Angewandte Chemie International Edition in English

Cover image for Vol. 23 Issue 2

February 1984

Volume 23, Issue 2

Pages 89–172

Currently known as: Angewandte Chemie International Edition

    1. Cover Picture (Angew. Chem. Int. Ed. Engl. 2/1984)

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198400891

      Thumbnail image of graphical abstract

      The cover shows the absorption bands (top) of a dye doped in minute con-centrations into an organic glass or polymers. The bands contain “holes” indented using a laser. The scheme at the bottom serves to illustrate the principle of photochemical hole burning. Further details are reprted by D. Haarer and J. Freidrich in their review article on page 96 ff.

  1. Reviews

    1. Top of page
    2. Reviews
    3. Communications
    4. Book Reviews
    1. Metal-Carbon and Metal-Metal Multiple Bonds as Ligands in Transition-Metal Chemistry: The Isolobal Connection (pages 89–99)

      Prof. Dr. F. Gordon A. Stone

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198400893

      Thumbnail image of graphical abstract

      An extremely fruitful principle in organometallic chemistry has proved to be the isolobal model developed by Roald Hoffmann. On the one hand, it enables many seemingly complicated reactions to be understood, and on the other, the systematic synthesis of novel compounds. An example is the stepwise addition of [Pt(cod)2] to 1, M = Pt, to afford the Pt3W2 complex 2.

    2. Routes to Functional Vesicle Membranes without Proteins (pages 100–113)

      Prof. Dr. Jürgen-Hinrich Fuhrhop and Dipl.-Chem. Joachim Mathieu

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198401001

      Thumbnail image of graphical abstract

      Fixation of reaction partners at appropriate distances is a prerequisite for vectorial reactions. In natural membranes the reaction centers are fixed by complexes with proteins. In synthetic vesicle membranes this is achieved, inter alia, by alignment of bolaamphiphiles (two head-groups) such as 1. Vesicles formed from compounds with chiral head-groups such as 2 can distinguish enantiomers.

    3. Photochemical Hole Burning: A Spectroscopic Study of Relaxation Processes in Polymers and Glasses (pages 113–140)

      Prof. Josef Friedrich and Prof. Dr. Dietrich Haarer

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198401131

      A special type of saturation spectroscopy in the optical region is the technique of photochemical hole burning. The holes—more preisely, indentations—are burned with laser irradiation into the absorption bands of dye molecules doped in trace amounts into a matrix. These holes are highly sensitive probes which provide information about the guest and host systems. Potential applications are, e.g., spectroscopy of biomolecules and in data storage.

  2. Communications

    1. Top of page
    2. Reviews
    3. Communications
    4. Book Reviews
    1. Stepwise Assembly of a Cluster with Four Different Metal Atoms (pages 140–141)

      Dipl.-Chem. Klaus Fischer, Dr. Manfred Müller and Prof. Dr. Heinrich Vahrenkamp

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198401401

      Thumbnail image of graphical abstract

      A construction kit for tetranuclear clusters contains MePCl2, Fe2(CO)9, KCo(CO)4, Ru3(CO)12, and Ph3PAuCl. Their stepwise combination leads to the cluster 1a in which the metal atoms adopt a “butterfly”- like arrangement. 1b is accessible in a similar way.

    2. A “Cluster-Centered” Acetylene-Vinylidene Rearrangement (pages 141–142)

      Dipl.-Chem. Wolfgang Bernhardt and Prof. Dr. Heinrich Vahrenkamp

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198401411

      The isomerization tBuC[TRIPLE BOND]CH[RIGHTWARDS ARROW]tBuHC[DOUBLE BOND]C[DOUBLE BOND] was achieved on the cluster Co2Ru (CO)9. Starting material and product were charterized by X-ray structure analysis. It appears plausible that initial migration of the acetylenic H atom to the metal leads to formation of an acetylide complex, which then tautomerizes in a second step to the vinylidene complex.—Reactions of this type are interesting, inter alia, as models for catalytic processes on solid surfaces.

    3. Enantioselective and Enantioconvergent Syntheses of Building Blocks for the Total Synthesis of Cyclopentanoid Natural Products (pages 142–143)

      Priv.-Doz. Dr. Hans-Joachim Gais and Dr. Karl L. Lukas

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198401421

      Thumbnail image of graphical abstract

      The cyclopentenoid lactone 1 and its enantiomer ent-1 were prepared enantiomerically pure on the mole scale from meso-tetrahydrophthalic acid anhydride. The key step is the partial saponification of dimethyl tetrahydrophthalate 2 with commercially available pig liver esterase.

    4. Stereoselective Synthesis of (E)-4-Hydroxy-2-alkenoic Acid Ester from Aldehydes and the d3-Building Block Ethyl Lithiopropiolate (pages 143–145)

      Priv.-Doz. Dr. Hans-Joachim Gais

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198401431

      Thumbnail image of graphical abstract

      For the (E)-4-hydroxy-2-alkenoic acid ester part-structure 1, which is widely distributed in natural products, a stereoselective synthesis has been worked out. For this purpose, a 4-functionalized 2-alkynoic acid ester, prepared from an aldehyde and Li compound 2, is reduced E-stereoselectively to 1. The range of application can be demonstrated using aldehyde 3.

    5. Asymmetric Total Synthesis of the Macrolides Brefeldin A and 7-epi-Brefeldin A (pages 145–146)

      Priv.-Doz. Dr. Hans-Joachim Gais and Dr. Thomas Lied

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198401451

      Thumbnail image of graphical abstract

      A novel, efficient strategy for the asymmetric total synthesis of brefeldin A 1 and its 7-epimer 2 is based on the building blocks and methods described in the two previous communications.

    6. Liquid-Crystalline 4-Bicyclohexylcarbonitriles with Extraordinary Physical Properties (page 147)

      Dr. Rudolf Eidenschink, Dr. Günther Haas, Dr. Michael Römer and Dr. Bernhard S. Scheuble

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198401471

      Thumbnail image of graphical abstract

      Liquid crystals, despite the presence of an axial cyano group, are formed by the compounds 2, which were prepared from starting materials 1 with an equatorial cyano group. The liquid-crystalline behavior of 1, but not that of 2, can be accounted for by existing theories.

    7. Aliphatic Polyethers, Basic Building Blocks from Naturally Occurring Humic Substances: Detection by Solid State 13C-NMR Spectroscopy (pages 147–149)

      Prof. Dr. Ernst Bayer, Dr. Klaus Albert, Dr. Wolf Bergmann, Dr. Kuno Jahns, Dr. Wolfram Eisener and Dipl.-Chem. Hans-Konrad Peters

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198401472

      The structure of humic substances has long been a subject of controversy. In particular, their higher oxygen content could not be explained. Studies in solution did little to help. CP-MAS-13C-NMR spectroscopy of the substances in the solid state has now permitted precise assignment of the structural elements. Aliphatic part-structures comprise the framework of humic substances; of the oxygen-containing groups, aliphatic ethers dominate.—These findings are also of importance in understanding the genesis of fossil fuels.

    8. (Ph4As)2[Cl5W(μ-N4)WCl5], a μ-Isotetrazenido(4–) Complex of Tungsten(VI) (page 149)

      Doz. Dr. Werner Massa, Dr. Richard Kujanek, Gerhard Baum and Prof. Dr. Kurt Dehnicke

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198401491

      A planar N4 star, which is bonded at two points to WCl5 moieties, is contained in the novel complex 1. This first isotetrazene derivative of a transition metal was characterized by X-ray structure analysis. Compounds of this type are precusors of N,N-bridge complexes.

      • equation image
    9. Trifluoroethylidynesulfur Trifluoride, F3C[BOND]C[TRIPLE BOND]SF3 (page 150)

      Dr. Brigitte Pötter and Prof. Dr. Konrad Seppelt

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198401501

      A carbon-sulfur triple bond is present in the title compound, which has been synthesized for the first time. The compound is a colorless gas which rapidly oligomerizes. The strong, very broad band in the IR gas spectrum at 1740 cm−1 can be unequivocally assigned to the C[TRIPLE BOND]S bond.

      • equation image
    10. A New Route to Iron-Sulfur Clusters: Synthesis and Structure of [(C2H5)4N]2Fe6S6I6 (pages 150–151)

      Dipl.-Chem. Wolfgang Saak, Dr. Gerald Henkel and Priv.-Doz. Dr. Siegfried Pohl

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198401502

      Thumbnail image of graphical abstract

      The preparation of the iodine-substituted Fe[BOND]S cluster [Fe6S6I6]2⊖1 was carried out by heating stoichiometric amounts of Fe, S8, I2, and I. 1 contains two Fe3S3 six-membered rings linked via six Fe[BOND]S bonds. The known clusters [Fe2S2I4]2⊖ and [Fe4S4I4]2⊖ were obtained analogously.

    11. Preparative Microbial Reduction of β-Oxoesters with Thermoanaerobium brockii (pages 151–152)

      Professor Dr. Dieter Seebach, Max F. Züger, Fabio Giovannini, Dr. Bernhard Sonnleitner and Professor Dr. Armin Fiechter

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198401511

      Thumbnail image of graphical abstract

      Cultures of thermophilic bacteria have been used for the first time on the laboratory scale in organic synthesis. The asymmetric reduction of some β-oxoesters 1 to the hydroxy esters 2 proceeded in good chemical and optical yields. For example: R [DOUBLE BOND] CH3 (ethyl ester), C2H5 (ethyl ester), and ClCH2 (methyl ester): ee = 80, 84 and 89%, respectively.

    12. 13C-NMR INADEQUATE Spectrum with Broad Band Decoupling by Supercycles (pages 152–153)

      Peter Bolte, Prof. Dr. Martin Klessinger and Dr. Konrad Wilhelm

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198401521

      The informational value of 13C-13C coupling constants has hardly yet been exploited, because they were extremely difficult to measure in molecules with 13C in natural abundance. Use of the “incredible natural abundance double quantum transfer experiment” method improves the situation. The combination of this method with an effective pulse sequence for proton decoupling now permits routine measurement of J(13C, 13C).

    13. Cyclic Carboxylic Acid-Organoboron Compounds with BHB Bridge Bonding (pages 153–155)

      Dr. Peter Idelmann, Dr. Gerhard Müller, Walter R. Scheidt, Wilhelm Schüssler, Prof. Dr. Roland Köster and Dr. K. Seevogel

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198401531

      Thumbnail image of graphical abstract

      An almost planar six-membered ring with 3c2e BHB bonding is formed as the product 1 of the reaction between pivalic acid and the diorganohydrorane 2 (9-borabicyclo[3.3.1]nonane, 9-BBN). Compounds such as 1 are allegedly intermediates in the reduction of carboxylic acids with boranes.

    14. Thermally Stable Ethylperoxyboron Unit by Regioselective Autoxidation (pages 155–156)

      Prof. Dr. Roland Köster and Günter Seidel

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198401551

      Thumbnail image of graphical abstract

      Distillable, five-membered hetrocycles such as 2 with the

      group are formed by autoxidation of the corresponding

      compounds 1. Depending on the combination of elements and oxidizing agent, the heterocycles can be converted either into

      species or six-membered rings with an additional ring O atom.

    15. Synthesis and Structure of a Five-Coordinate Manganese(I) Complex (pages 156–157)

      Prof. Dr. Otto J. Scherer, Dipl.-Chem. Jürgen Kerth and Prof. Dr. William S. Sheldrick

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198401561

      Thumbnail image of graphical abstract

      The 16-electron manganese(I) complex 1, with five ligands is astonishingly stable: It can even be handled for short periods of time in air! Crystal structure analysis of 1 establishes that the manganese has a distorted, square-pyramidal environment.

    16. The First Stable Methyleneoxophosphorane (pages 157–158)

      Prof. Dr. Rolf Appel, Dipl.-Chem. Falk Knoch and Dipl.-Chem. Holger Kunze

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198401571

      Thumbnail image of graphical abstract

      The oxidation of a P[DOUBLE BOND]C bond flanked by bulky groups in 1 to afford the [BOND]P(O)[DOUBLE BOND]C-group in 2 proceeds with ozone. 1 reacts with sulfur to yield the thio-analogue of 2.

    17. Sn3(NtBu)2(OtBu)2, A Molecule with a Novel, Heptaatomic, Polycyclic Framework (pages 158–159)

      Prof. Dr. Michael Veith and Dipl.-Chem. Walter Frank

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198401581

      Thumbnail image of graphical abstract

      The novel polycycle Sn3N2O2 is adopted by the framework of the product 1, which is stable up to 250°C and is obtained by reaction of Me2Si(NtBu)3Sn2 with Sn(OtBu)2. 1 is formed formally by “fusing” two trigonal SnN2OSn bipyramids at an SnN2 face.

    18. Isolation of a Sulfur-Rich Binary Mercury Species from a Sulfide-Containing Solution: [Hg(S6)2]2⊖, a Complex with Smath image Ligands (pages 159–160)

      Prof. Dr. Achim Müller, Jürgen Schimanski and Uwe Schimanski

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198401591

      Thumbnail image of graphical abstract

      The ion [S6HgS6]2⊖ can be viewed as an inorganic spiro compound. It is the first homoleptic complex with bidentate Smath image ligands. Formation of such ions in alkaline, sulfide-containing solutions is of general chemical (possible formation of unusual thiometallates), and also of analytical and minerological, interest.

    19. Novel Clusters of Cobalt and Nickel with Organophosphorus Ligands (pages 160–162)

      Prof. Dr. Dieter Fenske, Dipl.-Chem. Ramazan Basoglu, Dipl.-Chem. Johannes Hachgenei and Dipl.-Chem. Friedhelm Rogel

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198401601

      A surprisingly easy access to the preparation of transition-metal clusters is the reaction of MCl2 (M [DOUBLE BOND] Co, Ni) with PhP(SiMe3)2 and PPh3. In this way [Co43-PPh)4(PPh3)4] and [Ni8(X)44-PPh)6(PPh3)4] (X[DOUBLE BOND]Cl and CO) can be isolated. The paramagnetic complex with X [DOUBLE BOND] Cl contains 116 valence electrons and can be considered as a mixed-valence cluster of Ni0 and Ni1+.

    20. Optically Active α-Arylcarboxylic Acids by Kinetic Resolution: Pyrethroid Acids (pages 162–164)

      Prof. Dr. Christoph Rüchardt, Dipl.-Chem. Holger Gärtner and Dipl.-Chem. Ulrich Salz

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198401621

      Thumbnail image of graphical abstract

      By means of the chiral auxiliaries 1-m- and 1-p-pyridylethanols 2, racemic α-arylcarboxylic acids (as anhydrides 1) can be resolved into their enantiomers. One enantiomer accumulates in the ester 3 and the other in the acid 4. Interesting examples are 2-aryl-3-methylbutyric acids (pyrethroid acids).

    21. A Biphenylenediporphyrin: Two Cofacially Arranged Porphyrins with a Biphenylene Bridge (pages 164–165)

      Prof. Dr. Chi K. Chang and Ismail Abdalmuhdi

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198401641

      Thumbnail image of graphical abstract

      The strong tendency of the porphyrin framework to form permitted synthesis of the title compound 1 by successive reaction of biphenylenedicarbaldehyde with pyrrole and dipyrrylmethane derivatives. 1 forms a dicopper(II) complex with, as yet, unexplained properties.

    22. Highly Enantioselective Synthesis of a 2,3-Dihydroindole Mediated by N-Methylephedrine (pages 165–166)

      Robert Jan Vijn, Prof. Dr. W. Nico Speckamp, Bart S. de Jong and Dr. Henk Hiemstra

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198401651

      Thumbnail image of graphical abstract

      Cyclization of the prochiral starting material 1 to the almost enantiomerically pure product 2, R = n-Pr, proceeded in the presence of the chiral catalyst formed from n-BuLi and N-methylephedrine 3. (+)-3 leads to (−)-2 and (−)-3 to (+)-2 (>95%ee). However, this result was not achieved with other substituents R in 1.

    23. 1,2-Dioxetane: Synthesis, Characterization, Stability, and Chemiluminescence (pages 166–167)

      Prof. Dr. Waldemar Adam and Dr. Wilhelm J. Baader

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198401661

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      The extremely sensitive parent heterocycle 1 can be prepared at −40°C in CH2Cl2 from 2 using the Kopecky method. For the first time it has proved possible to recod spectra of 1 and to study its decomposition, which is accompanied by chemiluminescence.

    24. Total Synthesis of a Fortimicin Aglycone (pages 167–169)

      Jürgen Schubert, Dr. Reinhard Schwesinger and Prof. Dr. Horst Prinzbach

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198401671

      Thumbnail image of graphical abstract

      Novel broad band aminoglycoside antibiotics such as the fortimicins 2 contain cis-1,4-(deoxy)inosadiamines as aglycones. With 1, R[DOUBLE BOND]OH, as starting material convenient syntheses of enantiomerically pure 3-de-O-methylfortamine 3, R[DOUBLE BOND]H, of derivatives bearing protecting groups as well as of analogues were developed.

    25. Synthesis of New Amorphous Metallic Spin Glasses M2SnTe4 (M[DOUBLE BOND]Cr, Mn, Fe, Co): Solvent Induced Metal-Insulator Transformations (pages 169–170)

      Dr. Robert C. Haushalter, Dr. Charles M. O'Connor, Dr. Jeanne P. Haushalter, Dr. Arun M. Umarji and Dr. Gopal K. Shenoy

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198401691

      Precipitation of amorphous metallic spin glasses from solution is a novel, potentially general method. By this means, main-group metal polyanions are oxidized by transition-metal cations. The example which has been studied in most detail is Fe2SnTe4. This forms immediately as a black precipitate when methanolic solutions of anhydrous FeBr2 and K4SnTe4 are mixed at −20°C. The resistivity of pressed powder samples is low. In the presence of strong donor ligands, the Fe[BOND]Te bonds are selectively cleaved. Solid [Fe(en)2]2SnTe4 (orange) is an insulator.

  3. Book Reviews

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