Angewandte Chemie International Edition in English

Cover image for Vol. 36 Issue 11

June 16, 1997

Volume 36, Issue 11

Pages 1135–1221

Currently known as: Angewandte Chemie International Edition

    1. Cover Picture (Angew. Chem. Int. Ed. Engl. 11/1997)

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199711331

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      The cover picture shows the intense yellow luminescence that is triggered when crystals of the trinuclear gold(I) complex [Au3(CH3[BOND]COCH3)3] come in contact with a drop of solvent. The prerequisite for this solvent-stimulated luminescence is the prior irradiation with long-wavelength UV light. This luminescence was totally unexpected, and was first discovered during the isolation of the complex when the resulting crystals were filtered and subsequently washed. The two emission spectra clearly reveal that the yellow luminescence (lower right spectrum) cannot arise from the dissolved species (upper left spectrum). Investigations into the origins of this phenomenon are reported by A. L. Balch et al. on pages 1179ff.

  1. Reviews

    1. Top of page
    2. Reviews
    3. Highlights
    4. Communications
    5. Book Reviews
    1. Oxidative Transformations of Organic Compounds Mediated by Redox Molecular Sieves (pages 1144–1163)

      Dr. Isabel W. C. E. Arends, Prof. Dr. Roger A. Sheldon, Dr. Martin Wallau and Prof. Dr. Ulf Schuchardt

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199711441

      Incorporation of redox metals into the framework of zeolites and related molecular sieves considerably extends their utility in organic synthesis. The structural diversity—including variation of the redox metal as well as size and polarity of the micropores—provides the possibility of designing tailor-made solid catalysts for liquidphase oxidations under mild conditions with O2, H2O2, and RO2H as oxidants. Important considerations for designing or choosing a suitable catalyst based on molecular sieves can be derived from the numerous examples, some of which are even in industrial use, of oxidation of synthetically interesting compounds (alkenes, alcohols, aldehydes, amines, arenes) as well as the different methods for synthesizing redox molecular sieves (incorporation of redox metal by ion exchange by substitution of framework atoms or encapsulating a metal complex).

    2. Alkenylidenes in Organic Synthesis (pages 1164–1170)

      Prof. Dr. Wolfgang Kirmse

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199711641

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      Diversity and efficiency is offered by the method of converting ketones into cyclopentenes by selective intramolecular insertion of alkenylidenes R2C[DOUBLE BOND]C: into C[BOND]H bonds. The chain extension that converts an aldehyde into an alkyne can also be achieved with these carbenes. These two possibilities are generalized in the equation below.

  2. Highlights

    1. Top of page
    2. Reviews
    3. Highlights
    4. Communications
    5. Book Reviews
    1. “Hyt was of Gold, and Shon so Bryghte…”: Luminescent Gold(I) Compounds (pages 1171–1173)

      Priv.-Doz. Dr. Lutz H. Gade

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199711711

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      Photochemical switches, energy storage devices, or photochemical sensors are potential applications of luminescent gold complexes. The basis for this expectation is the spectacular discovery by Balch et al., who observed that a trinuclear gold complex (see picture) gave rise to an intense emission upon dissolution in an organic solvent after previous irradiation with near-UV light (Angew. Chem. Int. Ed. Engl.1997, 36, 1179).

    2. Enzymes and Transition Metal Complexes in Tandem—A New Concept for Dynamic Kinetic Resolution (pages 1173–1174)

      Dr. Rainer Stürmer

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199711731

      Some enzymes tolerate bases and transition metal catalysts at elevated temperatures—conditions which, for example, Williams et al. and Bäckvall et al. have shown are suitable for racemizing secondary alcohols by Meerwein–Ponndorf reduction/Oppenauer oxidation. Enzyme-catalyzed acylation under Meerwein-Pondorf-Varley conditions facilitates dynamic kinetic resolutions of alcohols.

  3. Communications

    1. Top of page
    2. Reviews
    3. Highlights
    4. Communications
    5. Book Reviews
    1. Silver-Tellurolate Polynuclear Complexes: From Isolated Cluster Units to Extended Polymer Chains (pages 1176–1179)

      Dr. John F. Corrigan, Prof. Dr. Dieter Fenske and Dr. William P. Power

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199711761

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      In the presence of tertiary phosphanes, AgCl reacts readily with the reagent Te(Ph)SiMe3 to yield silver-tellurolate polynuclear complexes. In the case of PMe3, the polymer [Ag103-TePh)10(PMe3)2] (shown below) is formed, in which the TePh ligands serve as both inter- and intracluster bridges.

    2. Solvent-Stimulated Luminescence from the Supramolecular Aggregation of a Trinuclear Gold(I) Complex that Displays Extensive Intermolecular AuċAu Interactions (pages 1179–1181)

      Jess C. Vickery, Dr. Marilyn M. Olmstead, Dr. Ella Y. Fung and Prof. Dr. Alan L. Balch

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199711791

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      Striking yellow luminescence is observed upon addition of a drop of solvent to colorless crystals of [Au3(CH3N[DOUBLE BOND]COCH3)3] that were previously irradiated with near-visible light. The trigonal prismatic stacking of individual molecules of the triangular cluster in the solid state (shown on the right) sheds light on the possible mechanisms for this luminescence.

    3. Remarkable Template Effect of a Lewis Acidic Receptor in Intramolecular Radical Cyclizations (pages 1181–1183)

      Dr. Takashi Ooi, Yasutoshi Hokke and Prof. Keiji Maruoka

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199711811

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      The bowl-shaped reaction environment created by the Lewis acid aluminum tris(2,6-diphenylphenoxide) has been utilized as an efficient template in intramolecular radical cyclizations. The pathway and the stereoselectivity of the radical cyclization can be altered by using this template. A schematic representation of the transition state of the template assisted reaction is shown on the right.

    4. Conjugate Allylation to α,β-Unsaturated Aldehydes with the New Chemzyme p-F-ATPH (pages 1183–1185)

      Dr. Takashi Ooi, Yuichiro Kondo and Prof. Keiji Maruoka

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199711831

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      Success at last: The 1,4-allylation of α,β-unsaturated aldehydes with selectivities up to 95/5 and yields of 83% has been achieved thanks to the newly developed Lewis acidic receptor p-F-ATPH (L = 2,6-(pFC6H4)2C6H3O. In addition to a coordination site for the aldehyde, this possesses an appropriate coordination site for a reactive nucleophile, as shown schematically on the right.

    5. Strong, Rapid Binding of a Platinum Complex to Thymine and Uracil Under Physiological Conditions (pages 1185–1187)

      Dr. Nicola Margiotta, Dr. Abraha Habtemariam and Prof. Dr. Peter J. Sadler

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199711851

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      Novel chelate ring-opening occurs when cytotoxic bis(aminoethylphosphanyl)platinum(II) binds rapidly to the N3 atom of the DNA base thymine (T) and RNA base uracil (U) at pH 7 in the presence of chloride ions (depicted on the right). This is in contrast to cisplatin, which shows little binding to thymine or uracil under similar conditions, and thus opens the possibility for base-specific attack on DNA and RNA.

    6. Formation of Isobenzenes by Thermal Isomerization of 1,3-hexadiene-5-yne Derivatives (pages 1187–1190)

      Prof. Dr. Henning Hopf, Dipl.-Chem. Harald Berger, Prof. Dr. Gerhard Zimmermann, Dr. Uta Nüchter, Prof. Dr. Peter G. Jones and Ina Dix

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199711871

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      Prototype of a new aromatization reaction: thermal rearrangement of 1,3-hexadiene-5-yne (1) to benzene (3) via isobenzene 2, a highly reactive benezene isomer. Trapping experiments with styrene and the behavior of arenes containing 1 as a subunit indicate that this isomerization is also suitable for preparing condensed arenes and fullerene fragments.

    7. Synthesis of 3,9,15,19,21,23-Hexaazakekulene (pages 1190–1191)

      Arnaud Tatibouët, Richard Hancock, Dr. Martine Demeunynck and Jean Lhomme

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199711901

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      Blue fluorescence is exhibited by the hexaazakekulene 1, the first fully aromatic heteroanalogue of kekulene. It was synthesized in four steps from formaldehyde and proflavine (3,6-diaminoacridine). Although 1 is insoluble in organic solvents, it is slightly soluble in strong acids such as methanesulfonic or trifluoroacetic acid—probably due to protonation.

    8. Stereoselective Synthesis of a C[BOND]Glycosidic Analog of N-Glucoasparagine (pages 1191–1192)

      Dipl.-Chem. Fred Burkhart, Dr. Matthias Hoffmann and Prof. Dr. Horst Kessler

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199711911

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      The orthogonally protected gylcosylated amino acid building block 1 for the synthesis of peptidomimetics was prepared by the coupling of an amino acid aldehyde with a glycosyl dianion of glucosamine. This new C-glycosylated amino acid displays an improved metabolic stability and thus an improved bioavailability because of the single carbon chain between the sugar residue and the amino acid and because of the C[BOND]C linkage at the anomeric center.

    9. Synthesis and Characterization of the Carbide Cubane Cluster [Fe3(CO)9Te43-CTeBr4)] with an Unusual Tetrahedral CTe4 Unit (pages 1193–1194)

      Dr. Jeffrey R. Eveland and Prof. Dr. Kenton H. Whitmire

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199711931

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      A carbide carbon atom as a vertex stabilized by coordination to the Lewis acid TeBr4 is a feature of the cubane-like cluster 1 shown on the right. This complex, which is indefinitely stable in the solid state but dissolves only in DMSO—and then with rapid decomposition—is the ultimate product in the reaction between [Te2Fe3(CO)9] and CBr4.

    10. Synthesis of the Bicyclic Core of CP-225,917 and CP-263,114 by an Intramolecular Diels–Alder Reaction (pages 1194–1196)

      Prof. Dr. K. C. Nicolaou, Dr. Michael W. Härter, Dr. Lee Boulton and Dr. Bernd Jandeleit

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199711941

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      New lead compounds with promising biological activity are represented by CP-225,917 and CP-263,114. An approach based on an intramolecular Diels-Alder reaction for the total synthesis of these compounds is exemplified by the synthesis of racemic bicyclo[4.3.1]dec-1(9),4-dienes 2a,b from triene 1.

    11. Metal-Free Bacterial Haloperoxidases as Unusual Hydrolases: Activation of H2O2 by the Formation of Peracetic Acid (pages 1196–1199)

      Dipl.-Chem. Martin Picard, Dr. Jürgen Gross, Dipl.-Chem. Ellen Lübbert, Dipl.-Lebensmittelchem. Sabine Tölzer, Susanne Krauss, Prof. Dr. Karl-Heinz van Pée and Prof. Dr. Albrecht Berkessel

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199711961

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      How does the catalytic set-up of a hydrolase activate H2O2 for enzymatic oxidations? The oxidizing species is a peracid, as these studies with the metal-free haloperoxidases CPO-P and CPO-T clearly show. The analogy between the hydrolase and haloperoxidase reactions is elucidated in the reactions below.

    12. Synthesis of Rotaxanes by Brief Melting of Wheel and Axle Components (pages 1199–1201)

      Dr. Mirko Händel, Dipl.-Chem. Marcus Plevoets, Dipl.-Chem. Sven Gestermann and Prof. Dr. Fritz Vögtle

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199711991

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      Fast and simple: Rotaxanes and pseudorotaxanes are synthesized by simply melting their wheel and axle components for one minute. The complementarity between the cavity of the wheel and the spatial demands of the stopper groups was designed to permit a temperature-controlled “slipping off” process in solution.

    13. A Convenient Way to Novel FeIV Complexes with Mixed N/S/P Coordination Spheres and “Innocent” Ligands (pages 1201–1203)

      Prof. Dr. Dieter Sellmann, Dipl.-Chem. Susanne Emig, Dr. Frank W. Heinemann and Dr. Falk Knoch

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199712011

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      A simple one-pot reaction with readily accessible compounds [Eq. (a)] provides a route to high-valent molecular FeIV complexes with a N/S/P coordination sphere. The FeIV character of the metal center, which is stabilized by π-donor bonds from the lone pairs of electrons of the amide N and thiolate S donors, is confirmed by spectroscopic and structural data of 1 (R [DOUBLE BOND] nPr). The L4− ligand is “innocent”!

    14. New Motifs in Aurophilic Self-Assembly: Synthesis and Structures of [Au(NH[DOUBLE BOND]CMe2)2]CF3SO3 and [Au(C[TRIPLE BOND]CSiMe3)(CNtBu)] (pages 1203–1205)

      Prof. Dr. José Vicente, Prof. Dr. María-Teresa Chicote, María-Dolores Abrisqueta, Rita Guerrero and Prof. Dr. Peter G. Jones

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199712031

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      Two new types of gold–gold interactions are described. Crystals of 1 contain polymeric chains with short contacts between cationic gold centers, while in 2 one gold atom is coordinated nearly trigonally by three others.

    15. Electron Transfer Induced C[BOND]S Bond Cleavage in Rhenium and Technetium Thioether Complexes: Structural and Chemical Evidence for π Back-Donation to C[BOND]S σ* Orbitals (pages 1205–1207)

      Gregory E. D. Mullen, Dr. Michael J. Went, Sigrid Wocadlo, Dr. Anne K. Powell and Dr. Philip J. Blower

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199712051

      The trends in carbon-sulfur bond length for complexes of 1,4,7-trithiacyclononane (9S3) provide compelling evidence that C[BOND]S σ* orbitals accept π-electron density from the metal. As the metal d-orbital energy and occupancy increase, this leads ultimately to cleavage of the C[BOND]S bonds with concomitant release of ethene in the Re and Tc complexes [Eq. (a)].

      • equation image
    16. Highly Enantioselective Reduction with Novel, Bridged NADH Models (pages 1207–1211)

      Dr. Nobuhiro Kanomata and Prof. Dr. Tadashi Nakata

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199712071

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      Biomimetic reduction of benzoylformate to mandelate with 97–99% ee was achieved with the diastereomeric, bridge NADH models (S,S)-1 and (R,S)-1. The oligomethylene bridge acts as an “enzyme wall” and hinders the approach of the substrate from one side of the dihydropyridine ring. Isomers 1 were synthesized from the corresponding bridged nicotinate precursor, which was prepared by the reaction of formyl-substituted (vinylimino)phosphorane with methyl propiolate.

    17. Enzymatic Resolution of Alcohols Coupled with Ruthenium-Catalyzed Racemization of the Substrate Alcohol (pages 1211–1212)

      Anna L. E. Larsson, B. Anders Persson and Prof. Jan-E. Bäckvall

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199712111

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      A specifically designed acyl donor, an efficient enzyme, and a stable and reliable ruthenium catalyst are fundamental for the resolution of the racemic alcohols described here (see scheme on the right). For R1 [DOUBLE BOND] Ph and R2 [DOUBLE BOND] Me, 100% conversion into the corresponding acetate was achieved with greater than 99.5% ee.

    18. Tris(tri-tert-butylsilyl)digallanyl (tBu3Si)3Ga2: A New Type of Compound for a Heavy Group 13 Element (pages 1213–1215)

      Prof. Dr. Nils Wiberg, Dipl.-Chem. Kerstin Amelunxen, Prof. Dr. Heinrich Nöth, Dr. Holger Schwenk, Prof. Dr. Wolfgang Kaim, Dr. Axel Klein and Dipl.-Chem. Thomas Scheiring

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199712131

      Blue-black trisupersilyldigallanyl, a new metastable inorganic radical, forms in the reaction of GaCl3 with tBu3SiNa in pentane at room temperature according to Equation (a). The X-ray structure analysis reveals that it contains a planar Si2GaIIGaI and a nearly linear GaIIGaISi framework; according to the ESR spectrum the unpaired electron resides in both Ga atoms. Surprisingly, the analogous reaction of AlCl3 and tBu3SiNa (Al instead of Ga in Equation (a)) does not lead to trisupersilyldialanyl, but to red tetrasupersilyldialane (tBu3Si)2Al–Al(SitBu3)2.

      • equation image
    19. Lithiation of a Simple Amine with a Large Excess of n-Butyllithium: The Remarkable Product (Ph2NLi) · [Ph(C6H4Li)NLi]2 · (nBuLi)2 · (Et2O)4 (pages 1215–1217)

      Robert P. Davies, Dr. Paul R. Raithby and Dr. Ronald Snaith

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199712151

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      What lithiates what? In a reaction between Ph2NH and excess nBuLi the aggregate 1 comprising nBuLi, monolitiated amine, and doubly lithiated amine units forms. The structure (see picture) raises interesting questions about lithiation reaction mechanisms.

  4. Book Reviews

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