Angewandte Chemie International Edition in English

Cover image for Vol. 33 Issue 1

January 17, 1994

Volume 33, Issue 1

Pages 3–129

Currently known as: Angewandte Chemie International Edition

    1. Cover Picture (Angew. Chem. Int. Ed. Engl. 1/1994)

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.199400011

      Thumbnail image of graphical abstract

      The cover picture shows the structural formula of taxol, R1 = Ph, R2 = OAc, superimposed on the needles of the European yew (photograph: S. C. Wilson, TIME-LIFE Magazine, USA). The source of this cytostatic agent till now has been the bark of the Pacific yew; however, about 3000 trees had to be sacrificed to obtain enough taxol to treat 500 patients. As a rapidly regenerable source of a precursor of taxol, the yew needles can help to remedy the situation, since the 10-deacetylbaccatin III isolable from them can be converted into, for instance, taxotere (R1 = tBuO, R2 = OH) or taxol. Nevertheless, more abundant taxol sources and methods to make taxol accessible by semisynthesis or total synthesis are being sought. The fascinating history of taxol, unfolding along the highly interwoven boundary between medicine, cellular biology, and organic chemistry, is summarized by Nicolaou et al. on pages 45–66.

    2. Graphical Abstract (Angew. Chem. Int. Ed. Engl. 1/1994) (pages 3–10)

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.199400031

  1. Reviews

    1. Top of page
    2. Reviews
    3. Highlights
    4. Communications
    5. Book Reviews
    6. New Books
    1. Chemistry and Biology of Taxol (pages 15–44)

      Prof. Dr. Kyriacos Costa Nicolaou, Dr. Wei-Min Dai and Mr. Rodney Kiplin Guy

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.199400151

      Is EXAFS spectroscopy a promising method? Yes, because the element-specific determination of local structures in situ is possible, regardless of the sample's physical state and even at very high dilution. In addition to the principle limitations of this method (differentiation cannot be made between neighboring elements in the periodic table, different backscatterers present at similar distances cannot yield unambiguous results), technical problems (only a few synchrotron radiation sources, data analysis only possible with extensive simulation programs) hinder the development. Although this method has not been in use for very long it has afforded interesting results, for example, in catalysis and the structural characterization of biological systems.

    2. X-Ray Absorption Spectroscopy of Amorphous Solids, Liquids, and Catalytic and Biochemical Systems—Capabilities and Limitations (pages 45–66)

      Prof. Dr. Helmut Bertagnolli and Dr. Teja S. Ertel

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.199400451

      Thumbnail image of graphical abstract

      A promising antineoplastic chemotherapeutic but hampered by severely limited availability, taxol is described here together with its biological effects and the efforts to increase its accessibility through chemical synthesis. The challenges for the synthetic chemist lie in the eight-membered ring, the densely packed nature of the molecule, and the many oxygen functionalities. An arbitrarily chosen example of an approach to the ABC ring system of taxol is the sequence from 1 through several steps to 2 and finally to 3.

  2. Highlights

    1. Top of page
    2. Reviews
    3. Highlights
    4. Communications
    5. Book Reviews
    6. New Books
    1. Cooperativity in Rh2 Complexes: High Catalytic Activity and High Regioselectivity in the Hydroformylation of Olefins (pages 67–69)

      Prof. Dr. Georg Süss-Fink

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.199400671

      Thumbnail image of graphical abstract

      A breakthrough in tailor-made homogeneous catalysts has been achieved by Stanley et al., who synthesized the rac-Rh2 complex 1 with a new tetraphosphane ligand, which catalyzes the hydroformylation of olefins with a high activity and extremely selectively. The combination of these important catalytic properties is traced back to the intramolecular interaction of the two Rh centers fixed by the ligand matrix.

    2. Oxidation of Weakly Activated C[BOND]H Bonds (pages 69–72)

      Dr. Oliver Reiser

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.199400691

      Thumbnail image of graphical abstract

      The functionalization of hydrocarbons by selective oxidation is of great technical importance. Two new, effective reagents, (perfluoroalkyl)oxaziridines 1a, b, hydroxylate the C[BOND]H bonds at tertiary C atoms with high selectivity and in good yield. It remains to be seen if they are more economical and efficient than the tried-and-true dioxiranes and RuCl3/NaIO4.

  3. Communications

    1. Top of page
    2. Reviews
    3. Highlights
    4. Communications
    5. Book Reviews
    6. New Books
    1. Free-Energy Relationship for Mesolytic Cleavage of C[BOND]C Bonds (pages 73–75)

      Prof. Dr. Przemyslaw Maslak, Thomas M. Vallombroso, Dr. William H. Chapman Jr. and Dr. Javier N. Narvaez

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.199400731

      Thumbnail image of graphical abstract

      What is the functional relationship between the kinetics and thermodynamics for an elementary reaction in solution? This fundamental question was investigated for unimolecular fragmentations of C[BOND]C bonds in radical ions of bibenzylic substrates such as 1. A Marcus-type free-energy relationship with a parabolic shape fitted the data well. The results imply that mesolytic cleavages have low intrinsic barriers (about 3 kcalmol−1).

    2. A Cluster-Bound Triply-Bridging Phosphorus Atom Coordinated to Four (Ph3P)Au+ Units: [Fe3(CO)9P{Au(PPh3)}4][BAr4] (pages 75–77)

      Deborah L. Sunick, Dr. Peter S. White and Prof. Cynthia K. Schauer

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.199400751

      Thumbnail image of graphical abstract

      The seven-coordinate phosphorus atom in the title compound is bound to a slightly distorted square-planar Au4 array (see structure on the right). Despite the fact that the phosphorus atom is donating all but two of its electrons to the Fe3 cluster, it is still able to act as a nucleus for the aggregation of four gold fragments.

    3. Competing Reactions of Silenes: [2+2], [4+2], and [6+2] Cycloadditions with Cycloheptadiene and Cycloheptatriene (pages 77–80)

      Dr. Wolfgang Ziche, Dr. Claudia Seidenschwarz, Prof. Norbert Auner, Dr. Eberhardt Herdtweck and Dr. Norbert Sewald

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.199400771

      Thumbnail image of graphical abstract

      Silabicyclo[4.2.1]nonadienes 3 are two of the products of the reaction of silene 1 and cycloheptatriene. Besides these unusual[6 + 2] cycloadducts, the [2 + 2] cycloadducts also arise, which isomerize into 3 upon heating. The [4 + 2] and [2 + 2] adducts of 1,3-cycloheptadiene and 1 form competitively; the [2 + 2] cycloadducts rearrange to give the Diels–Alder products.

    4. Synthesis of the First 2H-1-Aza-2-phosphirene Complexes (pages 80–82)

      Dr. Rainer Streubel, Dipl.-Chem. Jörg Jeske, Prof. Dr. Peter G. Jones and Dr. Regine Herbst-Irmer

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.199400801

      Thumbnail image of graphical abstract

      A novel compound with an unsaturated three-membered ring, 2H-1-aza-2-phosphirene, is present in complex 1. This unusual ligand is formed in a surprisingly simple way in the reaction of the corresponding amino(aryl)carbenepentacarbonyltungsten(0) complex with [bis(trimethylsilyl)methylene]chlorophosphane. The crucial step is the rearrangement of 2-aza-1-phospha-4-tungsta-1,3-butadiene to give the 2H-1-aza-2-phosphirene tungsten complex.

    5. A “Branched-Monomer Approach” for the Rapid Synthesis of Dendimers (pages 82–85)

      Dr. Karen L. Wooley, Dr. Craig J. Hawker and Prof. Dr. Jean M. J. Fréchet

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.199400821

      Thumbnail image of graphical abstract

      An accelerated route to the synthesis of dendritic macromolecules through the use of fractal components larger than the repeating unit is described. The first-generation bromide 1 and the second-generation novel branched AB4 monomer 2 can be used to prepare a highly regular fifth-generation poly(ether ester) dendrimer (Mr = 9371) in only three synthetic steps.

    6. Thermal Decomposition of Silver Oxide Monitored by Raman Spectroscopy: From AgO Units to Oxygen Atoms Chemisorbed on the Silver Surface (pages 85–86)

      Dr. Bruno Pettinger, Dr. Xinhe Bao, Dr. Ian Wilcock, Dr. Martin Muhler, Prof. Robert Schlögl and Prof. Gerhard Ertl

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.199400851

      When Ag7O8NO3 is heated in an O2-free atmosphere between 300 and 930 K, its AgO units (300–480 K) are transformed into Ag2O units (480–580 K) and ultimately into metallic Ag. A strongly chemisorbed Oγ species is found on the Ag surface at temperatures between 580 and 900 K which participates in the catalytic oxidation of methanol to give formaldehyde. The various O species were characterized by Raman spectroscopy.

    7. A Hexanuclear Gold(I) Complex: [{(Ph3PAu)2 C(PPh2AuPPh2)}2](ClO4)2 (pages 87–88)

      Dr. Eduardo J. Fernández, Dr. M. Concepción Gimeno, Prof. Dr. Peter G. Jones, Prof. Dr. Antonio Laguna, Prof. Dr. Mariano Laguna and José M. Lopez-de-Luzuriaga

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.199400871

      Thumbnail image of graphical abstract

      The pale yellow, air- and moisture-stable hexanuclear Au1 complex 1 contains a central Au2C2P4 eight-membered ring with two additional AuPPh3 groups coordinated to each peripheral carbon atom. The Au-Au distances in 1 are short and all Au atoms linearly coordinated.

    8. Aleuria aurantia Agglutinin Recognizes Multiple Conformations of α-L-Fuc-(1[RIGHTWARDS ARROW]6)-β-D-GlcNAc-OMe (pages 88–91)

      Dr. Thomas Weimar and Priv.-Doz. Dr. Thomas Peters

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.199400881

      Thumbnail image of graphical abstract

      A significant preference for the (1 [RIGHTWARDS ARROW] 6) linkage, but not for a particular conformation with regard to this bond is shown by the agglutinin from Aleuria aurantia when it binds to carbohydrates with the fucose residue. This is revealed by NMR spectroscopic studies on the rather flexible disaccharide 1, which showed that at least members of two major conformational families, gg and gt, are bound.

    9. Scalemic 2-Formyl-3-hydroxy[2.2]paracyclophane: A New Auxiliary for Asymmetric Synthesis (pages 91–92)

      Dr. Valeria Rozenberg, Dr. Vladimir Kharitonov, Dipl.-Chem. Dimitri Antonov, Dipl.-Chem. Elena Sergeeva, Dipl.-Chem. Andrei Aleshkin, Dr. Nickolai Ikonnikov, Dipl.-Chem. Svetlana Orlova and Prof. Dr. Yuri Belokon'

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.199400911

      Thumbnail image of graphical abstract

      A chiral analogue of salicylaldehyde, namely the [2.2]paracyclophane derivative 1, was synthesized and resolved into enantiomers. The potential use of the new recoverable chiral auxiliary is illustrated by the asymmetric synthesis of some β-hydroxy-α-amino acids.

    10. (Pentafluoro-λ6-sulfanyl)cyclopentadiene and Cyclopentadienylidenetetrafluoro-λ6-sulfane (pages 93–95)

      Dipl.-Chem. Axel Klauck and Prof. Dr. Konrad Seppelt

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.199400931

      Thumbnail image of graphical abstract

      A rigid trigonal-bipyramidal arrangement of substituents and consequently a rigid C[BOND]S bond are found in thione 2 at temperatures up to 180 °C. Compound 2 does not occur in the resonance-stabilized ylide-type resonance structure with an aromatic five-membered ring. It is formed by elimination of HF from cyclopentadiene 1, the anion of which should display a diverse coordination chemistry.

    11. Facile Reduction of a Dialkyl Zirconium(IV) Octaethylporphyrin (OEP) Complex by H2: Crystal Structure and Spectroscopic Characterization of [(OEP)ZrCH2SiMe3] (pages 95–97)

      Holger Brand and Prof. Dr. John Arnold

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.199400951

      Thumbnail image of graphical abstract

      The unusual stability of [(OEP)ZrCH2SiMe3] (1), which formally contains a ZrIII center and is formed by reaction of [(OEP)Zr(CH2SiMe3)2] with H2, is best explained by considering two resonance structures, a ZrIII metal-based radical and a zwitterionic porphyrin radical anion. OEP (octaethylporphyrin) is denoted by a circle in the formulas shown on the right.

    12. Trialkylstibanes as Bridging Ligands: Synthesis and Structure of the Dinuclear Complexes [Rh2Cl2(μ-SbiPr3)(μ-CR2)2] (pages 97–99)

      Dipl.-Chem. Peter Schwab, Dipl.-Chem. Norbert Mahr, Dr. Justin Wolf and Prof. Dr. Helmut Werner

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.199400971

      Thumbnail image of graphical abstract

      Not only CO, NO, and related molecules but also stibanes SbR3 can act as bridging ligands in dinuclear complexes. Compound 2, the first compound of this type, which is a accessible upon thermolysis of 1 and characterized by X-ray structure analysis, is remarkably stable. The SbiPr3 ligand is easily displaced by stibanes SbR3 containing smaller substituents R (Me, Et) and also by CNtBu without disturbing the carbene bridges.

    13. First Total Synthesis of (±)-Rabelomycin (pages 99–100)

      Prof. Karsten Krohn and Dipl.-Chem. Karamali Khanbabaee

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.199400991

      Thumbnail image of graphical abstract

      To hold the position for a labile hydroxyl group and to direct a regioselective deprotonation, the Si2Me5 group is introduced in the diene component 3, from which the antibiotic rac-rabelomycin (4) is accessible through cycloaddition and subsequent photooxygenation. This procedure emphasizes the usefulness of the pentamethylsilyllithium 2, readily prepared from disilane 1, for the synthesis of tertiary alcohols.

    14. Synthesis of N-Glycopeptide Clusters with Lewisx Antigen Side Chains and Their Coupling to Carrier Proteins (pages 101–103)

      Dr. Karsten von dem Bruch and Prof. Dr. Horst Kunz

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.199401011

      Thumbnail image of graphical abstract

      As a tumor-associated cell-antigen mimic, Lewisx trisaccharide determinant 1 was constructed with the azide function as anomeric protecting group with the aid of a 4-Mpm-protected (Mpm = methoxyphenylmethyl) fucosyl donor. Exchange of the OMpm functions for OAc groups furnishes a Lewisx trisaccharide stable enough against acid attack for glycopeptide synthesis. A glycopeptide with two Lewisx antigen side chains was deblocked and coupled to bovine serum albumin as well as to KLH (keyhole limpet hemocyanin). These synthetic glycoproteins simulate biantennary Lewisx antigen structures.

    15. Palladium-Catalyzed C[BOND]H Activation of tert-Butyl Groups: A Simple Synthesis of 1,2-Dihydrocyclobutabenzene Derivatives (pages 103–105)

      Dr. Gerald Dyker

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.199401031

      Thumbnail image of graphical abstract

      The tert-butyl group of 1 is surprisingly reactive in the presence of palladium catalysts. A domino coupling affords 1,2-dihydrocyclobutabenzene 2 in good yield (75%). The observed C[BOND]H activation can also be used for cross coupling reactions.

    16. Solvent-Free Volatile Alkoxides of the Alkaline-Earth Elements (pages 105–107)

      Prof. Dr. Wolfgang A. Herrmann, Norbert W. Huber and Thomas Priermeier

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.199401051

      Thumbnail image of graphical abstract

      At low temperatures and without decomposition, alkaline-earth alkoxides 1 (M = Ca, Sr, Ba) and an analogous cadmium complex sublime under vacuum, which makes these compounds possible candidates for chemical vapor deposition (CVD) techniques, for example, for the preparation of high-temperature superconductors. The high volatility of these alkoxides is in part a consequence of their unusually low degree of aggregation.

    17. Enantioselective Protonation of Simple Enolates: Chiral Imide as a Chiral Proton Source (pages 107–109)

      Dr. Akira Yanagisawa, Takeshi Kuribayashi, Tetsuo Kikuchi and Prof. Hisashi Yamamoto

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.199401071

      Thumbnail image of graphical abstract

      From Kemp's tricarboxylic acid the (S,S)-imide 1 and its enantiomer, as well as related imides, were synthesized. With this new chiral reagent, lithium enolates of α-monoalkylated cycloalkanones can be protonated. For instance, 2 can be transformed into 3.

    18. The Total Synthesis of cis-7,8-Dihydroxy-11,12-dehydrocalamenene by Regio- and Diastereo-selective Alkylation of Chiral η6-Arenetricarbonylchromium Complexes: An Unexpected Case of Nucleophilic Aromatic tele-Substitution with Methoxide as a Leaving Group (pages 109–111)

      Dr. Hans-Günther Schmalz, Dipl.-Chem. Markus Arnold, Dipl.-Chem. Jens Hollander and Dr. Jan W. Bats

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.199401091

      Thumbnail image of graphical abstract

      With complete diastereoselectivity and no loss of absolute stereochemical information, the chiral synthetic building block 1 is converted into 2, an advanced intermediate in the total synthesis of the antiinfective sesquiterpene 3. The reactivity of arene-Cr(CO)3 complexes is crucial to the synthetic strategy. TMS = SiMe3.

    19. trans-Chelating Chiral Diphosphane Ligands Bearing Flexible P-Alkyl Substituents (AlkylTRAPs) and their Application to the Rhodium-Catalyzed Asymmetric Hydrosilylation of Simple Ketones (pages 111–113)

      Dr. Masaya Sawamura, Ryoichi Kuwano and Prof. Dr. Yoshihiko Ito

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.199401111

      Thumbnail image of graphical abstract

      Not bulky substituents but flexible alkyl groups led to the hitherto highest enantioselectivities for the asymmetric hydrosilylation of simple ketones catalyzed by diphosphanerhodium complexes. The reduction of acetophenone in the presence of the diphosphane ligand 1, R = nPr,nBu, gave 92% ee, whereas with 1, R = Ph and R = iPr, ee values of only 15% and 1%, respectively, were achieved.

    20. Synthesis and Structure of the Disilagermirane R2Ge(SiR2)2 and the Solvent-Separated Ion Pair [Li([12]crown-4)2][GeR3]; (R = SiMe3) (pages 113–115)

      Dr. Andreas Heine and Priv.-Doz. Dr. Dietmar Stalke

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.199401131

      Thumbnail image of graphical abstract

      The disilagermirane 1 is obtained in good yields from (Me3Si)3 SiLi(thf) and GeCl2. The germyllithium compound 2 was also prepared; its anion, the higher homologue of the Si starting material for 1, might prove to be a versatile building block for a great variety of mixed three-membered rings containing the heavier elements of group 14.

    21. [(N-Lithio-N-mesitylsulfonyloxy-tert-butylcarbamate)2·(thf)3]: Crystal Structure of a Nitrenoid (pages 115–117)

      Prof. Dr. Gernot Boche, Christiane Boie, Ferdinand Bosold, Dr. Klaus Harms and Michael Marsch

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.199401151

      Thumbnail image of graphical abstract

      The N[BOND]O bond in 1 lengthens by roughly 6 pm when the neutral compound (X = H) is N-lithiated (X = Li). This key result of the first crystal structure analysis of a nitrenoid explains the facile replacement of the OR groups in nitrenoids R1(Li)OR2 by nucleophiles like R'Li and is in accord with calculational predictions. In the solid state 1 (X = Li) occurs as a Li-linked dimer with three Li-coordinating THF molecules, one of which bridges the two Li centers. R = 2,4,6-trimethylphenyl.

    22. Isopagodanes—Precursors of Unusual Cage Ions (pages 117–120)

      Dr. Markus Wollenweber, Dr. Rolf Pinkos, Jürgen Leonhardt and Prof. Dr. Horst Prinzbach

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.199401171

      Thumbnail image of graphical abstract

      Isopagodanes like the “square”, D2d-symmetric C20H20 [1.1.1.1] skeleton 1 may serve as precursors to unusual cage ions of very special geometry. The synthetic strategy for pagodanes could not be directly applied to isopagodanes. A detour, in which a [2 + 2] photocycloaddition replaced the unsuccessful [6 + 6] photocycloaddition, was ultimately successful.

    23. A Novel Reaction Sequence for the Coupling of Nucleophiles to Agarose with 2,2,2-Trifluoroethanesulfonyl Chloride (pages 120–123)

      Anastasios Demiroglou, Cornelia Bandel-Schlesselmann and Prof. Dr. Herbert P. Jennissen

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.199401201

      Thumbnail image of graphical abstract

      In a new reaction of tresyl chloride (CF3CH2SO2Cl) the nucleophilic attack on the tresylate is not between the activating group and the trifluoroethanesulfonate as expected, but between the sulfonate and the trifluoroethyl group. The coupling of alkylamines with “tresylated” agarose

      , for example, thus gives sulfamates [Eq. (a)].

    24. An Extraordinarily Violent Molecular Dissociation: The Unprecedented Kinetic Energy Release in the Decomposition of HONF+, a Singly Charged Metastable Ion (pages 123–125)

      Prof. Dr. Fulvio Cacace, Dr. Felice Grandinetti and Dr. Federico Pepi

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.199401231

      Thumbnail image of graphical abstract

      2.68 + 0.10 eV, the largest value by far for the kinetic energy release (KER) in the decomposition of metastable, singly charged ions was detected by mass spectrometry for the fragmentation of HONF+. Thus, the exceptionally large KER predicted by a theoretical analysis of the potential energy surface (calculated energy profile shown on the right) was also confirmed experimentally.

    25. Dialdehyde + Diamine—Polymer or Macrocycle? (pages 125–126)

      Prof. Dr. Henri Brunner and Dipl.-Chem. Hubert Schiessling

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.199401251

      Thumbnail image of graphical abstract

      The 24-membered macrocycle 1 is surprisingly generated from (S)-2,2′-dihydroxy-1,1′-binaphthyl-3,3′-dialdehyde [(S)-(2)] and (R,R)-1,2-diamino-1,2-diphenylethane, whereas in the same reaction (R)-2 yields the polymeric Schiff base as expected. Macrocycle 1 can be used for an economical and simple enantiomeric resolution of 2.

  4. Book Reviews

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

    1. Top of page
    2. Reviews
    3. Highlights
    4. Communications
    5. Book Reviews
    6. New Books
    1. New Books (Angew. Chem. Int. Ed. Engl. 1/1994) (page 129)

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.199401291

SEARCH

SEARCH BY CITATION