Angewandte Chemie International Edition in English

Cover image for Vol. 29 Issue 10

October 1990

Volume 29, Issue 10

Pages 1077–1176

Currently known as: Angewandte Chemie International Edition

    1. Cover Picture (Angew. Chem. Int. Ed. Engl. 10/1990)

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199010771

      Thumbnail image of graphical abstract

      Modern art or modern chemistry? This is a question which compellingly springs to mind on seeing the cover picture, which does in fact stem from the realms of modern structural chemistry: Molecular self-organization, metal-clusters, and topological structural chemistry are the themes concealed in the picture. In the eight-membered metal cluster [(OC)Pd(μ-NC)Mn(η-C5H4Me)(CO)2]4, four Pd atoms, four Mn atoms, and four bridging cyano ligands form two helix strands of opposite chirality: their axes are orthogonal, thus resulting in an overall meso structure of approximate S4 symmetry. The cover page computer graphic was generated—with the X-ray analytically determined atomic coordinates of the complex—by J.-P. Mage and P. Verley (Groupe IAO, Centre decalcul du CNRS, Strasbourg). More about the synthesis, structure, and properties of the complex is reported by P. Braunstein et al. on p. 1140ff.

  1. Reviews

    1. Top of page
    2. Reviews
    3. Communications
    4. Book Reviews
    1. Complexes of Carbon Monoxide and Its Relatives: An Organometallic Family Celebrates Its Birthday (pages 1077–1089)

      Prof. Dr. Helmut Werner

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199010773

      Thumbnail image of graphical abstract

      Ludwig Monds discovery of tetracarbonylnickel had far-reaching consequences beyond the bounds of carbonylmetal chemistry. Molecules isoelectronic with CO such as CS, CNH, and C = CH2, which are extremely short-lived in the free state, form very stable complexes with transition metals. Complexes of other species such as SiO, which has been detected both in the gas phase as well as at low temperatures, are still unknown. A possible way in which they could be prepared is shown in Equation (a). Do = donor, X = halide, L = ligand, M = transition metal.

    2. Aspartic and Glutamic Acid as Ligands to Alkali and Alkaline-Earth Metals: Structural Chemistry as Related to Magnesium Therapy (pages 1090–1103)

      Prof. Dr. Hubert Schmidbaur, Prof. Dr. Hans Georg Classen and Dr. Joachim Helbig

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199010901

      Thumbnail image of graphical abstract

      The therapeutic activity of magnesium preparations not only depends on the mode of administration orally or parenterally–but quite decisively also on the form of the preparation. Thus. e.g., pH value and ionic equilibrium in the body fluids should as far as possible remain unaffected, and side effects of the anionic and or of the complex components should be negligible: on the other hand, a high biological availability of the Mg ions is desirable. Amino acid-Mg complexes such as Mg(L-AspH)CI-·3H2O(part structure on the right) fulfill these criteria (black: O; dotted Mg: hatched: N).

    3. Complexes with Substituent-free Acyclic and Cyclic Phosphorus, Arsenic, Antimony, and Bismuth Ligands (pages 1104–1122)

      Prof. Dr. Otto J. Scherer

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199011041

      Thumbnail image of graphical abstract

      The palette of complexes with the heavier elements of the fifth main group ranges from sandwich complexes of the P- and As-analogues of cyclopentadiene and benzene to metal clusters with Sb and Bi atoms. Parallels to organic chemistry and solid-state chemistry are in evidence. The transformation shown on the right demonstrates the unusual reactivity of such compounds (Cp′ = η5-C5Me4Et).

  2. Communications

    1. Top of page
    2. Reviews
    3. Communications
    4. Book Reviews
    1. An N-Phosphino C-ThiophosphinoyI Nitrilimine as a Formal 1,4 Dipole: Synthesis of 1,2,3λ5-Diaza- and 1,2,4,3λ5-Triazaphosphinines (pages 1123–1125)

      Michel Granier, Dr. Antoine Baceiredo, Dr. Martin Nieger and Dr. Guy Bertrand

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199011231

      Thumbnail image of graphical abstract

      The phosphino substituent in the nitrilimine 1, R = NiPr2, reacts more rapidly than the nitrilimine unit with dipolarophiles. Thus with MeO2C-C= C-CO2Me the diazaphosphinine 2 is formed in 90% yield in the form of orange-red crystals. The initial step of this reaction could be an electrophilic attack at the lone pair of the λ3-phosphorus atom.

    2. Synthesis of Two TIIII Diacetonyl Compounds and Crystal Structure of [Tl{CH2C(0)Me}2(μ-CF3S03)(bpy)]2 (pages 1125–1126)

      Prof. Dr. José Vicente, Dr. JoséAntonio Abad, Mr. Gabriel Cara and Prof. Dr. Peter G. Jones

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199011251

      The diacetonyl complex 1 is accessible in 76% yield by simple reaction of T1(CF3SO3)3; with trifluorosulfonic acid in acetone. 1 reacts with 2,2′-bipyridine to form 2 in 81% yield. In the centrosymmetric dimer 2 the Tl atoms have a distorted six-coordinate geometry; the triflate ligands serve as bridges. Remarkable about the structure of 2 in the crystal and of 1 and 2 in solution is that the metal atom is C-coordinated and not O-coordinated.

      • equation image
    3. Organometallic Host-Guest Systems Representing Novel Charge-Transfer “Ion Pairs” with Three-Dimensional Electron-Donor Networks (pages 1126–1128)

      Dipl.-Chem. Stefan Eller, Dipl.-Chem. Martin Adam and Prof. Dr. R. Dieter Fisher

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199011261

      Methylviologen radical cations MV˙⊖ encapsulated in the three-dimensional network of the anions 1 are less readily oxidizable than in a zeolite-Y cage. The spatially apparently very flexible network of 1 also facilitates incorporation of bulky benzylviologen radical cations. Compared to electron acceptor-guestions such as MV2⊖ the anions 1 are stronger donors than their non-crosslinked analogues 2. M= Fe, Ru, Os.

      • equation image
    4. Isomerization of Benzoylalkylidene Sulfur Tetrafluorides C6H5–CO[BOND]CR[DOUBLE BOND]SF4 to Dihydrooxathietes (pages 1128–1129)

      Dipl.-Chem. Thomas Henkel, Dr. Thomas Krügerke and Prof. Dr. Konrad Seppelt

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199011281

      Thumbnail image of graphical abstract

      Dihydrooxathietes 3 instead of the expected benzoylalkylidene sulfur tetrafluorides 2 are formed upon treatment of 1 with NaOH. This reaction requires a twisting around the C[DOUBLE BOND]S bond, which can occur via rotation, pseudorotation or a combination of both mechanisms.

    5. Stereospecific Insertion of the Carbene Ligand of a Fischer Carbene Complex into Olefinic C[BOND]H Bonds (pages 1129–1131)

      Dr. Anette Wienand and Prof. Dr. Hans-Ulrich Reissig

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199011291

      Thumbnail image of graphical abstract

      The C(OMe)Ph ligand of 1 is inserted into the β-C-H bond of (E)- and (Z)-2 with high stereoselectivity and with inversion of the olefin configuration (3). In cyclohexane at 80°C, this is the main reaction, and not, as expected, the formation of cyclopropanes. The experimental findings suggest a formation of 3 via metallacyclobutanes, β-Syn -elimination, and reductive elimination.

    6. Catalytic Hydrosilylation or Hydrogenation at One Coordination Site of [Cp′Fe(CO)(X)] Fragments (pages 1131–1132)

      Prof. Dr. Henri Brunner and Dipl.-Chem. Konrad Fisch

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199011311

      Thumbnail image of graphical abstract

      The catalytic hydrosilylation of acetophenone with diphenysilane leading to 1 is quantitative when [Cp′Fe(CO)X] fragments are the catalytically active species. These fragments are formed from the Fe-complexes 2 by cleavage of phosphane (L [DOUBLE BOND] Ph2P-NMe-CHMe Ph, X[DOUBLE BOND]Me, Ac) or migration of a methyl group (L[DOUBLE BOND]Me, X[DOUBLE BOND]CO). Some of the complexes are also suitable as hydrogenation catalysts. Cp′[DOUBLE BOND]Cp, indenyl, l-tert-butylindenyl.

    7. Electrostatic Control of the Molecular and Crystal Structure of an Olefinic Double Betaine (pages 1132–1134)

      Prof. Dr. Robert Weiss, Dr. Reinhardt Roth, Dipl.-Chem. Rainer H. Lowack and Dr. Matthias Bremer

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199011321

      Thumbnail image of graphical abstract

      A chiral conformation in the solid state as well as a stacked structure with rhomboidal cavities are the result of electrostatic interactions of the four charged substituents in 1. This Z-configurated double betaine is obtainable in three steps starting from dichloromaleic anhydride and 4-dimethyl-aminopyridine.

    8. Phenyl-Linked Quinone-Substituted Porphyrin Trimers (pages 1134–1137)

      Prof. Jonathan L. Sessler and Vincent L. Capuano

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199011341

      Thumbnail image of graphical abstract

      The three photoreactive porphyrin moieties and two acceptor units in the molecule should make 1 a suitable model for investigating the mechanistic details of the initial charge separation process in photosynthetic reaction centers. The static and dynamic electronic spectra of 1 indicate a “super-exchange”, i.e. an efficient electron transfer from all three porphyrin units to the quinone units.

    9. [(Ph3P)2N]2[Os18Hg2C2(CO)42] a Photochemically Generated High-Nuclearity Cluster Which Reversibly Incorporates Metallic Mercury into Its Metal Core (pages 1137–1139)

      Eleni Charalambous, Lutz H. Gade, Dr. Brian F. G. Johnson, Thomas Kotch, Prof. Alistair J. Lees, Prof. Lord. Jack Lewis and Prof. Mary McPartlin

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199011371

      Thumbnail image of graphical abstract

      Photochromic behavior of a metal cluster has been observed for the first time. In the reaction depicted below, deep-violet 1 is photochemically cleaved to give burgundy-red 2and Hg, whereas in the absence of light the thermal Hg-reinsertion to give 1 takes place.

    10. Selective Deamidation of Peptide Amides (pages 1139–1140)

      Prof. Dr. Dörte Steinke and Dipl.-Biol. Maria-Regina Kula

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199011391

      The deamidation of peptide amides with a peptide amidase isolated from orange peel proceeds without peptide cleavage. The process is virtually insensitive with regard to the side chain of the C-terminal amino acid as long as this is S-configurated. Hence there should no longer be anything in the way of an increased use of the C-terminal amide protecting group in peptide syntheses.

    11. Novel Bonding Mode for a Cyanometalate Ligand: Synthesis and Crystal Structure of the Mn4Pd4 Cluster [(OC)Pd(μ-NC)Mn(η-C5H4Me)(CO)2]4 Containing an Orthogonal Arrangement of Helical Units (pages 1140–1143)

      Dr. Pierre Braunstein, Benoît Oswald, Prof. Antonio Tiripicchio and Prof. Marisa Tiripicchio Camellini

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199011401

      Thumbnail image of graphical abstract

      Two Mn-Pd-Pd-Mn chains bridged by four cyano ligands form the “backbone” of the title compound. Deep-violet, air-stable crystals are formed quantitatively from Na[CpMn(CN)(CO)2] and [Pd4(CO)4-(OAc)4] in toluene. The topologically interesting octanuclear cluster is the first example of a complex with M-M bonding and M-CN-M′ bridges.

    12. 2,3,4,5-Tetramethyl-1-sodiopyrrole: An Azacyclopentadienyl Ligand in a Novel Bridging Function (pages 1143–1144)

      Prof. Dr. Norbert Kuhn, Prof. Dr. Gerald Henkel and Dipl.-Chem. Jörg Kreutzberg

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199011431

      Thumbnail image of graphical abstract

      A combination of amide bridges and π-bonded dienyl ligands gives rise to the cross-linked, double-chain structure of 2,3,4,5-tetrame-thyl-1-natriopyrrole in the crystal. The bridging of three Na atoms by each pyrrole ligand leads to the coordination number five for the N-atom. The metal atom is seven-coordinated.

    13. α-Umpolung of Ketones via Enol Radical Cations: A Mechanistic Study (pages 1144–1146)

      Dr. Michael Schmittel, Ahmed Abufarag, Olaf Luche and Dipl.-Chem. Michael Levis

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199011441

      Thumbnail image of graphical abstract

      Since the radical cation of an enol is more stable than that of a ketone it is possible to functionalize ketones in the α-position with nucleophiles via their enol radical cations. A good example is the reaction 1 [RIGHTWARDS ARROW] 2. Suitable one-electron transfer reagents for this novel umpolung reaction are ammoniumyl salts such as 3.

    14. Isomerization versus Decarboxylation of Protonated Oxetanone: Comparison between Experimental Results and Theoretical Calculations (pages 1146–1147)

      Prof. Dr. Gregorio Asensio, Prof. Dr. Miguel A. Miranda, Dr. Julia Perez-Prieto, Maria J. Sabater and Dr. Antonio Simóon-Fuentes

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199011461

      Thumbnail image of graphical abstract

      In concentrated sulfuric acid, protonated 2-oxetanone I H behaves other than theoretically predicted. Instead of furnishing ethylene via cleavage of protonated carbon dioxide it isomerizes to the carbenium ion 2 H, which is in equilibrium with protonated acrylic acid. This proposed mechanism is supported by investigations with the 4-tBu analogue of 1 H; in this case the carbenium ion analogous to 2 H rearranges with methyl group migration leading to 3 H as product.

    15. A Novel Palladium-Catalyzed Carbonylation of Aromatic N-Chlorosulfonamidates to Arylsulfonyl Isocyanates (pages 1147–1148)

      Dr. Gábor Besenyei, Dr. Sándor Németh and Prof. Dr. Lászlò I. Simándi

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199011471

      The title reaction (a) enables a convenient, phosgene-free entry to arylsulfonyl isocyanates. Typical reaction conditions are temperatures of 20-100°C and CO pressures of 20-50 bar; in all cases the yields are over 70%. Arylsulfonyl isocyanates are important intermediates in the synthesis of herbicides and pharmaceutical products of the sulfonylurea type. M= Na, Karyl = phenyl, p-tolyl, 2-chlorophenyl, 2-bromophenyl, 2-naphthyl.

      • equation image
    16. Cooperative Interactions in Molecular Recognition–the Binding of Diamines to a Tetracarboxylic Acid (pages 1148–1150)

      Dr. Frank Ebmeyer and Dr. Julius Rebek Jr.

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199011481

      Thumbnail image of graphical abstract

      An allosteric effect seems to be responsible for the host molecule 1 forming 1:2 complexes with hydrazine, ethylenediamine, and 1,4-diazabicyclo[2.2.2]octane (DABCO), whereby the second association constant is respectively a factor of 50, 200, and 2 greater than the first. In the first two cases this positive cooperative interaction is much stronger than in ditopic crown ethers.

    17. Synthesis and Structure of a Diphosphadigalletane: A Novel Base-Stabilized Ga2P2 Ring System (pages 1150–1151)

      Prof. Alan H. Cowley, Prof. Richard A. Jones, Miguel A. Mardones, Dr. Jaime Ruiz, Prof. Jerry L. Atwood and Dr. Simon G. Bott

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199011501

      Thumbnail image of graphical abstract

      The lowering of the Lewis activity at the Gaatom by intramolecularly coordinating amino substituents is the essential prerequisite for the synthesis of the diphosphadigalletane 1. Analogous ring systems were hitherto known only for the lighter elements of groups 13 and 15. The Ga-P bond length of 2.338 Å is 0.1 Å shorter than the corresponding bond lengths in intermolecular donor-acceptor adducts of the composition (RRGaPRR)2.

    18. Facile Hydrogenation of the Central Cyclohexatriene of Tris(benzocyclobutadieno)benzene: Synthesis, Structure, and Thermal and Photochemical Isomerization of all-cis-Tris(benzocyclobuta)cyclohexane (pages 1151–1154)

      Debra L. Mohler, Prof. Dr. K. Peter C. Vollhardt and Dr. Stefan Wolff

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199011511

      Thumbnail image of graphical abstract

      A bond-fixed, planar cyclohexane skeletal framework characterizes the tribenzo-annelated cis-tris[2.2.2]-σ-homobenzene 1(R = H), which is formed from the cyclohexatriene precursor by hydrogenation. Above 125°C a tribenzocyclododecahexaene is formed by a concerted retro-[2 + 2+ 2]-cycloaddition. In contrast, 1 is converted photochemically into a novel polycycle.

    19. Structure of a Synthetic Trefoil Knot Coordinated to Two Copper(I) Centers (pages 1154–1156)

      Dr. Christiane O. Dietrich-Buchecker, Dr. Jean Guilhem, Dr. Claudine Pascard and Dr. Jean-Pierre Sauvage

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199011541

      Thumbnail image of graphical abstract

      There is no longer any doubt about the structure of the trefoil knotted compound that was first described in 1989. An X-ray structure analysis of the Cu-complexed compound confirms the structure derived from mass and NMR spectra. In addition it was found that this topologically interesting chiral compound crystallizes as an assembly of both enantiomers.

    20. Synthesis, Structure, and Catalase-Type Activity of a Novel Oxo-Bridged Tetranuclear Manganese Aggregate Exhibiting Short OċO Interactions (pages 1156–1158)

      Robert T. Stibrany and Dr. Sergiu M. Gorun

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199011561

      The complex anion of the Ba/Ca salt 1 is characterized by an oxo(hydroxo)-bridged MnII Mnmath imagecenter with an (O … H … O)3⊖ core. Ba2⊕ and Ca2⊕ ions are linked to the Mn4 center via hydrogen bonded water molecules. The Mn4 center has the same oxidation level as the S0 state of the reaction center of photosystem II (PSII). The catalase activity–evolution of O2 from H2O2–parallels that of both the S0 state of PSII and of Mn-pseudocatalases.

      • equation image
    21. The Tri-μ-amidobis[triamminecobalt(III)] Cation: The First Triply Amido-bridged Complex (pages 1158–1159)

      Dr. Walter Frank, Klaus Hoffmann and Prof. Dr. Ludwig Heck

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199011581

      Thumbnail image of graphical abstract

      The highly symmetric cation 1 of the salt 1-Br3, which is accessible by reaction of potassium amide in liquid ammonia with hexaminecobalt(III) perchlorate and precipitation with KBr. is an important exemplary intermediate of the condensation of ammine complexes. The trigonal-bipyramidal core of 1is elongated along the threefold axis.

    22. A Synthetic Allosteric System with High Cooperativity between Polar and Hydrophobia Binding Sites (pages 1159–1160)

      Prof. Dr. Hans-Jörg Schneider and Dipl.-Chem. Dieter Ruf

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199011591

      Thumbnail image of graphical abstract

      A lipophilic pocket is formed in 1 when metal ions such as Cu2⊕ or Zn2⊕ are added. This was confirmed by the finding that both the high-field shift of the α-H-NMR signals of naphthalene as well as the fluorescence intensity of dansylamide increase with metal-ion concentration in the presence of 1. The picture on the right (below) schematically shows the binding of a metal ion M and an organic molecule L.

    23. Host-Guest Complexes with Closed, Half-open, and Stretched Receptors: Hydrophobic Cavity Effects and Induced Pole-Dipole Interactions (pages 1161–1162)

      Prof. Dr. Hans-Jörg Schneider, Dipl.-Chem. Thomas Blatter and Patrick Zimmermann

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199011611

      Thumbnail image of graphical abstract

      The induction of dipoles by N centers apparently plays an essential role in the binding of lipophilic substrates to receptors. This follows from studies with a closed (type A), a half-open (type B), and a stretched (type C) receptor and several arenas, and dichloro- and diiodomethane.

    24. Macrocyclically Fixed Diarylhexatrienes (pages 1162–1164)

      Prof. Dr. Fritz Vögtle and Dipl.-Chem. Carlo Thilgen

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199011621

      Thumbnail image of graphical abstract

      Configurationally and conformationally fixed diarylhexatriene chromophores characterize the compounds 1 and 2, which were obtained by double McMurry coupling. The UV/VIS spectra indicate, both on grounds of the position as well as the number of bands, that 1 and 2 contain two chromophores and not one chromophore extending over the whole macrocycle. R[DOUBLE BOND]H, CH3.

    25. Stable Azirinimines? A Structural Corrigendum (pages 1164–1166)

      Dr. Klaus Banert, Elisabeth Reissaus, Prof. Dr. Hans-Jörg Deiseroth, Claus Peter Kluge and Eva-Maria Peters

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199011641

      Thumbnail image of graphical abstract

      Unfortunately, not the azirinimine 2, as was recently erroneously reported, but the structurally isomeric product 3 is formed upon reaction of the tosylate 1 with potassium cyanide and tetrabutylammonium chloride in nitromethane/ water. Final doubts were dispelled by an X-ray structure analysis of 3.

    26. Epoxidation of the P[DOUBLE BOND]C Double Bond of Phosphaalkene Complexes: X-Ray Crystal Structure Analysis of a Stable Oxaphosphirane Complex (pages 1166–1167)

      Mr. Siegfried Bauer, Dr. Angela Marinetti, Dr. Louis Ricard and Prof. Dr. François Mathey

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199011661

      Thumbnail image of graphical abstract

      P-complexed phosphaalkenes are not oxidized at the phosphorus; hence the result of the reaction of the W(CO)5 complex 1 with meta-chloroperbenzoic acid. The stable oxaphosphirane 2 is formed with retention of the trans-stereochemistry of the P[DOUBLE BOND]C double bond. The P[DOUBLE BOND]C bond in the ring (1.778 Å) is astonishingly short. Mes = 2,4,6-Me3C6H2.

    27. Nonradioactive Assay of DNA Hybridization by DNA-Template-Mediated Formation of a Ternary TbIII Complex in Pure Liquid Phase (pages 1167–1169)

      Dr. Andreas Oser and Prof. Dr. Günther Valet

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199011671

      Thumbnail image of graphical abstract

      A complex of one Tb3⊕ ion and two chelate ligands is preferentially formed when the ligands are directly adjacent through template-directed binding of a pair of appropriately modified oligodeoxyribonucleotides to complementary DNA. The Tb-complex is a fluorescence–resonance–energy transfer system (FRET) with long-lived Tb3⊕ fluorescence, and detection of a DNA hybridization in the liquid phase is possible. Due to the necessity of a close proximity of the two oligonucleotide probes the method is of special significance for the rapid identification of mutations, insertions, deletions, chromosome translocations, and splicing sites.

    28. Synthesis of D- and L-2-Amino-2-deoxyarabinose and 1,4-Dideoxy-1,4-iminolyxitol by (C2 + C3)-Nitroaldol Addition with 2-O-Benzylglyceraldehyde (pages 1169–1171)

      Dipl.-Chem. Volkmar Wehner and Prof. Dr. Volker Jäger

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199011691

      Thumbnail image of graphical abstract

      The highly stereoselective nitroaldol addition of nitroacetaldehyde diethylacetal 1 and 2-O -benzylglyceraldehyde 2 to give only two of the four possible diastereomers of 3 in the ratio 88:12 has opened up a productive entry to both enantiomers of 2-arabinosamine as well as to 1,4-dideoxy-1,4-iminolyxitol (glucosidase inhibitor). The total yield over eight steps to the lyxitol is 17%.

    29. Cyclization of N-Protected l-Amino-4-pentene-2,3-diols to lxyo-Configurated Deoxyimino Sugars (cis-Dihydroxypyrrolidines); Synthesis of Potential Glycosidase Inhibitors (pages 1171–1173)

      Prof. Dr. Volker Jäger and Dipl.-Chem. Walter Hümmer

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199011711

      Thumbnail image of graphical abstract

      The well-known halogen- or PdIII -catalyzed cyclizations of unsaturated amino alcohols could be extended to substrates with two free OH groups (e.g. 1 [RIGHTWARDS ARROW] 2; Z [DOUBLE BOND] COOCH2Ph). The iminolyxitol derivatives thereby accessible with high stereoselectivity in only few steps are of interest as potential glycosidase inhibitors.

    30. Fluorescence “Off–On” Signalling upon Linear Recognition and Binding of α,ω-Alkanediyldiammonium Ions by 9,10-Bis{(1-aza-4,7,10,13,16-pentaoxacyclooctadecyl)methyl}anthracene (pages 1173–1175)

      Dr. A. Prasanna de Silva and Dr. K. R. A. Samankumara Sandanayake

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199011731

      Thumbnail image of graphical abstract

      A drastic increase in the fluorescence quantum yield is observed when 1, which contains two crown ether units and a rigid fluorescing spacer, is allowed to react with an α,ω-alkanediyldiammonium ion of the “correct” chain length. Most effective is the pseudointramolecular cyclization when the alkanediyldiammonium ion has a C4 chain.

  3. Book Reviews

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