoto, Maki Iwahashi, Koji Nishida, Prof. Dr. Yuji Hayashi and Prof. Dr. Haruhisa Shirahama

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199609041

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      An asymmetric Diels-Alder reaction and an efficient construction of the A,B,D ring framework are the key steps of the highly stereoselective total synthesis of (-)-stenine (1). Alkaloids of this type of interest because of their possible applications in neuropharmacology.

    21. Multicomponent Molecular Systems Incorporating Porphyrins and Copper(I) Complexes: Simultaneous Synthesis of [3]- and [5]Rotaxanes (pages 906–909)

      Nathalie Solladié, Dr. Jean-Claude Chambron, Dr. Christiane O. Dietrich-Buchecker and Dr. Jean-Pierre Sauvage

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199609061

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      A copper(I)-templated synthesis furnishes rotaxanes, in which porphyrin subunits serve as bridges and bulky stoppers and the threaded rings contain chelating phenanthroline groups. A [5]rotaxane is shown schematically on the right, ○ = CuI, thick lines = phenanthroline units, ⋄ = porphyrins.

    22. Synthesis of Boron-Rich Lysine Dendrimers as Protein Labels in Electron Microscopy (pages 909–911)

      Dipl.-Biochem. Britta Qualmann, Dipl.-Biochem. Michael Manfred Kessels, Hans-Jürgen Musiol, Dr. Walter Daniel Sierralta, Prof. Dr. Peter Wilhelm Jungblut and Prof. Dr. Luis Moroder

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199609091

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      A novel approach from dendrimer chemistry for the synthesis of marker molecules containing eight carboranyl amino acids (MeCBA) (see structure on the right) overcomes the known inconveniences in the syntheses of linear peptide constructs. Marker molecules of this type should be able to be used in electron microscopy. R = protected peptide terminus.

  4. Book Reviews

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