Angewandte Chemie International Edition in English

Cover image for Vol. 17 Issue 7

July 1978

Volume 17, Issue 7

Pages 473–543

Currently known as: Angewandte Chemie International Edition

    1. Cover Picture (Angew. Chem. Int. Ed. Engl. 7/1978)

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.197804731

    2. Graphical Abstract (Angew. Chem. Int. Ed. Engl. 7/1978)

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.197804732

  1. Reviews

    1. Top of page
    2. Reviews
    3. Communications
    4. Abstracts
    5. Book Reviews
    1. Reflections on an Anniversary of Chemical Synthesis (pages 473–476)

      Prof. Dr. Gerhard Quinkert

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.197804733

      The significance of chemistry as a science and as a branch of industry, as well as its role in the evolution of scientific thought during the past 150 years, are thoughts which come to mind while contemplating the development of organic synthesis.

    2. Intramolecular Ene Reactions in Organic Synthesis (pages 476–486)

      Prof. Dr. Wolfgang Oppolzer and Prof. Dr. Victor Snieckus

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.197804761

      Thumbnail image of graphical abstract

      Thermal cyclization of dienes, enynes, enones, and similar unsaturated systems illustrate the preparative potential of the intramolecular ene reaction. A wealth of substituted, annelated, and bridged ring systems are accessible—regio- and stereo-selectively—in this way.

    3. Organic Reactions at Alumina Surfaces (pages 487–496)

      Gary H. Posner

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.197804871

      Thumbnail image of graphical abstract

      Addition, reduction, oxidation, substitution, elimination, and other reactions are induced in organic molecules absorbed on alumina, frequently under very mild conditions. Selective reduction of the formyl group in the chromone derivative (1) is a representative reaction.

    4. Ion Implantation into Semiconductors (pages 496–505)

      Dr. Christian Fritzsche

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.197804961

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      Precision doping of solids, e.g. for production of semiconductor components, can be accomplished by bombardment of substrate material with accelerated ions of dopant. Implantation of boron or phosphorus in silicon or of selenium in gallium arsenide can be cited as examples. Laser repair of radiation damage commands industrial interest.

    5. Cobalt-Catalyzed Pyridine Syntheses from Alkynes and Nitriles (pages 505–515)

      Priv.-Doz. Dr. Helmut Bönnemann

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.197805051

      Thumbnail image of graphical abstract

      Soluble organocobalt catalysts permit selective, single-step formation of substituted pyridines under mild conditions: mono-, di-, and tri-substituted pyridines are obtained at will from nitriles and alkynes.

  2. Communications

    1. Top of page
    2. Reviews
    3. Communications
    4. Abstracts
    5. Book Reviews
    1. More about π- and σ-Succinimidyl Radicals: Ring Opening Reactions (pages 515–516)

      Prof. Dr. Philip S. Skell, Dr. James C. Day and Joseph P. Slanga

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.197805151

      Thumbnail image of graphical abstract

      New ideas about the reactions of N-halosuccinimides help to rationalize many apparently contradictory observations. The key hypothesis is that σ-succinimidyl radicals undergo rapid and reversible cleavage whereas π radicals do not.

    2. Methylenesulfur Tetrafluoride H2C[DOUBLE BOND]SF4 (pages 516–518)

      Dipl.-Chem. Gert Kleemann and Priv.-Doz. Dr. Konrad Seppelt

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.197805161

      The new pentacoordinated species H2C[DOUBLE BOND]SF4, a gas stable up to at least 100°C, is not an ylide, but instead shows carbene-type reactions. The 19F- and 1H-NMR spectra are compatible with a Berry pseudorotation.

      • equation image
    3. 8,13-Dichloro-1,4-dimethyl-9-(3,5-dimethylbenzyl)triptycene: Atropisomerism about a Cmath image[BOND]CH2 Bond (pages 518–519)

      Dr. Gaku Yamamoto and Prof. Dr. Michinori Ōki

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.197805181

      Thumbnail image of graphical abstract

      Atropisomerism about the bond between the triptycene bridgehead and the benzyl group has been observed in compound (1) which contains two Cl and one CH3 group as peri-substituents. ap-(1) and sc-(1) coexist in a 1:2 equilibrium ratio at 80°C; the rotational barrier is 27 kcal/mol. Analogous 9-benzyltriptycenes with one or two peri-substituents have rotational barriers of ca. 13 and ca. 18 kcal/mol, respectively.

    4. Tetra-tert-butylcyclopentadienone (pages 519–520)

      Prof. Dr. Günther Maier and Dipl.-Chem. Stephan Pfriem

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.197805191

      Thumbnail image of graphical abstract

      The stable tetrahedrane derivative(3)—the very first alkyl-substituted tetrahedrane—has now been synthesized photochemically from the cyclopentadienone (1). 1H-NMR, 13C-NMR, mass, and IR spectra, as well as the reversible isomerization to (2), are compatible with the tetrahedrane structure. The unexpected stability of the compound is attributed to substitution of all four corners of the skeleton with bulky groups.—The starting material (1), which is also new could only be prepared under “forbidden conditions”.

    5. Tetra-tert-butyltetrahedrane (pages 520–521)

      Prof. Dr. Günther Maier, Dipl.-Chem. Stephan Pfriem, Dipl.-Chem. Ulrich Schäfer and Priv.-Doz. Dr. Rudolf Matusch

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.197805201

      Thumbnail image of graphical abstract

      The stable tetrahedrane derivative(3)—the very first alkyl-substituted tetrahedrane—has now been synthesized photochemically from the cyclopentadienone (1). 1H-NMR, 13C-NMR, mass, and IR spectra, as well as the reversible isomerization to (2), are compatible with the tetrahedrane structure. The unexpected stability of the compound is attributed to substitution of all four corners of the skeleton with bulky groups.—The starting material (1), which is also new could only be prepared under “forbidden conditions”.

    6. Lithium ortho-Lithiobenzyl Alkoxides (pages 521–522)

      Dipl.-Chem. Norbert Meyer and Prof. Dr. Dieter Seebach

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.197805211

      Thumbnail image of graphical abstract

      A new lithium reagent, lithium o-lithiobenzyl oxide (1), provides a facile entry to compounds of types (2) and (3). After transformation into an analogous reagent substituted benzyl alcohols react with benzaldehyde to give compounds of type (4). Products (2) to (4) cannot be synthesized from phthalic acid derivatives.

    7. Simple Method for the Esterification of Carboxylic Acids (pages 522–524)

      Bernhard Neises and Prof. Dr. Wolfgang Steglich

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.197805221

      Addition of 4-dimethylaminopyridine (DMAP) accelerates the dicyclohexylcarbo-diimide (DCC)-activated esterification of carboxylic acids to such an extent that side reactions are eliminated and even sensitive acids such 2,5-cyclohexadiene-1-carboxylic acid readily form the tert-butyl ester. DMAP has so far been used mainly as acylation catalyst.

      • equation image
    8. Photochemical Reductive trans-Elimination from trans-Diazidotetracyanoplatinate(IV) (pages 524–525)

      Prof. Dr. Arnd Vogler, Dipl.-Chem. Alfred Kern and Prof. Dr. Jürgen Hüttermann

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.197805241

      The first light-induced reductive trans elimination has been observed with the trans-configurated PtIV complex (1). The primary photochemical step leads, via simultaneous two-electron reduction avoiding a PtIII intermediate, to two N3 radicals which afford N2 and N atoms at low temperature.

      • equation image
    9. A Simple Synthesis of 2′-Deoxy-2′-fluorocytidine by Nucleophilic Substitution of 2,2′-Anhydrocytidine with Potassium Fluoride/Crown Ether (page 525)

      Priv.-Doz. Dr. Rudolf Mengel and Dr. Wilhelm Guschlbauer

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.197805251

      Thumbnail image of graphical abstract

      Fluorination of anhydrocytidine (1) to give deoxyfluorocytidine (2), a precursor of pharmacologically interesting compounds can be accomplished with DMF/KF/crown ether with rigorous exclusion of water. Traces of water transform (1) into (3).

    10. High-Pressure Carbonylation of Metal-Coordinated Carbenes and Hydrogenolysis of the Ketene Complexes (pages 525–526)

      Dr. Wolfgang A. Herrmann and Johann Plank

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.197805252

      Thumbnail image of graphical abstract

      A model of a step in the Fischer-Tropsch synthesis has been found in the newly accomplished high-pressure carbonylation of the carbene complexes (1) to the ketene complexes (2). Hydrogenolysis of (2) is also new.

    11. Reactivity of Phenyl Vinyl Selenide with Nucleophiles and Bases (pages 526–527)

      Dipl.-Chem. Mireille Sevrin, Dipl.-Chem. Jean N. Denis and Prof. Dr. Alain Krief

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.197805261

      Thumbnail image of graphical abstract

      Four possible reactions of phenyl vinyl selenide (CH2[DOUBLE BOND]CH[BOND]SePh) have been discovered on treatment with nucleophiles or bases: Se[BOND]C cleavage, addition, metalation, elimination. The reaction pathway is very sensitive to solvent and reaction conditions. The species (1), (2), and/or (3) may be formed initially with nBuLi, and (3) and/or (4) (+acetylene) with LiN(iPr)2.

    12. Synthesis and Structure of the Tetradecker Complex Bis(tricarbonylmanganese-μ, η-thiadiborolene)iron (pages 527–528)

      Prof. Dr. Walter Siebert, Dipl.-Chem. Christian Böhle, Dr. Carl Krüger and Dr. Yi-Hung Tsay

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.197805271

      Thumbnail image of graphical abstract

      The first tetradecker complex(2) contains four planes of ligands (two C2B2S rings as π6- and two (CO)3 groups as σ6-electron donors) which are held together by three d6 metal ions. Compound (2) is synthesized by heating of (1) with Mn2(CO)10 and [CpFe(CO)2]. The resulting triple-decker complex is transformed into the salt [(C6H6)Fe·(1)·Mn(CO)3]+AlClmath imagevia ligand exchange. Thermolysis of the salt gives the orange-red (2).

    13. 4-Alkoxy-1-phenylphosphacyclohexadiene [RIGHTWARDS ARROW] 1-Alkoxy-1-phenyl-λ5-phosphorin Rearrangement (pages 528–530)

      Prof. Dr. Gottfried Märkl, Dipl.-Chem. Rainer Liebl and Alois Hüttner

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.197805281

      Thumbnail image of graphical abstract

      An entry to C-monosubstituted λ5-phosphorins(2) is provided by rearrangement of the phosphacyclohexadienes (1). The arsenic compounds corresponding to (1) form λ3-arsenins under analogous conditions.

    14. Synthesis of N-Methyliminosulfur Tetrafluoride, CH3N[DOUBLE BOND]SF4, from the Cation CH3NSFmath image (page 530)

      Dr. Rüdiger Mews

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.197805301

      Stepwise addition of polar reagentsmath image[BOND]math image to N[TRIPLE BOND]SF3(1) was formerly impossible in the case of “methyl fluoride”; the salt (2) and the tetrafluoride (3) are stable compounds.

      • equation image
    15. An Organometallic Complex with Coordinatively Bound Water: [{(η-C5H5)2Ti(H2O)}2O]S2O6 (page 531)

      Prof. Dr. Ulf Thewalt and Dipl.-Phys. Gerhard Schleussner

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.197805311

      Thumbnail image of graphical abstract

      The first organotitanium complex with H2O as inner-sphere ligand has now been characterized by X-ray structure analysis. Compound (1), 2X = dithionate, is formed from (C5H5)2TiCl2 and Na2S2O6·2H2O in water.

    16. 12-[2.2]Paracyclophane)chromium(0) (pages 531–532)

      Prof. Dr. Christoph Elschenbroich, Dipl.-Chem. Reinhart Möckel and Dipl.-Chem. Ulrich Zenneck

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.197805312

      Thumbnail image of graphical abstract

      Insertion of a chromium atom between the benzene rings of [2,2]paracyclophane has been accomplished by co-condensation of this ligand with chromium atoms at −196°C. Among other products, (1) is accompanied by bis(η6-[2.2]paracyclophane)chromium(0). The novel complex (1) can be sublimed and survives eight days' standing in HCl.

    17. Higher-Order Derivative Spectrophotometry for the Fine Resolution of UV/VIS Spectra (pages 532–533)

      Univ.-Doz. Dr. Gerhard Talsky, Dipl.-Chem. Lothar Mayring and Hans Kreuzer

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.197805321

      Low-noise, reproducible UV/VIS spectra up to the 7th derivative can now be plotted on-line with the aid of a novel analog computer unit. Optimum resolution is usually achieved up to the 4th derivative: all shoulders, terraces, and points of inflection of unipolar signals are generally transformed into bipolar signals. Numerous applications exist.

    18. Complex Stabilization by Bifurcated Hydrogen Bonds: Bis[2-(o-methoxyphenoxy)ethoxyethyl] Ether-Thiourea (page 534)

      Dr. Il-Hwan Suh and Prof. Dr. Wolfram Saenger

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.197805341

      Thumbnail image of graphical abstract

      The hydrogen bonds in the polyether-thiourea complex(1) belong to a very rare type: each H atom of the thiourea guest molecule is linked to two O atoms of the polyether; the resulting bridges emanating from NH are reminiscent of two-pronged forks.

    19. Directed Synthesis of [Mo3S13]2−, an Isolated Cluster Containing Sulfur Atoms in Three Different States of Bonding (page 535)

      Prof. Dr. Achim Müller, Dr. Sabyasachi Sarkar, Dr. Ram Gopal Bhattacharyya, Dr. Siegfried Pohl and Mechtild Dartmann

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.197805351

      Thumbnail image of graphical abstract

      Transition metal-suffer clusters, possessing interest as model compounds for bioinorganic chemistry, have previously been prepared mainly by unusual reactions and in frequently low yields. The synthesis of (NH4)2[Mo3S(S2)6]·½H2O has now been accomplished in aqueous solution from MoCl4(py)2 and ammonium polysulfide.

    20. Optically Active Polyvinyl Compounds with Chirality in the Main Chain (pages 535–537)

      Prof. Dr. Günter Wulff, Dr. Karl Zabrocki and Dipl.-Chem. Johann Hohn

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.197805352

      Thumbnail image of graphical abstract

      Linear polymer chains containing chiral regions are formed on radical copolymerization of p-vinylphenylboronic acid, bound to a D-mannitol template, with methyl methacrylate. After removal of the template, the optically active co-polymer contains asymmetric triads such as I.

    21. Directed Cooperativity and Site Separation of Mercapto Groups in Synthetic Polymers (pages 537–538)

      Prof. Dr. Günter Wulff and Dr. Ilona Schulze

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.197805371

      Thumbnail image of graphical abstract

      A polymeric model system, sensitive only to the distance between the functional groups, is obtained by copolymerization of (1) with styrene and/or divinylbenzene. After reduction the sulfur is present largely as SH groups which can be reoxidized almost completely to S[BOND]S bridges. A highly pronounced site separation of SH groups could be accomplished (<5% reoxidation) in comparable experiments with (2).

    22. A New High-Pressure Phase of Barium Disilicide (pages 538–539)

      Dr. Jügen Evers, Gilbert Oehlinger and Prof. Dr. Armin Weiss

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.197805381

      Thumbnail image of graphical abstract

      A three-dimensional network made up of three-coordinate Si atoms is present in a new cubic high-pressure phase of BaSi2. On treatment at high pressure and high temperature, the isolated Si4 tetrahedra of the normal-pressure phase can polymerize not only to the known puckered Si layers but also to the regular three-dimensional structure (1).

  3. Abstracts

    1. Top of page
    2. Reviews
    3. Communications
    4. Abstracts
    5. Book Reviews
    1. ABSTRACTS (page 540)

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.197805401

  4. Book Reviews

    1. Top of page
    2. Reviews
    3. Communications
    4. Abstracts
    5. Book Reviews
    1. Book Review: Reaction Mechanisms in Organic Chemistry. By F. Badea (page 542)

      Jürgen Sauer

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.197805421

    2. Book Review: Vibrational Spectra of Organometallic Compounds. By E. Maslowsky, Jr. (page 542)

      Helmut Fischer

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.197805422

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