Angewandte Chemie International Edition in English

Cover image for Vol. 20 Issue 3

March 1981

Volume 20, Issue 3

Pages 217–302

Currently known as: Angewandte Chemie International Edition

    1. Cover Picture (Angew. Chem. Int. Ed. Engl. 3/1981)

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198102171

    2. Graphical Abstract (Angew. Chem. Int. Ed. Engl. 3/1981)

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198102172

  1. Reviews

    1. Top of page
    2. Reviews
    3. Communications
    4. Book Reviews
    1. Target Directed Drug Synthesis: The Aminoacyl-tRNA Synthetases as Possible Targets (pages 217–223)

      Priv.-Doz. Dr. Friedrich von der Haar, Dipl.-Biochem. Hans-Joachim Gabius and Prof. Dr. Friedrich Cramer

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198102173

      The “tailor-made” pharmaceutical is an old dream. An ideal pharmacon should inhibit the pathological process or the parasitical organism to a maximum while causing minimal harm to the human body. In order to achieve this, use must be made of metabolic differences between the pathological or parasitical and the normal human metabolism. The pharmaceutical should act upon the important central process. Such a process is the “proofreading” step in protein biosynthesis, which exhibits species specific differences.

    2. Advances in Organophosphorus Chemistry Based on Dichloro(methyl)phosphane (pages 223–233)

      Prof. Klaus Weissermel, Dr. Hanns-Jerg Kleiner, Dr. Manfred Finke and Dr. Utz-Hellmuth Felcht

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198102231

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      Phosphonic, phosphinic and phosphonous acid derivatives have been synthesized in large numbers in the last decade from the industrially readily accessible dichloro(methyl)phosphane. The derivatives thus obtained are of interest, inter alia, as intermediates for Pharmaceuticals, crop-protection and flame retardent agents.

    3. Darwin and Molecular Biology (pages 233–241)

      Prof. Dr. Manfred Eigen

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198102331

      Darwin's principle of selection has proved to be a physically based natural law, which controls the evolution of replicative molecular systems. The course of evolution can be mathematically formulated and experimentally tested under laboratory conditions.

    4. Biliproteins (pages 241–261)

      Dr. Hugo Scheer

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198102411

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      Biliproteins are light harvesting pigments in photosynthesis, and light sensory pigments, in e.g., cyanobacteria and red algae. Bile pigments serve as chromophoric groups. The functions of the pigments as light harvesters and information transducers on a molecular level are discussed.

  2. Communications

    1. Top of page
    2. Reviews
    3. Communications
    4. Book Reviews
    1. Interconversion of the Chromophore Systems of Porphyrinogen and 2,3,7,8,12,13-Hexahydroporphyrin (pages 261–263)

      Dr. Jon Eigill Johansen, Dr. Virginia Piermattie, Dipl. Naturwiss. ETH Christof Angst, Dipl. Naturwiss. ETH Eva Diener, Dr. Christoph Kratky and Prof. Dr. Albert Eschenmoser

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198102611

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      The search for reaction conditions under which a non-oxidative isomerization(1)[RIGHTWARDS ARROW](2)takes place has now met with success. The corphinoid-type structure (2) is of interest in connection with corrin biosynthesis.

    2. Cyclization of a Seco-porphyrinogen to Nickel(II) C,D-Tetradehydrocorrinates (pages 263–265)

      Dipl. Naturwiss. ETH Christof Angst, Dr. Christoph Kratky and Prof. Dr. Albert Eschenmoser

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198102631

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      The first C,D-tetrahydrocorrinates were obtained by the title reaction (1)[RIGHTWARDS ARROW](2). Besides cttt-(2), nine diaslereomers are formed.

    3. Electrophilic Reactions of Aryl- and Heteroaryl(triniethyl)silanes with a Remarkable Nucleophilic Catalysis (pages 265–266)

      Prof. Dr. Franz Effenberger and Dipl.-Chem. Wolfgang Spiegler

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198102651

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      Of preparative importance and mechanistic interest are the reactions of aryl-trimethylsilanes (1), in which X is an anion-stabilizing substituent, with electrophiles in the presence of hard bases. The yields are good.

    4. Nucleophilic Catalysis of Reactions of Tricarbonyl(trimethylsilylarene)chromium Complexes with Electrophiles (pages 266–267)

      Prof. Dr. Franz Effenberger and Dipl.-Chem. Klaus Schöllkopf

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198102661

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      The introduction of numerous substituents into benzene derivatives is possible with (1) as starting material. For example, reaction of (1) with ketones in the presence of KOtBu leads to products which are substituted with the (readily cleavable) [BOND]CR2[BOND]OsiMe3 instead of with SiMe3.

    5. Synthesis and ESR Characterization of the Triplet Species μ-(η66-Biphenyl)-bis[(η6-benzene)vanadium] (pages 267–269)

      Prof. Dr. Christoph Elschenbroich and Dipl.-Chem. Jürgen Heck

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198102671

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      A novel paramagnetic intersandwich compound, the title compound (1), has now been obtained from the extremely air-sensitive di(μ-benzene)vanadium(0). In (1), the unpaired electrons couple with both 51V-nuclei.

    6. A Simple Route to a New Type of Cyclophane (pages 269–270)

      Doz. Dr. Juri Juriew, Tatjana Skorochodowa, Doz. Dr. Jewgeni Merkuschew, Doz. Dr. Werner Winter and Prof. Dr. Herbert Meier

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198102691

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      The first application of photochemical cycloaddition in cyclophane synthesis led to a novel type of cyclophane. The product (1), R = C6H5, is formed from mesitylene via tristyrylbenzene in only two steps.

    7. Isolation of a Highly Strained Bicyclic Alkyne (pages 270–271)

      Prof. Dr. Herbert Meier, Dipl.-Chem. Cornelius Schuh-Popitz and Dr. Hermann Peiersen

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198102701

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      Being a cyctoalkyne and a bicyclo[n.1.0]-derivative at the same time is a unique feature of the compounds (1a) and (1b). Both were generated from the corresponding tricyclic selenadiazoles. (1) is isolable, (1b) can be trapped.

    8. Polymethinic Ring Compounds and the Polymethinic Carbonyl Group (pages 271–272)

      Prof. Dr. Siegfried Kulpe

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198102711

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      The properties of tetraaminobenzoquinones such as(1)are better understood if one assumes that they contain polymethinic carbonyl groups (2). In these groups the C[DOUBLE BOND]O bond is neither drastically lengthened nor is the stretching vibrational frequency drastically shifted bathochromically.

    9. Stereochemistry of Substitution at the Cyclopropane Ring in 7-Aminonorcaranes (pages 273–274)

      Prof. Dr. Elmar Vilsmaier, Dipl.-Chem. Wolfgang Tröger and Michael Gewehr

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198102731

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      The cation(2)with unopened three-membered ring is involved as intermediate in substitution reactions of the deuterated dimorpholinonorcaranes (1). In the reaction (1)[RIGHTWARDS ARROW](2), R1[BOND]R2 = (CH2)2O(CH2)2, the exo-substituent is cleaved off with ≥95% selectivity.

    10. A Convenient Synthesis of “Homoazulene” (1,5-Methano[10]annulene) (pages 274–275)

      Prof. Dr. Lawrence T. Scott, Dr. William R. Brunsvold, Mark A. Kirms and Dr. Ihsan Erden

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198102741

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      Our present understanding of cyclic conjugation in non-benzenoid systems is based in part on investigations of bridged annulenes such as (1) and (2). The new method presented here permitted the first synthesis of (1) in large amounts.

    11. Tricarbonyl(1-methyl-3,5-diphenyl-λ4-thiabenzene)chromium(O) (pages 279–280)

      Dr. Lothar Weber

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198102791

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      Are λ4-thiabenzenes ylides or heteroarenes? For the first time it has been possible to stabilize a λ4-thiabenzene by complexation. In (1) (X-ray structure analysis) the system behaves as an ylide.

    12. A Novel Method for Preparation of Ansapeptides; Synthesis of Model Peptide Alkaloids (pages 280–281)

      Prof. Dr. Ulrich Schmidt, Ing. Helmut Griesser, Dr. Albrecht Lieberknecht and Dr. Jörg Talbiersky

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198102801

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      The preparation of 14-membered peptide alkaloids was first investigated on model educts such as the pentafluorophenyl esters (1), Z = benzyloxycarbonyl. On the basis of these investigations it was subsequently possible to develop a method for the synthesis of dihydrozizyphin G (2), A[BOND]A = CH2[BOND]CH2, as the first compound of this type.

    13. Synthesis of Dihydrozizyphin G (pages 281–282)

      Prof. Dr. Ulrich Schmidt, Dr. Albrecht Lieberknecht, Helmut Griesser and Dr. Johannes Häusler

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198102811

      Thumbnail image of graphical abstract

      The preparation of 14-membered peptide alkaloids was first investigated on model educts such as the pentafluorophenyl esters (1), Z = benzyloxycarbonyl. On the basis of these investigations it was subsequently possible to develop a method for the synthesis of dihydrozizyphin G (2), A[BOND]A = CH2[BOND]CH2, as the first compound of this type.

    14. Configurational Isomerization of N,N-Disubstituted Hydroxylamido(1-)-O,N-Molybdenum(VI) Complexes (pages 282–283)

      Dr. Edgar Hofer, Dipl.-Chem. Wolfgang Holzbach and Prof. Dr. Karl Wieghardt

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198102821

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      For the NMR-spectroscopically detectable configurational isomerization of the complexes(1), R = benzyl, ethyl, and of the thioxoanalogue MoS2(Et2N[BOND]O)2 a rapid dissociation of the Mo[BOND]N bond on the NMR time-scale is proposed, followed by rotation-inversion at the nitrogen and re-formation of the Mo[BOND]N bond.

    15. Synthesis of a Borato(phosphoniomethanide)(phosphoniooxide)Ligand and Its Organoberyllium Complex (pages 283–284)

      Prof. Dr. Hubert Schmidbaur and Dr. Erwin Weiss

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198102831

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      The novel bidentate ligand(1) has been obtained in a multistep synthesis as the lithium complex. Reaction of this complex with BeCl2 affords the spirocyclic, volatile beryllium complex [(1)]2Be.

    16. Synthesis and Crystal Structure of a (η5-C5H5)(CO)2-Molybdenum Bicyclophosphoranide: The first Transition Metal Complex with a “R4P”-Ligand (pages 284–285)

      Dr. Joachim Wachter, Dr. Bernard F. Mentzen and Prof. Dr. Jean G. Riess

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198102841

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      Tetravalent phosphorus with negative charge is present in a phosphoranide. The ligand (1), formally a phosphoranide, is contained in the title compound, which, moreover, is characterized by a MoPO three-membered ring (X-ray structure analysis). Such a ring has not been observed before.

    17. The Stereospecificity of Brefeldin A Cyclization (pages 286–287)

      Dipl.-Chem. Peter Raddatz and Prof. Dr. Ekkehard Winterfeldt

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198102861

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      A novel example of long-range interactions in macrolide systems is provided by ring closure of the ester (1). The C-15 epimer mixture cyclizes with high stereoselectivity (10:1) to a lactone, which can be converted into 4-epi-15-epi-brefeldin.

    18. Addition of Ynamines to Vinylketenes (page 287)

      Dr. Karl Heinz Dötz, Barbara Trenkle and Dr. Ulrich Schubert

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198102871

      Thumbnail image of graphical abstract

      The surprising formation of the bicyclo-[3.1.0]-derivative(1) instead of a four-membered ring in the reaction of O[DOUBLE BOND]C[DOUBLE BOND]CR[BOND]CR[DOUBLE BOND]CX[BOND]OMe and MeC[TRIPLE BOND]C[BOND]Net2 is explained in terms of secondary reactions (R = SiMe3, X=pF3CC6H4).

    19. Intramolecular Nucleophilic Addition in a Thiolatobridged “Crown-like” Iridium Complex (pages 287–288)

      Jean Devillers, Dominique de Montauzon and Prof. Dr. René Poilblanc

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198102872

      An iridium complex exhibiting several unusual properties, the title compound (2), is formed on reaction of (1) with an excess of hexafluoro-2-butyne at −196 °C. X-ray structure analysis confirms the six-membered ring of three S-, two IrII-atoms and one IrI-atom, the different bonding of the alkane ligands, and the coordination of a S atom.

      • equation image
    20. Reactions of Carbon Suboxide with Platinum(O) Complexes (pages 288–289)

      Prof. Dr. Gastone Paiaro and Dr. Luciano Pandolfo

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198102881

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      The skeleton of carbon suboxide remains intact on reaction with two platinum complexes. With (PPh3)2Pt(C2H4) the metallacyclopropane (1) is formed; with (PPh3)2Pt(O2) the dioxametallacyclopentane (2).

    21. Reactions of Carbon Suboxide with Rhodium(I) Complexes (pages 289–290)

      Prof. Dr. Gastone Paiaro and Dr. Luciano Pandolfo

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198102891

      The decomposition of carbon suboxide in the presence of two rhodium(I)-complexes leads to CO and C2O. With (PPh3)3RhCl, (1) and polymeric C2O are formed, with [(C8H14)2RhCl]2 the polymers (2) and cyclooctene. Pyridine can “dissolve” the Cl-bridge in (2); a dimer is formed.

      • equation image
    22. Reaction of Platinum(II) N,N-Dialkyldithiocarbamates with Diphenylphosphane Sulfide (pages 290–291)

      David M. Anderson, Professor Dr. E. A. V. Ebsworth, Dr. T. Anthony Stephenson and Dr. Malcolm D. Walkinshaw

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198102901

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      Novel Anions(1)and new dinuclear complexes(2) are some of the products which have been found during studies on the reactions of Pt(S2CNR2)2 with Ph2P(S)H (R [DOUBLE BOND] Et, iPr).

    23. Tetramethylcyclopropanone and Isopropylidene(dimethyl)thiirane via Photolysis of Reluctant 3,3,5,5-Tetramethyl-1-pyrazolines; Influence of Solvent and Temperature on the Competition between [3+2]- and [4+1]-Photocycloelimination (pages 291–292)

      Prof. Dr. Helmut Quasit and Dipl.-Chem. Andreas Fuss

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198102911

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      The photolysis of 1-pyrazolines of type(1) holds numerous surprises. Thus, irradiation of (1), X = O, in deuterated benzene, cyclohexane or acctonitrile (1a) gave without filter the products (3) and (4), whose ratio depends on the conditions. (2a) could be trapped with CD3OD. When X = S in (1), only (5) is formed.

    24. Naturally Occurring Cyclopropenone Derivatives (pages 292–293)

      Prof. Dr. Ferdinand Bohlmann, Dr. Jasmin Jakupovic, Dipl.-Chem. Lutz Müller and Angelika Schuster

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198102921

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      The cyclopropenone structure of the plant components(1)and(2), as well as of an isoiner with eudesmane partial structure was recognized, in particular, by NMR and IR spectroscopy. Synthetic cyclohexylcyclopropenone served for comparison.

    25. Biosynthesis of Natural Porphyrins: Studies with Isomeric Hydroxymethylbilanes on the Specificity and Action of Cosynthetase (pages 293–295)

      Prof. Dr. Alan R. Battersby, Dr. Christopher J. R. Fookes, Dr. George W. J. Matcham and Dr. Pramod S. Pandey

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198102931

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      The Cosynthetase-catalyzed cyclization(1)[RIGHTWARDS ARROW](2), which proceeds with “inversion” of ring D, does not start with rearrangement into the open-chain isomer with inverted ring D.

    26. “Chemical Mutation” by Amino Acid Exchange in the Reactive Site of a Proteinase Inhibitor and Alteration or Its Inhibitor Specifity (pages 295–296)

      Dr. Herbert R. Wenzel and Prof. Dr. Harold Tschesche

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198102951

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      By chemical intervention in the reactive center of an enzyme-inhibitor it has been possible to replace lysine by valine, i.e. by a non-basic amino acid. Hitherto, this was possible via an enzymatic pathway only in exceptional cases. The native Kunitz inhibitor (1) from bovine organs inhibits trypsin very strongly, but hardly inhibits leukolytic elastase at all; the chemically modified product (2) is a very good inhibitor for elastase from human leukocytes. The method is capable of generalization.

    27. Novel 4-Amino-2-azabutadienes and 1-Aminobutadienes; Syntheses of Pyridines, Benzenes, and Azoles (pages 296–297)

      Prof. Dr. Rudolf Gompper and Dr. Ulrich Heinemann

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198102961

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      4-Amino-2-azabutadienes with multivariable substituents enable convenient syntheses of 2,3,4,6-tetrasubstituted pyridines and oxazoles, thiazoles, and imidazoles.

    28. Aminopyridines, Aminpyrimidines, and Tris(dimethylamino)benzene from (Aza)Vinamidinium and (Aza)Pentamethinium Salts (pages 297–298)

      Prof. Dr. Rudolf Gompper and Dipl.-Chem. Ulrich Heinemann

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198102971

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      Cyclizations to amino-substituted pyrimidines and pyridines can be carried out with the azapentamethinium salts (1) and (2). These compounds are obtainable from the corresponding vinamidinium salts.

    29. σ-Framework Radical Cations–A Novel Type of Reactive Intermediates (pages 298–300)

      Dr. Peter Gölitz and Prof. Dr. Armin de Meijere

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198102981

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      A general method for the generation of novel σ-framework radical cations such as (2) uses 1-trifluoromethylazo-substituted polycycles as starting material. In the photolysis of the cations of type (1) the N2-deficient cations are formed; this indicates formation of the intermediary species (2).

    30. Cobaltaheterocycles by [3+2]-Cycloaddition of an Acetimidoylcobalt Complex with Acetone and Acetonitrile (pages 300–301)

      Prof. Dr. Helmut Werner, Dipl.-Chem. Bernd Heiser and Dr. Alfred Kühn

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198103001

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      The high nucleophilicity of the acctimidoyl N-itom in [C5H5Co(Pme3)Me(CNMe)]I enables [3+2]-cycloadditions with acetone and acetonitrile, whose multiple bonds are only slightly activated. With acetonitrile, (1) is formed. The analogous acetimidoyl complex of rhodium forms no rhodaheterocycles.

  3. Book Reviews

    1. Top of page
    2. Reviews
    3. Communications
    4. Book Reviews
    1. Book Review: The Biosynthesis of Mycotoxins. Ed. by P. S. Steyn (pages 301–302)

      Franz Lingens

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198103011

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