Angewandte Chemie International Edition in English

Cover image for Vol. 19 Issue 4

April 1980

Volume 19, Issue 4

Pages 231–332

Currently known as: Angewandte Chemie International Edition

  1. Reviews

    1. Top of page
    2. Reviews
    3. Communications
    4. Book Reviews
    1. Viroids: A Class of Subviral Pathogens (pages 231–243)

      Priv.-Doz. Dr. Hans J. Gross and Prof. Dr. Detlev Riesner

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198002313

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      Even smaller than viruses and bacteriophages, but cyclic and likewise infectious: this description applies to viroids. They have no coat protein and consist of ribonucleic acid (ca. 360 nucleotides). The potato spindle tuber viroid has now been completely characterized by chemical methods.

    2. Photochemical Rearrangements and Fragmentations of Benzene Derivatives and Annelated Arenes (pages 243–275)

      Prof. Dr. Gerd Kaupp

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198002431

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      The intramolecular reactions of electronically excited benzene derivatives are the topic of a systematic study. The classification adopted permits inclusion of all known reaction types. Selected examples (about 150 formula blocks) illustrate the text.

    3. Heterocyclic Analogues of Methylenecyclopropanes (pages 276–289)

      Prof. Dr. Gerrit L'abbé

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198002761

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      Three-membered heterocycles having an exocyclic double bond of type (1) warrant particular interest on account of their ring strain and their fascinating chemical properties. The article reports such compounds, with O, S, and N as heteroatoms, which have been isolated, detected as intermediates, or suspected as such.

    4. Polarized Low-Temperature Crystal Spectra of Inorganic Complexes (pages 290–301)

      Dr. Peter Day

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198002901

      The information gained from electronic spectra is greatly increased if they are recorded under the conditions given in the title. Many of the bands thus measured can be reliably assigned; these assignments permit testing of theories of electronic structure.

  2. Communications

    1. Top of page
    2. Reviews
    3. Communications
    4. Book Reviews
    1. The Dynamic Behavior of 2,4,6-Cycloheptatriene-1-carbaldehyde (pages 301–302)

      Dr. Metin Balci, Dipl.-Chem. Hartmut Fischer and Prof. Dr. Harald Günther

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198003011

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      Valence isomerization and additional ring inversion have been observed in 2,4,6-cycloheptatriene-1-carbaldehyde (R[DOUBLE BOND]CHO) below −134 °C. No other monosubstituted cycloheptatrienes are known to show this dynamic behavior.

    2. A Facile Route to a Sensitive Terpene Alcohol—Regio-unselective Metalation of α-Terpinene as Key Step (page 303)

      Prof. Dr. Manfred Schlosser, Dr. Herbert Bosshardt, Annelis Walde and Manfred Stähle

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198003031

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      The almost forgotten compound anthemol(3) has been synthesized by the proven one-pot procedure for the synthesis of allylic and dienylic alcohols. Surprisingly, metalation of (1) gives not only the pentadienylpotassium compound (2a) but also the isomers (2b) and (2c), which should be energetically favored.

    3. α-Carbamoyloxymethyl-Substituted Lithium Enethiolates from 1-(N,N-Dimethylcarbamoylthio)-2-methyl-1-propenyllithium (pages 303–304)

      Priv.-Doz. Dr. Dieter Hoppe, Dr. Ludger Beckmann and Dr. Rainer Follmann

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198003032

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      An entry to the little-investigated enethiolates (or thioenolates) such as (3) is provided by the reaction of the thioester (1) with tBuLi. Key step is H/Li exchange to form (2). This nucleophilic building block transfers a latent enethiolate group.

    4. 1,5-Dihydropentalene by Tandem Carbene-Carbene Rearrangement (pages 304–305)

      Dr. Udo H. Brinker and Dipl.-Chem. Ilona Fleischhauer

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198003041

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      A new type of carbene-carbene rearrangement transforms (1) in a single synthetic step into 1,5-dihydropentalene. 12C-labeling suggests the reaction course shown below.

    5. Mechanism of the Pyrylium/Pyridinium Ring Interconversion. Mild Preparative Conditions for Conversion of Amines into Pyridinium Ions (page 306)

      Prof. Dr. Alan R. Katritzky, Dr. Ruben H. Manzo, Jeremy M. Lloyd and Dr. Ranjan C. Patel

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198003061

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      Successive base and acid catalysis in the transformation of pyrylium (1) into pyridinium ions (2) permits drastic reduction of reaction time (depending upon R) and/or of the temperature.

    6. 9,10-Benzotricyclo[6.2.2.02,7]dodeca-3,5,9,11-tetraene—A Diels-Alder Adduct of Benzene and Naphthalene (pages 307–308)

      Dr. Wolfram Grimme and Dipl.-Chem. Hans Günter Köser

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198003071

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      Only indirectly accessible, the Diels-Alder adduct of the two simplest arenes(1) warrants attention; it has now been synthesized for the first time. Cycloreversion to benzene and naphthalene has been studied kinetically.

    7. (+)-(2R)-5,5′-Dimethyl-2,2′-spirobi(2,3-dihydro-1H-cyclopenta[a]naphthalene)—A Chiral Spirohydrocarbon Containing Orthogonal Naphthalene Units (page 308)

      Dr. Horst Neudeck and Prof. Dr. Karl Schlögl

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198003081

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      The study of chiroptical properties is facilitated by the optically active 2,2′-spirobiindanes, e.g. derivatives of (1). (+)-(2), accessible from (2R)-(1) in a multistep synthesis, is highly promising owing to the mutually perpendicular naphthalene units.

    8. Carbon Monoxide/Water as a Reducing Agent: Formation of Selane from Selenium (pages 308–309)

      Prof. Dr. Noboru Sonoda, Dr. Kiyoshi Kondo, Kiyoyuki Nagano, Nobuaki Kambe and Fumihiko Morimoto

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198003082

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      A catalytic cycle for hydrogenation with CO/H2O in homogeneous phase is still far off. However, reaction (a) which proceeds quantitatively (presumably via SeCO and HSeCOOH) at 25 °C/1 bar suggests that such a cycle may be found.

    9. X-Ray Structure Analysis of Bis(O,O′-diphenyldithiophosphato)tin(II), a Bicyclic Dimer Held Together by η6-C6H5/SnII Interactions (pages 309–310)

      Dr. J. L. Lefferts, Dr. M. B. Hossain, Dr. K. C. Molloy, Prof. Dr. D. van der Helm and Prof. Dr. J. J. Zuckerman

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198003091

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      A dimeric tin complex of highly unusual structure has been obtained as part of a program to synthesize biocidal tin compounds [eq. (1)]. Two ligands are normal chelating agents, and two form bridges; two η6-C6H5-SnII interactions stabilize the dimer.

      • equation image
    10. 1,2,3-Triazolo[4,5-d][1,3]thiazine, a New Heterocyclic System (pages 310–315)

      Prof. Dr. Adrien Albert and Dr. Albert Dunand

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198003101

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      A new heterocycle(1) of C2N3[BOND]C4NS type, of potential pharmaceutical interest, has been prepared from a triazole derivative. (1) can be readily S-methylated and subjected to further transformations

    11. Exceedingly Mild Desulfurization of Thiols by Sodium Triethylhydroborate and Transition Metal Chlorides (pages 315–316)

      Prof. Dr. Howard Alper and Trish L. Prince

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198003151

      Hydrocarbons can be obtained from thiols at room temperature/−78 °C with the new reduction system given below. The procedure is suitable for aromatic, benzylic, and aliphatic thiols; CoCl2 can be used instead of FeCl2. Other chlorides are less effective.

      • equation image
    12. General Method for Preparation of Multidentate Fluorophosphane Ligands (page 316)

      Ernest R. Cromie, George Hunter and Dr. David W. H. Rankin

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198003161

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      Multidentate ligands with OPF2 groups are accessible by reaction of organic or inorganic compounds ROH with bis(difluorophosphino)sulfide (S(PF2)2). The syntheses of (1) and (2) are typical examples.

    13. 195Pt-NMR Spectroscopy of Catalytically Active Complexes. Extremely Large Spin-Spin Coupling between Platinum and Tin (pages 316–317)

      Dr. Karl-H. A. Ostoja Starzewski and Dr. Paul S. Pregosin

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198003162

      An extremely high coupling constant of 28954 Hz (1J(195Pt119Sn))—the highest one-bond spin-spin coupling yet found—has been measured for [PtCl(SnCl3)(PEt3)2]. In combination with SnCl2, platinum-phosphane complexes are excellent homogeneous catalysts for hydrogenation and hydroformylation reactions. 195Pt-NMR spectroscopy is extremely sensitive to changes of the coordination sphere and is therefore well suited to the study of such catalysts.

    14. Metal-Catalyzed Synthesis of Cyclic Carbonates from Carbon Dioxide and Oxiranes (pages 317–318)

      Dr. Michael Ratzenhofer and Priv.-Doz. Dr. Horst Kisch

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198003171

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      Use of CO2 in organic synthesis, e.g. for production of (2), formerly required 100–200 °C and 5–200 atm. Catalysts such as MoCl5/PPh3, AlCl3/PPh3, etc. now permit working under normal conditions.

    15. Synthesis of the Epimeric 4-Methyl Derivatives of endo-endo- and exo-endo- Tetracyclo[6.2.1.13,6.02,7]dodecane (pages 318–319)

      Priv.-Doz. Dr. Dieter Lenoir and Dr. Robert M. Frank

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198003181

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      A need for model compounds for examining steric hindrance in highly strained cycloaliphatic compounds prompted synthesis of compounds (1) and (2) and their isomers with exo-endo instead of endo-endo skeleton. The greater strain of (2) with inside methyl group is evident in the IR and NMR spectrum.

    16. 2-tert-Butyl-2H-isoindole: A Partner for Reactions with Electrophiles (page 320)

      Prof. Dr. Richard Kreher and Dipl.-Ing. Götz Use

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198003201

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      A rare case among the bicyclic 10π-heteroarenes having o-quinonoid structure is that of 2-tert-butyl-2H-isoindole (1), for it can be protonated, alkylated, and subjected to electrophilic coupling with arenediazonium salts to give azo compounds.

    17. Structure of Metal-Free Corrinoids from Rhodopseudomonas sphaeroides (page 321)

      Dr. Bernd Dresow, Dr. Gerhard Schlingmann, Dr. William S. Sheldrick and Dr. Volker B. Koppenhagen

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198003211

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      Metal-free corrinoids are formed on a gram scale by the purple bacterium Rhodopseudomonas sphaeroides under cobalt-deficient conditions; the compounds arising are (1) and the corresponding a,c-diamide. Such compounds could serve, e.g., as starting materials for vitamin B12 analogues with other metals.

    18. Structure of Yellow Metal-Free and Yellow Cobalt-Containing Corrinoids (pages 321–322)

      Dr. Gerhard Schlingmann, Dr. Bernd Dresow, Dr. Volker B. Koppenhagen, Dipl.-Chem. Wulf Becker and Dr. William S. Sherldrick

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198003212

      The biologically inactive yellow metal-free corrinoids produced in large amounts by bacteria might be of use in the synthesis of vitamin B12 antimetabolites. X-ray structure analysis of a “yellow” Co(CN)2-containing model compound revealed that the side chain c forms a lactam ring. The yellow metal-free corrinoids are probably similar in structure. Incorporation of Co and treatment with KCN transforms them into biologically active red corrinoids (with opening of the lactam ring).

    19. A Pyrazine-Bridged Heme Dimer Absorbing at 800 nm (pages 322–323)

      Prof. Dr. Jürgen-Hinrich Fuhrhop, Dr. Mohamed Baccouche and Dipl.-Chem. Marlies Bünzel

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198003221

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      The first molecular complex of heme with semiequimolar amount of an axial ligand has been detected on titration of an alkaline heme solution with pyrazine by its electronic spectrum. Thus pyrazine permits photoinduced electron transfer over ca. 1 nm between the porphyrin planes (vertical lines).

    20. Matrix Isolation of OSiS: IR Spectroscopic Evidence for the Si[DOUBLE BOND]S Double Bond (pages 323–324)

      Dr. Hansgeorg Schnöckel

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198003231

      The O[DOUBLE BOND]Si[DOUBLE BOND]S molecule has been isolated in an argon matrix and studied by IR spectroscopy. The force constants for SiS and SiO are 4.86 ± 0.06 and 9.0 ± 0.1 [102 N m−1], and the bond orders are 1.9 and 2.01, respectively. OSiS is the first SiIV compound with a Si[DOUBLE BOND]S double bond.

    21. Novel Selenoantimonate(III) Anions in Ba4Sb4Se11 (pages 324–325)

      Dr. Gerhard Cordier, Ralph Cook and Prof. Dr. Herbert Schäfer

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198003241

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      Three different isolated anionic SbSe groups—the very first selenoantimonate(III) ions—are present in Ba4Sb4Se11. Formal linkage of pyramids to give dinuclear entities was not previously known for SbIII compounds. (Gray circles represent Sb; white circles Se.)

    22. Dimerization of S6O to S12O2: Crystal Structure Analysis of S12O2·2SbCl5·3CS2 (pages 325–326)

      Prof. Dr. Ralf Steudel, Dipl.-Chem. Jürgen Steidel and Priv.-Doz. Dr. Joachim Pickardt

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198003251

      The first complex of a homocyclic sulfur oxide—itself formed from S6O in an otherwise unprecedented dimerization—is the title compound, which arises from S6O, SbCl5, and solvent CS2 at −50 °C. In the crystal, the SbCl5 groups together with the bridging O atoms have approximately octahedral geometry. The conformation of the S12 ring in the complex differs drastically from that in cyclo-S12.

    23. Syntheses with Metalloid Derivatives: Preparation of Macrocyclic Dicarbamates (pages 326–327)

      Dr. Abraham Shanzer, Dipl.-Chem. Nava Shochet, Dr. Dov Rabinovich and Dr. Felix Frolow

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198003261

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      The utility of covalently bonded metalloid templates is demonstrated by syntheses with (a) Bu2SnO and (b) Me2Si(NCO) (or Me2Si(NCS)2). Approach (a) leads to macrocycles from diols and diisocyanates, and approach (b) gives unsymmetrically substituted heterocycles from symmetrical reactants (Im [DOUBLE BOND] imidazolyl).

    24. Syntheses with Metalloid Derivatives: Preparation of Heterocycles (pages 327–328)

      Dr. Abraham Shanzer

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198003271

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      The utility of covalently bonded metalloid templates is demonstrated by syntheses with (a) Bu2SnO and (b) Me2Si(NCO) (or Me2Si(NCS)2). Approach (a) leads to macrocycles from diols and diisocyanates, and approach (b) gives unsymmetrically substituted heterocycles from symmetrical reactants (Im [DOUBLE BOND] imidazolyl).

    25. Coupling of Well-Established Organotransition Metal Chemistry Donor Groups to Multielectron Ligands (pages 328–329)

      Prof. Dr. Thomas Kauffmann, Dipl.-Chem. Johann Ennen, Dipl.-Chem. Harald Lhotak, Dipl.-Chem. Alfons Rensing, Dipl.-Chem. Fritz Steinseifer and Annegret Woltermann

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198003281

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      A variety of tailor-made four-electron ligands could contribute to more effective syntheses with transition metal compounds. Examples: on treatment with Ph2PLi and LiC5H4[BOND](CH2)2[BOND]CHLi-pyridyl, (1) gives the ligands (2) and (3), respectively; with PhAsLi2/FeCl2 and pyridyl-CHLi2/FeCl2, compound (1) gives the ansa-ferrocenes (4a) and (4b).

  3. Book Reviews

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

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