Angewandte Chemie International Edition in English

Cover image for Vol. 19 Issue 12

December 1980

Volume 19, Issue 12

Pages 947–1050

Currently known as: Angewandte Chemie International Edition

    1. Cover Picture (Angew. Chem. Int. Ed. Engl. 12/1980)

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198009471

    2. Graphical Abstract (Angew. Chem. Int. Ed. Engl. 12/1980)

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198009472

  1. Reviews

    1. Top of page
    2. Reviews
    3. Communications
    4. Author Index
    5. Subject Index
    1. 1,5,-Electrocyclizations—An Important Principle of Heterocyclic Chemistry (pages 947–973)

      Prof. Rolf Huisgen

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198009473

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      The electrocyclic process of pentadienyl anion ⇌ cyclopentenyl anion type—which is comparatively unimportant in the all-carbon system and not even achieved in the parent hydrocarbon—provides a convenient means of classifying a wealth of ring closures and ring cleavages of the corresponding hetero compounds.

    2. Thermal and Photochemical Transformations of Hetero-1,3,5-hexatrienes into Five-Membered Rings—Possible Pericyclic Reactions (pages 973–983)

      Prof. Dr. Manapurathu V. George, Dr. Abijit Mitra and Dr. Kutikat B. Sukumaran

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198009731

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      Examples of the title reaction, classified according to the nature (N, O, S, Si) and number (1 to 4) of the heteroatoms, are considered systematically in this article. An example taken from the diaza series is illustrated below.

    3. Reversible Topotactic Redox Reactions of Solids by Electron/Ion Transfer (pages 983–1003)

      Prof. Dr. Robert Schöllhorn

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198009831

      Inclusion reactions in electrically conducting host phases take place with simultaneous uptake of electrons and ions in the solid. Apart from the long-known classical examples, recent years have seen the discovery of numerous host lattices ranging from inorganic compounds with three-dimensional network structures to organic solids with molecular lattices. The electronic state of the host lattice changes on inclusion of the (ionic) guest species.

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  2. Communications

    1. Top of page
    2. Reviews
    3. Communications
    4. Author Index
    5. Subject Index
    1. 2,3,5,6,7,8-Hexakis(methylene)bicyclo[2.2.2]octane (pages 1003–1004)

      Dipl.-Chem. Olivier Pilet and Prof. Dr. Pierre Vogel

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198010031

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      The first permethylenated bicyclic, the title compound (1), was synthesized in several steps from (2). Compound (1) forms colorless crystals. The hedgehog-shaped molecule suggests the name “hericenes” (Latin name for hedgehog = hericeus) for such polycyclics.

    2. Oxygen Atoms Produced by Microwave Discharge: Reaction with Arenes (pages 1004–1005)

      Elazar Zadok, Bonita Sialom and Prof. Dr. Yehuda Mazur

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198010041

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      The oxidation of arenes in the liquid phase with atomic oxygen—generated by a microwave discharge—leads essentially to phenols, formed directly or by exchange of the substituents for OH, and to products with oxidized side chains. The relative yields are shown.

    3. New Arene(dicarbonyl)chromium Chelates: Application to Asymmetric Synthesis of Amines (pages 1005–1006)

      Dr. Arlette Solladié-Cavallo, Jean Suffert and Jean-Luc Haesslein

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198010051

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      A new entry to chiral amines is presented for reaction of (1S)-(1) with CH3Li. The amine (−)-(2) is formed in 98% chemical and 94% optical yield.

    4. Phosphorus Triiodide and Diphosphorus Tetraiodide, New Reagents for Deprotecting Acetals and Ketals (pages 1006–1007)

      Dipl.-Chem. Jean-Noël Denis and Prof. Dr. Alain Krief

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198010061

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      The mild transformation of acetals and ketals (1) into aldehydes and ketones (2) can be accomplished in organic solvents, often below room temperature, with the readily accessible reagents PI3 and P2I4. Water is usually added to the reaction mixture only during work-up.

    5. Water Gas Shift Reaction with the Aid of Selenium/Platinum Catalyst (page 1007)

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

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198010071

      A new catalyst for the water gas shift reaction is metallic selenium/platinum black. Conversion of CO into CO2 was at most 43% after 20 h at 200°C/ca. 30 bar CO. Both these elements are necessary for the catalytic formation of H2 and CO2. The reaction could proceed via H2Se: H2Se/platinum black is also suitable for use as a catalyst.

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    6. Selenium-Catalyzed Reduction of Aromatic Nitro Compounds to Amines by CO/H2O in the Presence of Triethylamine (page 1008)

      Toshiyuki Miyata, Dr. Kiyoshi Kondo, Prof. Dr. Shinji Murai, Dr. Tsuneaki Hirashima and Prof. Dr. Noboru Sonoda

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198010081

      Reductions with components of water gas (CO/H2O) can be catalyzed by selenium; thus nitroarenes are transformed in the presence of metallic selenium and triethylamine into arylamines. H2Se may plausibly be assumed as the reaction species. In a control experiment, nitrobenzene and H2Se underwent quantitative conversion (under N2) into aniline.

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    7. Photoreduction of Ketones and Aldehydes to Alcohols with Hydrogen Selenide (pages 1008–1009)

      Nobuaki Kambe, Dr. Kiyoshi Kondo, Prof. Dr. Shinji Murai and Prof. Dr. Noboru Sonoda

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198010082

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      A new application of H2Se in organic synthesis is seen in the photoreduction of carbonyl compounds (1). Unlike most other reducing agents, H2Se does not lead to 1,2-diols, but instead to monoalcohols.

    8. Reduction of Carbonyl Compounds by Aluminum Telluride and H2O or D2O (page 1009)

      Nobuaki Kambe, Dr. Kiyoshi Kondo, Satoru Morita, Prof. Dr. Shinji Murai and Prof. Dr. Noboru Sonoda

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198010091

      The reduction of carbonyl compounds with H2Te generated in situ leads conveniently and very mildly to alcohols. The method offers particular advantages in the production of deuterated alcohols with the aid of Al2Te3 and D2O, which is far more favorably priced than any deuterated reducing agent.

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    9. Reduction of Aromatic Nitro, Nitroso, Hydroxylamino, Azo, and Azoxy Compounds with Hydrogen Telluride from Aluminum Telluride and Water (pages 1009–1010)

      Nobuaki Kambe, Dr. Kiyoshi Kondo and Prof. Dr. Noboru Sonoda

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198010092

      H2Te generated in situ reduces aromatic nitrogen compounds. Nitroarenes afford arylamines; azoxybenzene, azobenzene, and nitrosobenzene are transformed into hydrazobenzene; and hydroxylamine gives aniline. Azoxybenzene, azobenzene, and nitrosobenzene are possible intermediates of the reduction of nitrobenzene.

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    10. Electrophilic Amination of Cyclopentadienyllithium Compounds (pages 1010–1011)

      Dipl.-Chem. Michael Bernheim and Prof. Dr. Gernot Boche

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198010101

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      A general entry to cyclopentadienylamines(3) is provided by the reaction of (1) with the hydroxylamine derivative (2). On reaction with nBuLi, (3b) forms the isolable salt Li[C5H4NMe2], which gives a diaminoferrocene with FeCl2.

    11. Chemo- and Diastereoselective Addition of Alkyl- and Aryltitanium(IV) Compounds to Aldehydes and Ketones (pages 1011–1012)

      Prof. Dr. Manfred T. Reetz, Dipl.-Chem. Rainer Steinbach, Dipl.-Chem. Jürgen Westermann and Roland Peter

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198010111

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      CC bond formation with organotitanium compounds has many advantages. Thus aldehydes react considerably faster than ketones: for instance, PhTi(O-iPr)3 gives > 90% of (1), and 4-tert-butylcyclohexanone forms a 18:82 mixture of equatorial and axial alcohol (2) with Me2TiCl2.

    12. Thermal Rearrangement of Tetrakis(phenylimino)cyclobutane and Crystal Structure of Tetraphenylsquaramidine (pages 1012–1013)

      Prof. Dr. Hans Jürgen Bestmann, Dr. Eberhard Wilhelm and Dr. Günter Schmid

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198010121

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      A puzzle? A man on the moon? No: it's the structure of tetraphenylsquaramidine · 2CH3OH in the crystal. The compound is formed by reduction of the cyclobutane derivative (Ph[DOUBLE BOND]N[BOND]C)4, which in turn surprisingly rearranges to the long-known blue indigo dianil.

    13. Synthesis under High Pressure: Michael Addition (pages 1013–1014)

      Prof. Dr. Kiyoshi Matsumoto

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198010131

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      Good prospects for hitherto unsuccessful Michael additions exist on application of pressure in the kbar region. Thus the adduct (1) is formed at room temperature/10 kbar within 70 h in 93% yield.

    14. syn-1,6-Imino-8,13-methano[14]annulene (pages 1015–1016)

      Prof. Dr. Emanuel Vogel, Dr. Ulrich Brocker and Dr. Heinz Junglas

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198010151

      Thumbnail image of graphical abstract

      The expected aromatic character is indeed found in the title compound (1) now synthesized for the first time. The 90 MHz 1H-NMR spectrum shows the NH proton to be exo oriented. The chemical shifts of the CH2 protons differ by 3.6 ppm.

    15. 1H-Azepine: NMR Spectroscopic and Chemical Characterization (pages 1016–1018)

      Prof. Dr. Emanuel Vogel, Dr. Hans-Josef Altenbach, Dipl.-Chem. Jacob-Matthias Drossard, Dr. Hans Schmickler and Dr. Hartmut Stegelmeier

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198010161

      Thumbnail image of graphical abstract

      1H-Azepine (1)—generated by a new method in solution at −78°C—could be characterized for the first time as a practically uniform seven-membered ring valence tautomer by its 1H- and 13C-NMR spectra. (1) polymerizes very readily. It forms 3H-azepine (2) with catalytic amounts of acid or base. (2) can be vacuum distilled, albeit with considerable losses.

    16. Intramolecular Oxidative Cyclization of 3-Benzyl-1,2,3,4-tetrahydroisoquinolines (pages 1018–1019)

      Dr. Johannes Hartenstein, Dipl.-Phys. Theo Heigl and Dr. Gerhard Satzinger

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198010181

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      Nature seemed to have overlooked 3-benzyl-1,2,3,4-tetrahydroisoquinolines, which is surprising in view of the enormous importance of 1-benzyl isomers. Model reactions on tetraalkoxy derivatives have now afforded the polycyclics (1) resembling natural morphinadienones.

    17. Total Reversibility of the Addition and Transylidation of Trialkyl(alkylidene)phosphoranes to Metal-Coordinated Carbon Monoxide (pages 1019–1020)

      Dipl.-Chem. Herbert Blau and Prof. Dr. Wolfgang Malisch

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198010191

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      The reactivity of phosphorus ylides towards carbonyl(cyclopentadienyl) complexes has been examined for the first time in the case of MeC5H4(CO)3Mn. This complex reacts with Me3P[DOUBLE BOND]CH2 (molar ratio 1:2) via ylide addition and transylidation to give the phosphorylated phosphonium manganoacylate (1), in a completely reversible reaction. The starting materials are recovered on dissolution of (1).

    18. Phosphorus Ylide Carbene Complexes of Manganese—Synthesis and Structure (pages 1020–1021)

      Prof. Dr. Wolfgang Malisch, Dipl.-Chem. Herbert Blau and Dr. Ulrich Schubert

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198010201

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      The first X-ray structure analysis of an ylide carbene complex has been performed on the manganese compound (1). This compound is accordingly to be regarded as a zwitterionic olefin of type (B).

    19. Metal-Assisted Reaction of Carbon Disulfide with the “Etriphos” Phosphane Ligand: Synthesis and Structure of [(Etriphos)Fe{S2C(Et2PCH2)2CMe2}](BF4)2 (pages 1021–1022)

      Dr. Claudio Bianchini, Dr. Andrea Meli, Dr. Annabella Orlandini and Prof. Dr. Luigi Sacconi

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198010211

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      The diamagnetic complex (2) containing pentacoordinate iron and a new bidentate disulfido ligand is formed on reaction of “Etriphos” (1) with CS2 and Fe(BF4)2·6H2O.

    20. Reversal of Stability in the Benzene/Dewar-Benzene System (pages 1022–1023)

      Prof. Dr. Günther Maier and Dipl.-Chem. Klaus-Albert Schneider

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198010221

      Thumbnail image of graphical abstract

      Thermal transformation of a benzene derivative into a Dewar benzene derivative has now been observed for the first time: dimethyl 3,4,5,6-tetra-tert-butylphthalate forms the Dewar benzene derivative (1) in 90% yield on heating to 120°C.

    21. Cobalt Mediated [2 + 2 + 2]-Cycloadditions: A Simple Route to Substituted Cyclopentadienones (pages 1023–1024)

      Dr. Ernst R. F. Gesing, Jeffrey P. Tane and Prof. Dr. K. Peter C. Vollhardt

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198010231

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      The production and oxidative demetalation of disilylcyclopentadienonecobalt complexes (1), n = 2–4, have now been accomplished in preparatively useful yields. These findings are of interest in connection with the synthesis of cyclopentanoid natural products.

    22. Polymetallic Complexes: Complexation of the Triangular Faces of Clusters by the Tripod Ligand, HC(PPh2)3 (pages 1024–1025)

      Dr. Anita A. Arduini, Dr. Ali A. Bahsoun, Prof. John A. Osborn and Christian Voelker

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198010241

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      Stabilization of the M4 cluster in M4(CO)12 carbonyl complexes by the “tripod” ligand HC(PPh2)3 is accomplished in almost quantitative yield with elimination of 3 CO. In the case of Co2Rh2(CO)12, the ligand adds only to the CoRh2 faces (and not to the Co2Rh faces).

    23. Template Synthesis of Clusters using the Tripod Ligand HC(PPh2)3 Ni3(CO)6(tripod) (pages 1025–1026)

      Prof. J. A. Osborn and Dr. George G. Stanley

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198010251

      The stepwise synthesis of the nickel cluster(3) from Ni(CO)4 and the “Tripod” ligand illustrates a possible application of this tris(phosphane). The first trinuclear nickel(0) complex is formed via (1) (with chelated Ni(CO)2 and a free PPh2 group) and (2) (with Ni(CO)3 attached to this group).

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    24. Novel Photocycloadditions of Dibromomaleimides to 1,3-Dimethyl-6-azauracil (pages 1026–1027)

      Dr. Géza Szilágyi and Prof. Dr. Heinrich Wamhoff

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198010261

      Thumbnail image of graphical abstract

      Possible model reactions for photochemotherapy are the photoreactions of pyrimidine bases and their aza analogues with cyclophilic molecules. The title reaction leads in high yields to (1), R = H, CH3 (depending upon the educt). No alkylation products are formed.

    25. A Photochemical Route to (7±)-Estrone (pages 1027–1029)

      Prof. Dr. Gerhard Quinkert, Dr. Wolf-Dietrich Weber, Dr. Ulrich Schwartz and Dr. Gerd Dürner

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198010271

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      In a convergent total synthesis of a steroid according to the principle A + D [RIGHTWARDS ARROW] AD [RIGHTWARDS ARROW] ABCD, the phototransient (1) (type AD) plays a central role. The starting materials are inexpensive and the reaction shows extreme regio- and diastereoselectivity.

    26. Asymmetric Total Synthesis of (+)-Estrone (pages 1029–1030)

      Prof. Dr. Gerhard Quinkert, Dr. Ulrich Schwartz, Dipl.-Chem. Herbert Stark, Dr. Wolf-Dietrich Weber, Dipl.-Chem. Helmut Baier, Dipl.-Chem. Friedheld Adam and Dr. Gerd Dürner

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198010291

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      Naturally occurring (+)-estrone (4) has been synthesized by the route described in the previous communications, except that the chiral D ring component is used. The key intermediate (1) forms the product (4) via the phototransient, see above, and (2) and (3).

    27. Selective Inclusion of Alcohols with a New Pyridino Crown (pages 1030–1032)

      Dr. Edwin Weber and Prof. Dr. Fritz Vögtle

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198010301

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      The highly variable crown ethers are a veritable treasure trove for host molecules, as demonstrated by the pyridino crowns (1) discovered in a systematic search. They (selectively) form 2:1 inclusion complexes (host:guest) with straight-chain alcohols up to C7H15OH.

    28. Cycloadditions with Silver Ion-Stabilized (2RS,3RS)-3-Methoxy-trans-Cycloheptene (pages 1032–1033)

      Dr. Heiner Jendralla

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198010321

      Thumbnail image of graphical abstract

      Stable trans-cycloheptene derivative (2a) and (2b) are formed by deamination of (1) in methanol in the presence of AgClO4 and AgO3SCF3. The expected cycloadducts, e.g. (3), are formed by reaction of (2a) with dienes, e.g. 1,3-cyclohexadiene.

    29. Li12Si7, a Compound Having a Trigonal Planar Si4 Cluster and Planar Si5 Rings (pages 1033–1034)

      Prof. Dr. Hans Georg von Schnering, Dr. Reinhard Nesper, Dipl.-Ing. Jan Curda and Prof. Dr. Karl-Friedrich Tebbe

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198010331

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      Three-pointed planar Si4 stars with unelucidated bonding and planar Si5 rings have been found in Li12Si7. In the formulation shown below with x = 4 and y = 10 the star could be an excited tetrahedrane state as Simath image; for x = y = 8 the star would be Simath image and isoelectronic with the carbonate ion.

    30. Planar Four-Coordinated Silicon? (page 1034)

      Prof. Dr. Jack D. Dunitz

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198010341

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      The exceptionally sensitive crystalline compound bis(o-phenylenedioxy)silane(1) was synthesized in 1979 by Meyer and Nagorsen as the first molecule with planar tetracoordinated silicon. In the absence of a detailed X-ray structure analysis, statements about the structure of (1) were based on arguments of crystallographic symmetry. According to Dunitz this argumentation has two weak points. Moreover, the chemical identity of the crystals examined does not appear to be established beyond all doubt. Nevertheless, (1) could be the first compound with planar tetracoordinated silicon.

    31. Planar Four-Coordinated Silicon—A Reply (page 1034)

      Prof. Dr. Günter Nagorsen and Dr. Heinrich Meyer

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198010342

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      The exceptionally sensitive crystalline compound bis(o-phenylenedioxy)silane(1) was synthesized in 1979 by Meyer and Nagorsen as the first molecule with planar tetracoordinated silicon. In the absence of a detailed X-ray structure analysis, statements about the structure of (1) were based on arguments of crystallographic symmetry. According to Dunitz this argumentation has two weak points. Moreover, the chemical identity of the crystals examined does not appear to be established beyond all doubt. Nevertheless, (1) could be the first compound with planar tetracoordinated silicon.

  3. Author Index

    1. Top of page
    2. Reviews
    3. Communications
    4. Author Index
    5. Subject Index
    1. Author Index (pages 1035–1038)

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198010351

  4. Subject Index

    1. Top of page
    2. Reviews
    3. Communications
    4. Author Index
    5. Subject Index
    1. Subject Index (pages 1039–1050)

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198010391

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