• Issue

    Angewandte Chemie International Edition: Volume 43, Issue 12

    1443-1603
    March 12, 2004

Cover Picture: Combinatorial Catalysis with Bimetallic Complexes: Robust and Efficient Catalysts for Atom-Transfer Radical Additions (Angew. Chem. Int. Ed. 12/2004)

  • Page: 1443
  • First Published: 09 March 2004

Highly efficient Rh–Ru catalysts for atom-transfer radical additions have been discovered in a fast screening assay. The catalyst library used in this assay was generated in situ by mixing chloro-bridged complexes of RuII, RuIII, RuIV, RhI, RhIII, IrI, IrIII, PdII, and PtII with three different RuII–phosphane complexes. On page 1520 ff., K. Severin and co-workers describe the structures and reactivities of the new catalysts.

Amine-Catalyzed Epoxidation of Alkenes: A New Mechanism for the Activation of Oxone

  • Pages: 1460-1462
  • First Published: 09 March 2004
Amine-Catalyzed Epoxidation of Alkenes: A New Mechanism for the Activation of Oxone

Some of the most promising systems emerging for the catalytic asymmetric epoxidation of alkenes involve the activation of oxone (active constituent KHSO5). The discovery of catalysis by amines is an exciting development in this area of organocatalysis, and a new mechanism for the activation of oxone has been advanced with important consequences (see scheme).

A New Arene Synthesis—Or: How Inert Is the Cyclopentadienyl Ligand?

  • Pages: 1463-1464
  • First Published: 09 March 2004
A New Arene Synthesis—Or: How Inert Is the Cyclopentadienyl Ligand?

A nice Cp recipe: The reaction of 1 with benzonitrile is a novel arene synthesis developed by Xi, Takahashi, and co-workers. Formally it is the breakdown of a cyclopentadienyl ligand into a C2 fragment and a C3 fragment which are then incorporated into a benzene and pyridine derivative, respectively. This synthetic variant has possible interesting applications in the preparation of oligoarenes.

Metal Carboxylates with Open Architectures

  • Pages: 1466-1496
  • First Published: 09 March 2004
Metal Carboxylates with Open Architectures

Metal carboxylates form a variety of fascinating open-framework structures (see picture). In this Review the synthesis, structure, and properties of various families of metal carboxylates, as well as organic–inorganic hybrid structures involving carboxylates, are presented. The use of carboxylate ligands as linking groups is of particularly interest.

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A Red, Green, and Blue (RGB) Polymeric Electrochromic Device (PECD): The Dawning of the PECD Era

  • Pages: 1498-1502
  • First Published: 09 March 2004
A Red, Green, and Blue (RGB) Polymeric Electrochromic Device (PECD): The Dawning of the PECD Era

Completing RGB color space: The electrochemical and optical properties of the first electrochemically prepared conducting polymer that is green in its neutral form are reported. The extreme stability of this polymer after 10 000 double potential steps makes it the best and only candidate for providing the missing third leg of RGB color space (red, blue, and green reflection; see picture) required for polymeric electrochromics.

Three-Dimensional Frameworks of Gallium Selenide Supertetrahedral Clusters

  • Pages: 1502-1505
  • First Published: 09 March 2004
Three-Dimensional Frameworks of Gallium Selenide Supertetrahedral Clusters

Humidity-dependent electrical conductivity, which suggests possible applications in sensors, is exhibited by OCF-6GaSe, an open-framework gallium selenide assembled from T3 (Ga10Se2010−) supertetrahedral clusters (picture, left). Furthermore, materials based on T4 (Zn4Ga16Se3514−, right), the largest supertetrahedral selenide cluster so far, were also obtained.

Preparation of Mesoporous Silica Monoliths with Ordered Arrays of Macrochannels Templated from Electric-Field-Oriented Hydrogels

  • Pages: 1505-1507
  • First Published: 09 March 2004
Preparation of Mesoporous Silica Monoliths with Ordered Arrays of Macrochannels Templated from Electric-Field-Oriented Hydrogels

Silica monoliths with ordered arrays of micrometer-scale columns were fabricated from polyacrylamide gel templates. The preparation of the template involves the charged comonomer, N-acryloyl glycine, and is controlled by an externally applied electric field. This approach gives rise to the self-organization of columnar density patterns in the template (left; bar=10μm) that are recovered in the silica monoliths upon impregnation with tetramethylorthosilicate and subsequent calcination (right).

A 3D Hybrid Network Containing Large Spherical Cavities Formed through a Combination of Metal Coordination and Hydrogen Bonding

  • Pages: 1507-1511
  • First Published: 09 March 2004
A 3D Hybrid Network Containing Large Spherical Cavities Formed through a Combination of Metal Coordination and Hydrogen Bonding

The hole story: A microporous material with cavities that have an internal volume of 1850 Å3 has been formed from simple starting materials by combining them first through covalent coordination, and then through hydrogen-bonding interactions. The capsules in the 3D network can function as hosts for guest molecules such as triphenylmethane, sodium tetraphenylborate, and triptycene (see picture).

Ordered Self-Assembly and Electronic Behavior of C60–Anthrylphenylacetylene Hybrid

  • Pages: 1512-1516
  • First Published: 09 March 2004
Ordered Self-Assembly and Electronic Behavior of C60–Anthrylphenylacetylene Hybrid

A functional hybrid molecule, C60–MPAA, has been designed and synthesized by taking advantage of the excellent physical and chemical properties of C60 and nanoscale ordering of anthryl-based self-assembled monolayers (SAMs). The SAM of C60–MPAA exhibits stable and highly ordered 2D arrays that form an oblique lattice at room temperature and exhibit interesting electronic properties.

Site-Specific Introduction of Sialic Acid into Insulin

  • Pages: 1516-1520
  • First Published: 09 March 2004
Site-Specific Introduction of Sialic Acid into Insulin

More gain, less pain: A new long-acting insulin (see structure) was created by the enzymatic introduction of sialyllactose into mutant insulins. The glycosylation site was introduced into the insulin by point mutation without loss of biological activity. The experimental results with mice clearly demonstrated that the introduction of a sialic acid residue is crucial in prolonging glucose-lowering activity in the blood.

Combinatorial Catalysis with Bimetallic Complexes: Robust and Efficient Catalysts for Atom-Transfer Radical Additions

  • Pages: 1520-1524
  • First Published: 09 March 2004
Combinatorial Catalysis with Bimetallic Complexes: Robust and Efficient Catalysts for Atom-Transfer Radical Additions

A radical alternative? Two highly efficient catalysts for atom-transfer radical additions were discovered in a parallel screening of bimetallic complexes. Both catalysts contain a rhodium-centered fragment (blue), which is connected through three chloro bridges to a ruthenium-centered fragment (red).

Thermal and Photochemical Properties of 4′,7-Dihydroxyflavylium in Water–Ionic Liquid Biphasic Systems: A Write–Read–Erase Molecular Switch

  • Pages: 1525-1527
  • First Published: 09 March 2004
Thermal and Photochemical Properties of 4′,7-Dihydroxyflavylium in Water–Ionic Liquid Biphasic Systems: A Write–Read–Erase Molecular Switch

Switching colors: 4′,7-Dihydroxyflavylium (AH+) in water–ionic liquid biphasic systems can be used as a write–read–erase system. In acid media, the chalcone (Ct) form is soluble in ionic liquids and is thermally metastable, but reacts photochemically (write) to give the yellow flavylium salt, which can be optically read without being erased. The system is prepared for a new cycle by two consecutive pH “jumps”.

Ionic Perylenetetracarboxdiimides: Highly Fluorescent and Water-Soluble Dyes for Biolabeling

  • Pages: 1528-1531
  • First Published: 09 March 2004
Ionic Perylenetetracarboxdiimides: Highly Fluorescent and Water-Soluble Dyes for Biolabeling

Dying to be seen: A series of water-soluble and highly fluorescent perylenetetracarboxdiimides (PDIs) have been synthesized in high yields by introducing charged groups into the bay region of PDI (see picture; C gray, H white, S yellow, O red). They can be used for staining living cells as they are nontoxic.

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Minimal Functional Model of Hemostasis in a Biomimetic Microfluidic System

  • Pages: 1531-1536
  • First Published: 09 March 2004
Minimal Functional Model of Hemostasis in a Biomimetic Microfluidic System

The proof of the model is in the function: A minimal model of hemostasis (a complex biochemical network responsible for blood coagulation) may be implemented with only three chemical reactions, which creates a biomimetic functional microfluidic system that is capable of repairing itself (as modeled in the figure). This simple system shows threshold response and sensitivity to flow similar to that observed in hemostasis.

Shape Effect in Nanoparticle Self-Assembly

  • Pages: 1536-1540
  • First Published: 09 March 2004
Shape Effect in Nanoparticle Self-Assembly

Particle anisotropy determines the way nanoparticles self-assemble, as shown in the picture. Gold and silver spheroids, rods, and plates with length-to-width ratios ranging from 1 to 25 show different liquid-crystalline order structures. These structures are analogous to the entropy-driven ordering that occurs at high volume fractions and is useful for large-scale ordering or shape separation.

Pt Hollow Nanospheres: Facile Synthesis and Enhanced Electrocatalysts

  • Pages: 1540-1543
  • First Published: 09 March 2004
Pt Hollow Nanospheres: Facile Synthesis and Enhanced Electrocatalysts

A facile large-scale preparation of Pt hollow nanospheres (see TEM image) makes use of Co nanoparticle as sacrificial templates. The nanospheres exhibit enhanced electrocatalytic activity. This method has been extended to the fabrication of industrially potentially useful Au, Pd, and other mono- and multimetallic hollow nanospheres.

The X-ray Structure of a Vinyl Cation

  • Pages: 1543-1546
  • First Published: 09 March 2004
The X-ray Structure of a Vinyl Cation

Thermodynamic stabilization by two β-silyl substituents and essentially nonnucleophilic reaction conditions are prerequisites for the preparation of the first structurally well-characterized vinyl cation 1 (see structure). The occurrence of β-SiC hyperconjugation in 1 is indicated by unusually long SiCβ bonds.

A Three-Dimensional Mesoporous Titanosilicate Support for Gold Nanoparticles: Vapor-Phase Epoxidation of Propene with High Conversion

  • Pages: 1546-1548
  • First Published: 09 March 2004
A Three-Dimensional Mesoporous Titanosilicate Support for Gold Nanoparticles: Vapor-Phase Epoxidation of Propene with High Conversion

Direct selective gas-phase epoxidation of propene with commercially viable conversion has been achieved with catalysts consisting of gold nanoparticles (3–5 nm) supported on large-pore (>7 nm) silylated mesoporous titanosilicates with Ba(NO3)2 as a promoter. The picture provides a plausible mechanism for the synergetic cooperation of the Au and Ti sites, which is superimposed onto a TEM image of the material.

Renewable Alkanes by Aqueous-Phase Reforming of Biomass-Derived Oxygenates

  • Pages: 1549-1551
  • First Published: 09 March 2004
Renewable Alkanes by Aqueous-Phase Reforming of Biomass-Derived Oxygenates

A clean stream of alkanes from renewable biomass resources is obtained through aqueous-phase reforming in a single reactor. Alkanes are produced from biomass-derived sorbitol through a bifunctional pathway (see scheme) that involves the dehydration of sorbitol on acid sites (SiO2/Al2O3) and hydrogenation of intermediates on a metal catalyst under a H2 atmosphere. Hydrogen is produced from sorbitol and water on the metal catalyst in the same reactor.

Side-Wall Opening of Single-Walled Carbon Nanotubes (SWCNTs) by Chemical Modification: A Critical Theoretical Study

  • Pages: 1552-1554
  • First Published: 09 March 2004
Side-Wall Opening of Single-Walled Carbon Nanotubes (SWCNTs) by Chemical Modification: A Critical Theoretical Study

In contrast to earlier theoretical studies and experimental expectation, full high-level (B3LYP/6-31G*) computations on various nanotube models reveal that SWCNTs with O, NH, CH2, and SiH2 addends favor opened structures rather than three-membered rings. Furthermore, the diagonal CC bonds in (8,0) zigzag nanotubes, rather than CC bonds parallel to the axis, are the favorable sites for chemical modification.

Self-Assembled Aggregates of IgGs as Templates for the Growth of Clusters of Gold Nanoparticles

  • Pages: 1555-1558
  • First Published: 09 March 2004
Self-Assembled Aggregates of IgGs as Templates for the Growth of Clusters of Gold Nanoparticles

Immunoglobulin G templates: Clusters of gold nanoparticles are grown (see picture) from templates formed from the self-assembly of immunoglobulin Gs (IgGs) by using a synthetic divalent antigen. Carbohydrates inherent to IgGs create local nucleation centers for the electroless deposition of gold.

Enantioselective Total Synthesis of Batzelladine A

  • Pages: 1559-1562
  • First Published: 09 March 2004
Enantioselective Total Synthesis of Batzelladine A

One-step formation of an enone from a primary alcohol has been effectively applied in the total synthesis of batzelladine A (1). Successive 1,3-dipolar cycloadditions with a subsequent cyclization were used to form the tricyclic guanidine subunit of this natural product, which has the strongest inhibitory activity of HIV gp120-CD4 binding among the batzelladines.

Dimeric Aminoglycosides as Antibiotics

  • Pages: 1562-1566
  • First Published: 09 March 2004
Dimeric Aminoglycosides as Antibiotics

Double duty: Dimeric aminoglycoside antibiotics were designed by linking neamine or nebramine cores with various tethers differing in length and composition. The resulting dimeric aminoglycosides displayed high affinity for the 16S A site of ribosomal RNA (a representation of the complex is shown here) and were effective against various aminoglycoside-resistant bacterial strains.

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Enantioselective Mannich-Type Reaction Catalyzed by a Chiral Brønsted Acid

  • Pages: 1566-1568
  • First Published: 09 March 2004
Enantioselective Mannich-Type Reaction Catalyzed by a Chiral Brønsted Acid

No metal required: The Mannich-type reaction of ketene silyl acetals 2 with aldimines 1 proceeded highly enantioselectively to afford the syn isomer of β-aminoesters 3 with up to 96 % ee under the influence of a chiral Brønsted acid 4 derived from (R)-BINOL.

Chemical Synthesis of a Skeleton Structure of Sperm CD52—A GPI-Anchored Glycopeptide

  • Pages: 1569-1573
  • First Published: 09 March 2004
Chemical Synthesis of a Skeleton Structure of Sperm CD52—A GPI-Anchored Glycopeptide

Going native: A highly convergent synthetic strategy was established to prepare a skeleton structure of sperm CD52 antigen (depicted), which represents the first chemical synthesis of a complex, all natively linked glycosylphosphatidylinositol (GPI)–glycopeptide conjugate.

Theoretical Search for Very Short Metal–Actinide Bonds: NUIr and Isoelectronic Systems

  • Pages: 1573-1576
  • First Published: 09 March 2004
Theoretical Search for Very Short Metal–Actinide Bonds: NUIr and Isoelectronic Systems

Cumulated triple bonds: A new class of molecules, the isoelectronic series of NUIr, (depicted) has been postulated and theoretically studied. The bond between the actinide and the 5d-metal atom is very short and is shown to correspond to triple bonding. The NU bond is also a triple bond.

Efficient Hydration of Nitriles to Amides in Water, Catalyzed by Ruthenium Hydroxide Supported on Alumina

  • Pages: 1576-1580
  • First Published: 09 March 2004
Efficient Hydration of Nitriles to Amides in Water, Catalyzed by Ruthenium Hydroxide Supported on Alumina

A broad range of amides is accessible in excellent yield (>99 %) by hydration of the corresponding nitriles in water in the presence of the supported ruthenium catalyst Ru(OH)x/Al2O3 (see scheme). For example, the industrially important conversion of acrylonitrile into acrylamide was achieved in quantitative yield and better than 99 % selectivity. The catalyst can be reused without loss of catalytic activity and selectivity.

Modular Synthesis of Ruthenium-Labeled Diaryl Ether Peptoids

  • Pages: 1581-1583
  • First Published: 09 March 2004
Modular Synthesis of Ruthenium-Labeled Diaryl Ether Peptoids

A packet of sandwiches: A new concept of modular assembly of novel, metal-labeled biooligomers starting from amino acid sandwich complexes is introduced. The first diaryl ether tetrapeptoid containing two ruthenium-sandwich labels is prepared (see picture; Boc=tert-butoxycarbonyl), it should now be possible to prepare longer peptoids by repetitive methods.

Directed Reduction of Six-Membered Nitrogen Heterocycles—Selective Formation of Polynuclear Titanium Complexes

  • Pages: 1583-1587
  • First Published: 09 March 2004
Directed Reduction of Six-Membered Nitrogen Heterocycles—Selective Formation of Polynuclear Titanium Complexes

Two, three, four, or eight N-heterocycles react in the coordination sphere of titanium(II) compounds to give polynuclear titanium complexes (see picture, red=TiCp2, blue=N, white=C). Simultaneously occurring CC couplings mark a new strategy for the synthesis of self-assembled compounds of the early transition metals.

Efficient, Copper-Catalyzed, Aerobic Oxidation of Primary Alcohols

  • Pages: 1588-1591
  • First Published: 09 March 2004
Efficient, Copper-Catalyzed, Aerobic Oxidation of Primary Alcohols

An additive is the key to success: Catalytic amounts of N-methylimidazole are crucial for the aerobic oxidation of primary aliphatic alcohols in the presence of CuCl, 1,10-phenanthroline (phen), and di-tert-butyl azodicarboxylate (DBAD). This reaction, under neutral conditions, yields the aldehydes quantitatively and selectively without overoxidation to the carboxylic acids.

Aminoglycoside Microarrays To Study Antibiotic Resistance

  • Pages: 1591-1594
  • First Published: 09 March 2004
Aminoglycoside Microarrays To Study Antibiotic Resistance

On to the next round! A sensitive microarray of immobilized aminoglycosides was used to study the binding of antibiotics to resistance-causing enzymes (see picture). This, in combination with other methods, will lead to the identification of new antibiotics that bind weakly to these enzymes and strongly to the therapeutic targets.

Mixed Helices—A General Folding Pattern in Homologous Peptides?

  • Pages: 1594-1597
  • First Published: 09 March 2004
Mixed Helices—A General Folding Pattern in Homologous Peptides?

You may now exchange rings! “Mixed helices” along a peptide sequence, in which rings of different sizes are held together by hydrogen bonds in alternating directions (see picture), prove to be a general folding principle in homologous α-, β-, γ-, and δ-peptides.

Preview: Angew. Chem. Int. Ed. 12/2004

  • Page: 1603
  • First Published: 09 March 2004