• Issue

    Angewandte Chemie International Edition: Volume 52, Issue 30

    7607-7885
    July 22, 2013

Cover Pictures

Free Access

Cover Picture: Light-Regulated Stapled Peptides to Inhibit Protein–Protein Interactions Involved in Clathrin-Mediated Endocytosis (Angew. Chem. Int. Ed. 30/2013)

  • Page: 7607
  • First Published: 01 July 2013
Cover Picture: Light-Regulated Stapled Peptides to Inhibit Protein–Protein Interactions Involved in Clathrin-Mediated Endocytosis (Angew. Chem. Int. Ed. 30/2013)

Remote control of membrane traffic is described by E. Giralt, P. Gorostiza, et al. in their Communication on page 7704 ff. Photoswitchable inhibitors of protein–protein interactions have been applied to photoregulate clathrin-mediated endocytosis in living cells. Traffic light peptides constitute a new tool to control cell signaling in spatiotemporally defined patterns and can be used to dissect the role of clathrin-mediated endocytosis in receptor internalization and in cell growth, division, and differentiation.

Free Access

Inside Cover: A Chemo-Enzymatic Approach for Site-Specific Modification of the RNA Cap (Angew. Chem. Int. Ed. 30/2013)

  • Page: 7608
  • First Published: 21 June 2013
Inside Cover: A Chemo-Enzymatic Approach for Site-Specific Modification of the RNA Cap (Angew. Chem. Int. Ed. 30/2013)

Targeting the mRNA cap by a chemo-enzymatic approach opens up new possibilities in mRNA isolation and visualization. In their Communication on page 7874 ff. A. Rentmeister and co-workers present a novel two-step approach for the regiospecific labeling of the m7G cap, a hallmark of eukaryotic mRNAs. They make use of a trimethylguanosine variant capable of transferring reactive groups from AdoMet analogues to the cap. The transferred residues are amenable to click reactions.

Free Access

Inside Back Cover: Shaping Micelles: The Interplay Between Hydrogen Bonds and Dispersive Interactions (Angew. Chem. Int. Ed. 30/2013)

  • Page: 7887
  • First Published: 27 June 2013
Inside Back Cover: Shaping Micelles: The Interplay Between Hydrogen Bonds and Dispersive Interactions (Angew. Chem. Int. Ed. 30/2013)

Unraveling the inverse micelle structure of propofol, a potent general anesthetic, through a combination of mass-resolved laser-based spectroscopic techniques and high-level quantum-mechanical calculations is presented by J. A. Fernández et al. in their Communication on page 7772 ff. In propofol, highly directional hydrogen bonds impose a framework on which the rest of the noncovalent interactions are built to give the micelle its final shape, leaving a characteristic signature in the infrared spectrum.

Free Access

Back Cover: Highly Conductive Aluminum Textile and Paper for Flexible and Wearable Electronics (Angew. Chem. Int. Ed. 30/2013)

  • Page: 7888
  • First Published: 21 June 2013
Back Cover: Highly Conductive Aluminum Textile and Paper for Flexible and Wearable Electronics (Angew. Chem. Int. Ed. 30/2013)

Wearable electronics require highly conductive fibrous materials, which can now be fabricated at room temperature. In their Communication on page 7718 ff., H. M. Lee, S. H. Ko, and co-workers demonstrate that cotton or paper fibers can be impregnated and coated with Al atoms from the precursor Al{O(C4H9)2}. The fibrous materials exhibit excellent electrical conductivity, as well as enduring mechanical strength, which is indicative of their potential applications for flexible and wearable electronics.

Graphical Abstract

Author Profile

Janine Cossy

  • Pages: 7634-7635
  • First Published: 02 April 2013
Janine Cossy

“What I look for first in a publication is the abstract and schemes. The most important thing I learned from my parents is to work hard. …︁” This and more about Janine Cossy can be found on page 7634–7635.

Book Review

Acids and Bases. Solvent Effects on Acid–Base Strength. By Brian G. Cox.

  • Page: 7638
  • First Published: 21 June 2013
Acids and Bases. Solvent Effects on Acid–Base Strength. By Brian G. Cox.

Oxford University Press, 2013. 160 pp., softcover, $ 45.00.—ISBN 978-0199670529

Highlights

Energy Harvesting

Nanofluidics for Giant Power Harvesting

  • Pages: 7640-7641
  • First Published: 17 June 2013
Nanofluidics for Giant Power Harvesting

Nanochannels for power generation: The confinement of fluid motion in a single boron nitride nanotube can provide an efficient means of power harvesting owing to the osmotically driven streaming current under a salt concentration difference (see picture). Devices based on this principle may open a new avenue in the exploration for new sources of renewable energy.

Sustainable Chemistry

More Sustainable Formation of CN and CC Bonds for the Synthesis of N-Heterocycles

  • Pages: 7642-7644
  • First Published: 17 June 2013
More Sustainable Formation of C<span class='icomoon'></span>N and C<span class='icomoon'></span>C Bonds for the Synthesis of N-Heterocycles

Heterocycles made green: New methodologies for the synthesis of pyrroles were recently developed based on domino Ir- and Ru-catalyzed amination and alkylations of alcohols. The concept provides a greener approach to interesting N-heterocyclic compounds.

Minireview

Total Synthesis

The Winding Pathway to Erythropoietin Along the Chemistry–Biology Frontier: A Success At Last

  • Pages: 7646-7665
  • First Published: 17 June 2013
The Winding Pathway to Erythropoietin Along the Chemistry–Biology Frontier: A Success At Last

Going native: The total synthesis of a homogeneous erythropoietin, possessing the native amino acid sequence and chitobiose glycans at each of the three wild-type sites of N glycosylation, has been accomplished. Herein is an account of the decade-long research effort en route to this formidable target compound.

Review

Bioorganometallic Chemistry

Bioactive Luminescent Transition-Metal Complexes for Biomedical Applications

  • Pages: 7666-7682
  • First Published: 13 June 2013
Bioactive Luminescent Transition-Metal Complexes for Biomedical Applications

Metal-based theranostics: This Review highlights recent examples of biologically active luminescent metal complexes that can target and probe a specific biomolecule, and offers insight into the future potential of luminescent metal-based therapeutics for the investigation and treatment of human diseases.

Communications

Bioorganic Chemistry

Polymer Nanomicelles for Efficient Mucus Delivery and Antigen-Specific High Mucosal Immunity

  • Pages: 7684-7689
  • First Published: 13 June 2013
Polymer Nanomicelles for Efficient Mucus Delivery and Antigen-Specific High Mucosal Immunity

Micelles for mucosal immunity: A mucosal vaccine system based on γ-PGA nanomicelles and viral antigens was synthesized. The intranasal administration of the vaccine system induces a high immune response both in the humoral and cellular immunity (see picture).

Bioorganometallics

The Ferroquine Antimalarial Conundrum: Redox Activation and Reinvasion Inhibition

  • Pages: 7690-7693
  • First Published: 13 June 2013
The Ferroquine Antimalarial Conundrum: Redox Activation and Reinvasion Inhibition

Metal health: Ferroquine is a ferrocene-based analogue of the antimalarial drug chloroquine. In addition to the primary mechanism of quinoline action, fluorescent probe studies in infected red blood cells show another mechanism is at work. It is based on the production of HO. in the acidic and oxidizing environment of the digestive vacuole of the malaria parasite and implies that, with ferroquine, reinvasion can be inhibited.

Enantioselective Catalysis

Combining NHC–Cu and Brønsted Base Catalysis: Enantioselective Allylic Substitution/Conjugate Additions with Alkynylaluminum Reagents and Stereospecific Isomerization of the Products to Trisubstituted Allenes

  • Pages: 7694-7699
  • First Published: 18 June 2013
Combining NHC–Cu and Brønsted Base Catalysis: Enantioselective Allylic Substitution/Conjugate Additions with Alkynylaluminum Reagents and Stereospecific Isomerization of the Products to Trisubstituted Allenes

All-catalytic route to trisubstituted allenes: The first examples of catalytic enantioselective allylic substitution reactions that involve alkyne-based nucleophiles and lead to products having tertiary stereogenic centers are followed by an exceptionally stereospecific amine-catalyzed isomerization to trisubstituted allenes (see picture; NHC=N-heterocyclic carbene).

Asymmetric Synthesis

Remarkable Configurational Stability of Magnesiated Nitriles

  • Pages: 7700-7703
  • First Published: 19 June 2013
Remarkable Configurational Stability of Magnesiated Nitriles

Quaternary stereocenters: Chiral α-magnesiated nitriles can be formed by deprotonation and are configurationally stable at low temperature, even for acyclic examples. These can be trapped with electrophiles to give enantiomerically enriched quaternary substituted products (see scheme; TMP=2,2,6,6-tetramethylpiperidine).

Optopharmacology

Light-Regulated Stapled Peptides to Inhibit Protein–Protein Interactions Involved in Clathrin-Mediated Endocytosis

  • Pages: 7704-7708
  • First Published: 17 June 2013
Light-Regulated Stapled Peptides to Inhibit Protein–Protein Interactions Involved in Clathrin-Mediated Endocytosis

Control of membrane traffic: Photoswitchable inhibitors of protein–protein interactions were applied to photoregulate clathrin-mediated endocytosis (CME) in living cells. Traffic light (TL) peptides acting as “stop” and “go” signals for membrane traffic can be used to dissect the role of CME in receptor internalization and in cell growth, division, and differentiation.

Demethylases/Hydroxylases

Open Access

Is JmjC Oxygenase Catalysis Limited to Demethylation?

  • Pages: 7709-7713
  • First Published: 20 June 2013
Is JmjC Oxygenase Catalysis Limited to Demethylation?

Jobs on the side: Substrate selectivity studies indicate that members of the biomedically important JmjC demethylase family of histone Nε-methyllysine demethylases are capable of catalyzing the de-N-alkylation of groups other than N-methyl and can catalyze reactions that form stable hydroxylated products. The differences in binding preferences in this set of enzymes may be helpful in the design of selective inhibitors.

Protein–Ligand Binding

The Binding of Benzoarylsulfonamide Ligands to Human Carbonic Anhydrase is Insensitive to Formal Fluorination of the Ligand

  • Pages: 7714-7717
  • First Published: 20 June 2013
The Binding of Benzoarylsulfonamide Ligands to Human Carbonic Anhydrase is Insensitive to Formal Fluorination of the Ligand

It's the water that matters. Pairs of benzo- and perfluorobenzoarylsulfonamide ligands bind to human carbonic anhydrase with a conserved binding geometry, an enthalpy-driven binding, and indistinguishable binding affinities (see picture). These data support the pervasive theory that the lock-and-key model disregards an important component of binding: the water, which fills the binding pocket of the protein and surrounds the ligand.

Conductive Fibrous Materials

Highly Conductive Aluminum Textile and Paper for Flexible and Wearable Electronics

  • Pages: 7718-7723
  • First Published: 07 June 2013
Highly Conductive Aluminum Textile and Paper for Flexible and Wearable Electronics

Light to wear: Aluminum coated fibrous materials with excellent electrical conductivity and mechanical endurance are fabricated at room temperature by a chemical solution process. The resulting aluminum-coated conductive papers and threads can be used in electric circuits for flexible and wearable electronics.

Asymmetric Fluorination

Enantioselective Fluoroamination: 1,4-Addition to Conjugated Dienes Using Anionic Phase-Transfer Catalysis

  • Pages: 7724-7727
  • First Published: 13 June 2013
Enantioselective Fluoroamination: 1,4-Addition to Conjugated Dienes Using Anionic Phase-Transfer Catalysis

Chiral-anion phase-transfer catalysis (PTC) has been applied towards the enantioselective fluorocyclization reactions of 1,3-dienes. The method affords unprecedented fluorinated benz[f]isoquinoline and octahydroisoquinoline products in high yields and up to 96 % ee. New fluorinated amine reagents outperformed Selectfluor in the desired transformation.

3D Metallomacrocycles

Self-Assembly of a Supramolecular, Three-Dimensional, Spoked, Bicycle-like Wheel

  • Pages: 7728-7731
  • First Published: 13 June 2013
Self-Assembly of a Supramolecular, Three-Dimensional, Spoked, Bicycle-like Wheel

Where there′s a wheel, there′s a way: The terpyridine-based title system has been synthesized through a facile self-assembly process. Two tris(terpyridine) ligands possessing angles of either 120° or 60° between adjacent tpy units were mixed with a stoichiometric amount of Zn2+ (2:6:12) to generate the desired coordination-driven bicycle-like wheel (90 % yield).

Hierarchical Assembly

Simulation-Assisted Self-Assembly of Multicomponent Polymers into Hierarchical Assemblies with Varied Morphologies

  • Pages: 7732-7736
  • First Published: 17 June 2013
Simulation-Assisted Self-Assembly of Multicomponent Polymers into Hierarchical Assemblies with Varied Morphologies

As you like it: The synthesis of supramolecular hierarchical nanostructures with designed morphologies has been realized through computer-simulation-guided multicomponent assembly of polypeptide-based block copolymers and homopolymers. By adjusting the attraction between hydrophobic polypeptide rods, as well as other parameters such as the molar ratio of copolymers and the rigidity of polymers, a variety of morphologies were obtained.

Supported Catalysts

Rationalization of Interactions in Precious Metal/Ceria Catalysts Using the d-Band Center Model

  • Pages: 7737-7741
  • First Published: 18 June 2013
Rationalization of Interactions in Precious Metal/Ceria Catalysts Using the d-Band Center Model

A correlation between ceria reducibility and the precious-metal d-band center is reported for ceria-supported precious-metal catalysts. The results could provide the missing link to fully explain the occurrence of strong metal–support interaction (SMSI) and hydrogen spillover in catalysts that consist of dispersed metals in contact with reducible metal oxides.

Quadruplex Formation

Combination of i-Motif and G-Quadruplex Structures within the Same Strand: Formation and Application

  • Pages: 7742-7746
  • First Published: 14 June 2013
Combination of i-Motif and G-Quadruplex Structures within the Same Strand: Formation and Application

Peaceful coexistence: A double quadruplex composed of an i-motif and a G-quadruplex was constructed within one oligonucleotide strand (see picture). The defined double-quadruplex structure can serve as a NOTIF logic gate on the basis of the fluorescence of crystal violet.

Biosensors

DNA Origami as a DNA Repair Nanosensor at the Single-Molecule Level

  • Pages: 7747-7750
  • First Published: 13 June 2013
DNA Origami as a DNA Repair Nanosensor at the Single-Molecule Level

The folding of DNA molecules by DNA origami is used in a nanosensor to analyze enzymatic DNA repair activity of hAGT. The method uses conformational changes that condition α-thrombin interaction with DNA aptamers, and illustrates the use of DNA origami as a proteinrecognition biosensor.

Organic Semiconductors

Doping of Organic Semiconductors: Impact of Dopant Strength and Electronic Coupling

  • Pages: 7751-7755
  • First Published: 19 June 2013
Doping of Organic Semiconductors: Impact of Dopant Strength and Electronic Coupling

Molecular doping: The standard model for molecular p-doping of organic semiconductors (OSCs) assumes integer charge transfer between OSC and dopant. This is in contrast to an alternative model based on intermolecular complex formation instead. By systematically varying the acceptor strength it was possible to discriminate the two models. The latter is clearly favored, suggesting strategies for the chemical design of more efficient molecular dopants.

Luminescent Probes

Activatable Probes Based on Distance-Dependent Luminescence Associated with Cerenkov Radiation

  • Pages: 7756-7760
  • First Published: 13 June 2013
Activatable Probes Based on Distance-Dependent Luminescence Associated with Cerenkov Radiation

Let me get my nanoruler: Activatable probes based on radionuclide and quantum dots (QDs) were constructed using DNA as a linker. Cerenkov radiation from 64Cu was used to excite the QDs in a distance-dependent manner. The luminescence was lowest nearest to the QD and increased with distance.

Supramolecular Catalysis

Supramolecular Assemblies of Amphiphilic L-Proline Regulated by Compressed CO2 as a Recyclable Organocatalyst for the Asymmetric Aldol Reaction

  • Pages: 7761-7765
  • First Published: 17 June 2013
Supramolecular Assemblies of Amphiphilic L-Proline Regulated by Compressed CO2 as a Recyclable Organocatalyst for the Asymmetric Aldol Reaction

Compressed CO2 triggers the formation of amphiphilic proline supramolecular assemblies in water, which catalyze the asymmetric aldol reaction without any additives. Compressed CO2 can dynamically regulate the size of the assemblies and subsequently the catalyst activity and selectivity. Furthermore, CO2 provides the merit of easy separation and purification, making the process sustainable and recyclable.

DNA Nanotechnology

Open Access

Rigid DNA Beams for High-Resolution Single-Molecule Mechanics

  • Pages: 7766-7771
  • First Published: 21 June 2013
Rigid DNA Beams for High-Resolution Single-Molecule Mechanics

Bridging the gap: Rigid DNA linkers (blue, see picture) between microspheres (green) for high-resolution single-molecule mechanical experiments were constructed using DNA origami. The resulting DNA helical bundles greatly reduce the noise generated in studies of conformation changes using optical tweezers and were applied to study small DNA secondary structures.

Supramolecular Chemistry

Shaping Micelles: The Interplay Between Hydrogen Bonds and Dispersive Interactions

  • Pages: 7772-7775
  • First Published: 10 June 2013
Shaping Micelles: The Interplay Between Hydrogen Bonds and Dispersive Interactions

A subtle interplay: In the formation of a 1.6 nm micelle containing up to six molecules of propofol, a hydrogen-bond network is shown to influence the structure of the micelle, whereas the nonpolar groups arrange in such a way that the remaining noncovalent interactions are maximized. Such globular structures present a characteristic signature in the IR spectrum that will allow their identification in more complex media.

Sensor Materials

Electric Current Test Paper Based on Conjugated Polymers and Aligned Carbon Nanotubes

  • Pages: 7776-7780
  • First Published: 17 June 2013
Electric Current Test Paper Based on Conjugated Polymers and Aligned Carbon Nanotubes

Making sense: A novel polyacetylene composite material with incorporated aligned carbon nanotubes shows rapid changes in both fluorescent intensity and color appearance in response to applied electric currents, and these electrochromatic transitions remain reversible even after a thousand cycles. The composite material is anticipated to be suitable for various other sensing applications.

Self-Assembly

Switchable Catalytic Activity: Selenium-Containing Peptides with Redox-Controllable Self-Assembly Properties

  • Pages: 7781-7785
  • First Published: 19 June 2013
Switchable Catalytic Activity: Selenium-Containing Peptides with Redox-Controllable Self-Assembly Properties

Mimicking nature: The reversible formation of self-assembled nanostructures of selenium-containing peptides can be controlled by redox triggers (see scheme, VC=vitamin C). As a consequence, the catalytic activity of these peptides is switchable. These results should lead to the development of nature-mimicking smart materials with promising properties.

Polymer Receptors

Rationally Designed Polymer Hosts of Fullerene

  • Pages: 7786-7790
  • First Published: 13 June 2013
Rationally Designed Polymer Hosts of Fullerene

A class of its own: A new class of fullerene C60 hosts—polymeric in nature—has been developed by careful design of the molecular structure of the polymer repeat unit and the mode of interaction between the repeat unit and C60 (see picture). As these hosts are synthesized by free-radical polymerization, polymer hosts with various chemical compositions and architectures can be constructed readily by appropriate design of the receptor monomer.

[8]Circulenes

Synthesis, Structural Analysis, and Properties of [8]Circulenes

  • Pages: 7791-7794
  • First Published: 21 June 2013
Synthesis, Structural Analysis, and Properties of [8]Circulenes

Polygons: [8]Circulenes were easily prepared by Pd-catalyzed annulations of tetraiodotetraphenylenes with alkynes. Their saddle-shaped structure with an [8]radialene character was identified by X-ray crystallography. Similar to 1,3,5,7-cyclooctatetraene, they have a tub-shaped eight-membered ring, but all of the bond lengths and bond angles are almost equal. Variable-temperature NMR investigations showed interesting dynamic behavior.

Homogeneous Catalysis

Gold-Catalyzed Cyclizations of cis-Enediynes: Insights into the Nature of Gold–Aryne Interactions

  • Pages: 7795-7799
  • First Published: 20 June 2013
Gold-Catalyzed Cyclizations of cis-Enediynes: Insights into the Nature of Gold–Aryne Interactions

Golden aryne? Gold aryne complexes are inferred as transition states in dual gold-catalyzed cyclizations of cis-enediynes (see scheme; DCE=1,2-dichloroethane). They are better described as ortho-aurophenyl cations, which react with weak nucleophiles and undergo facile intramolecular insertions into C(sp3)H bonds. Indanes, fused heteroarenes, and phenol derivatives are readily prepared using this method.

Quantum Dots

Carbon-Based Dots Co-doped with Nitrogen and Sulfur for High Quantum Yield and Excitation-Independent Emission

  • Pages: 7800-7804
  • First Published: 11 June 2013
Carbon-Based Dots Co-doped with Nitrogen and Sulfur for High Quantum Yield and Excitation-Independent Emission

Helpful elements: A facile bottom-up method using citric acid and L-cysteine as a precursor has been developed to prepare graphene quantum dots (GQDs) co-doped with nitrogen and sulfur. A new type and high density of surface state of GQDs arises, leading to high yields (more than 70 %) and excitation-independent emission. FLQY=fluorescence quantum yield.

Complex Ceramic Structures

Designing Smart Particles for the Assembly of Complex Macroscopic Structures

  • Pages: 7805-7808
  • First Published: 18 June 2013
Designing Smart Particles for the Assembly of Complex Macroscopic Structures

Particle get-together: Surface functionalization with a branched copolymer surfactant is used to create responsive inorganic particles that can self-assemble in complex structures. The assembly process is triggered by a pH switch that reversibly activates multiple hydrogen bonds between ceramic particles (see picture; yellow) and soft templates (n-decane; green).

Synthetic Methods

Catalytic Regioselective Oxidation of Glycosides

  • Pages: 7809-7812
  • First Published: 18 June 2013
Catalytic Regioselective Oxidation of Glycosides

Discrimination among equals: A catalytic method for the selective oxidation of unprotected glycosides, both monosaccharides and disaccharides, has been developed. The resulting ketosaccharides are isolated in moderate to excellent yields. This approach provides a basis for protecting-group-free synthetic transformations of carbohydrates.

Metal Clusters

Ion Exchange of Protons by Coinage Metals to Give Gold and Silver Encapsulation within a Pseudo-D2d Distorted Face-Capped Pd14 Cubic Kernel: [(μ14-M)Pd22(CO)20(PEt3)8]+ (M=Au, Ag)

  • Pages: 7813-7817
  • First Published: 17 June 2013
Ion Exchange of Protons by Coinage Metals to Give Gold and Silver Encapsulation within a Pseudo-D2d Distorted Face-Capped Pd14 Cubic Kernel: [(μ14-M)Pd22(CO)20(PEt3)8]+ (M=Au, Ag)

Heart of gold (or silver): The pseudo-D2d distorted MPd14 cubic kernel of [(μ14-M)Pd22(CO)20(PEt3)8]+ cations, with M=Au (1), Ag (2), has an encapsulated M atom (see picture; yellow) coordinated to eight cubic corner (black) and six face-capping Pd atoms (gray). Compounds 1 and 2 were obtained (28–60 % yields) from two-step/one-pot reactions of a Pd10 precursor with CF3CO2H followed by coinage-metal ion exchange of protons.

Natural Products

Total Synthesis and Stereochemical Assignment of Baringolin

  • Pages: 7818-7821
  • First Published: 18 June 2013
Total Synthesis and Stereochemical Assignment of Baringolin

The thiopeptide antibiotic baringolin has been synthesized, and its structure and stereochemistry have been confirmed. The use of a strategy based on palladium-catalyzed cross-couplings permitted a modular construction of this natural product.

Anthracimycin, a Potent Anthrax Antibiotic from a Marine-Derived Actinomycete

  • Pages: 7822-7824
  • First Published: 17 June 2013
Anthracimycin, a Potent Anthrax Antibiotic from a Marine-Derived Actinomycete

Licensed to kill: A new antibiotic, anthracimycin (see scheme), produced by a marine-derived actinomycete in saline culture, shows significant activity toward Bacillus anthracis, the bacterial pathogen responsible for anthrax infections. Chlorination of anthracimycin gives a dichloro derivative that retains activity against Gram-positive bacteria, such as anthrax, but also shows activity against selected Gram-negative bacteria.

Arenes

Domino Synthesis of Fluorine-Substituted Polycyclic Aromatic Hydrocarbons: 1,1-Difluoroallenes as Synthetic Platforms

  • Pages: 7825-7828
  • First Published: 14 June 2013
Domino Synthesis of Fluorine-Substituted Polycyclic Aromatic Hydrocarbons: 1,1-Difluoroallenes as Synthetic Platforms

Rather crafty: 1,1-Difluoroallenes bearing an aryl group and a cyclopentene moiety undergo indium(III)-catalyzed Friedel–Crafts-type cyclization with subsequent ring expansion and dehydrogenation to afford fluorinated polycyclic aromatic hydrocarbons in high yields. The introduction of an Ar group was effected by in situ halogenation of the intermediary indium species and a subsequent Suzuki–Miyaura reaction.

Radiochemistry

Nickel-Mediated Radioiodination of Aryl and Heteroaryl Bromides: Rapid Synthesis of Tracers for SPECT Imaging

  • Pages: 7829-7832
  • First Published: 18 June 2013
Nickel-Mediated Radioiodination of Aryl and Heteroaryl Bromides: Rapid Synthesis of Tracers for SPECT Imaging

Rapid and efficient radioiodination of aryl and heteroaryl bromides has been achieved using a nickel(0)-mediated halogen-exchange reaction. This transformation gives direct access to [123I]- and [125I]-imaging agents for single photon emission computed tomography (SPECT), such as 5-[123I]-A85380 (see scheme, Boc=tert-butyloxycarbonyl, cod=1,5-cyclooctadiene, TFA=trifluoroacetic acid).

Asymmetric Catalysis

Catalytic Asymmetric Hydrogenation of δ-Ketoesters: Highly Efficient Approach to Chiral 1,5-Diols

  • Pages: 7833-7836
  • First Published: 14 June 2013
Catalytic Asymmetric Hydrogenation of δ-Ketoesters: Highly Efficient Approach to Chiral 1,5-Diols

High turnover: An highly efficient catalytic asymmetric hydrogenation of δ-aryl-δ-ketoesters has been realized by using the chiral spiroiridium catalyst (R)-1. Chiral 1,5-diol products are obtained with excellent enantioselectivity and turnover numbers (TONs) as high as 100 000. TOF=turnover frequency.

Oxidative Cross-Coupling

Palladium(II)-Catalyzed Dehydrogenative Cross-Coupling between Two Curn:x-wiley:14337851:media:ANIE201303099:tex2gif-inf-1H Bonds: Unexpected CC Bond Formation

  • Pages: 7837-7840
  • First Published: 18 June 2013
Palladium(II)-Catalyzed Dehydrogenative Cross-Coupling between Two C<span class='icomoon'></span>H Bonds: Unexpected CC Bond Formation

CC bond construction: A palladium-catalyzed oxidative Curn:x-wiley:14337851:media:ANIE201303099:tex2gif-inf-2H/Curn:x-wiley:14337851:media:ANIE201303099:tex2gif-inf-3H cross-coupling is shown to forge CC bonds rather than Curn:x-wiley:14337851:media:ANIE201303099:tex2gif-inf-4Curn:x-wiley:14337851:media:ANIE201303099:tex2gif-inf-5 bonds through reactions of indolin-2-ones or benzofuran-2-ones with O-benzoyl hydroxylamines in the absence of an added oxidant.

Trifluoromethylation

Trifluoromethylation Reactions for the Synthesis of β-Trifluoromethylamines

  • Pages: 7841-7844
  • First Published: 13 June 2013
Trifluoromethylation Reactions for the Synthesis of β-Trifluoromethylamines

A multitalented system: N-Migratory oxytrifluoromethylation and one-pot three-component reactions of allylamines as well as the aminotrifluoromethylation of alkenyl amines all proceeded efficiently in the presence of the Togni reagent (1) and CuI to afford a variety of β-trifluoromethylamine derivatives (see scheme).

Synthetic Methods

Carbonylation of Propargyl Carbamates with Palladium(II) Bisoxazoline Catalysts: Efficient Synthesis of 5-Methoxy-3(2H)-furanones

  • Pages: 7845-7849
  • First Published: 20 June 2013
Carbonylation of Propargyl Carbamates with Palladium(II) Bisoxazoline Catalysts: Efficient Synthesis of 5-Methoxy-3(2H)-furanones

Palladium and CO: Carbonylation of 1 with [Pd(tfa)2(±)-L1] (tfa=trifluoroacetate) affords the spirofuranone 2 with inversion of the stereochemistry at C17 in 96 % yield. C17-epi-1 also gave the same product 2 with retention of the stereochemistry at C17. Labelling studies show that 13CO was incorporated into the C5′ position of the furanone ring. The first asymmetric version of this new reaction was achieved.

CC Bond Cleavage

Selective Curn:x-wiley:14337851:media:ANIE201303376:tex2gif-inf-1Csp Bond Cleavage: The Nitrogenation of Alkynes to Amides

  • Pages: 7850-7854
  • First Published: 26 June 2013
Selective C<span class='icomoon'></span>Csp Bond Cleavage: The Nitrogenation of Alkynes to Amides

Breakthrough: A novel catalyzed direct highly selective Curn:x-wiley:14337851:media:ANIE201303376:tex2gif-inf-3Csp bond functionalization of alkynes to amides has been developed. Nitrogenation is achieved by the highly selective Curn:x-wiley:14337851:media:ANIE201303376:tex2gif-inf-5Csp bond cleavage of aryl-substituted alkynes. The oxidant-free and mild conditions and wide substrate scope make this method very practical.

Synthesis Design

Chemical Synthesis of Biologically Active Monoglycosylated GM2-Activator Protein Analogue Using N-Sulfanylethylanilide Peptide

  • Pages: 7855-7859
  • First Published: 13 June 2013
Chemical Synthesis of Biologically Active Monoglycosylated GM2-Activator Protein Analogue Using N-Sulfanylethylanilide Peptide

Going to SEA(lide): Total chemical synthesis of a 162-residue glycoprotein analogue of the monoglycosylated human GM2-activator protein (GM2AP) was achieved. Key steps were the use of N-sulfanylethylanilide (SEAlide) peptides in the kinetic chemical ligation synthesis of a large peptide fragment, and a convergent native chemical ligation for final fragment assembly.

Photoredox Catalysis

A Mild, One-Pot Stadler–Ziegler Synthesis of Arylsulfides Facilitated by Photoredox Catalysis in Batch and Continuous-Flow

  • Pages: 7860-7864
  • First Published: 19 June 2013
A Mild, One-Pot Stadler–Ziegler Synthesis of Arylsulfides Facilitated by Photoredox Catalysis in Batch and Continuous-Flow

Visible advance: A mild, one-pot Stadler–Ziegler process for CS bond formation has been developed. The method employs the photoredox catalyst [Ru(bpy)3Cl2]⋅6 H2O irradiated with visible light. A variety of aryl–alkyl and diaryl sulfides were prepared from readily available arylamines and aryl/alkylthiols in good yields. The use of a photo microreactor led to a significant improvement with respect to safety and efficiency.

CH Activation

Enantioselective CH Arylation Strategy for Functionalized Dibenzazepinones with Quaternary Stereocenters

  • Pages: 7865-7868
  • First Published: 19 June 2013
Enantioselective C<span class='icomoon'></span>H Arylation Strategy for Functionalized Dibenzazepinones with Quaternary Stereocenters

Tada! Highly functionalized chiral dibenzazepinones are obtained by a mild palladium(0)-catalyzed enantioselective CH arylation with excellent selectivities by using simple taddol phosphoramidite ligands. The amide tether allows exclusive regioselectivity through a rare eight-membered palladacycle intermediate.

Asymmetric Catalysis

Catalytic Enantioselective Difluoroalkylation of Aldehydes

  • Pages: 7869-7873
  • First Published: 18 June 2013
Catalytic Enantioselective Difluoroalkylation of Aldehydes

Copper-catalyzed bond scission of pentafluorobutane-1,3-diones generates difluoroenolates that react with aldehydes to give a wide range of chiral α,α-difluoro-β-hydroxy ketones within a few hours in up to 99 % yield and 92 % ee. The synthetic utility of this reaction is demonstrated with the stereoselective synthesis of a chiral anti-1,3-diol exhibiting a central difluoromethylene unit and efficient conversion to a 2,2-difluoro-3-hydroxy carboxylic acid.

Messenger RNA

A Chemo-Enzymatic Approach for Site-Specific Modification of the RNA Cap

  • Pages: 7874-7878
  • First Published: 21 June 2013
A Chemo-Enzymatic Approach for Site-Specific Modification of the RNA Cap

Capped and gowned: A two-step approach can be used to site-specifically modify the 5′-cap of eukaryotic mRNAs. First, a trimethylguanosinesynthase variant recognizes the m7G cap structure and introduces bioorthogonal groups using S-adenosyl-L-methionine-based cosubstrates. Then, the enzymatically introduced reporter groups are further modified by thiol–ene or CuAAC click chemistry (see scheme).

Molecular Switches

An Azobenzene Unit Embedded in a Cyclopeptide as a Type-Specific and Spatially Directed Switch

  • Pages: 7879-7882
  • First Published: 19 June 2013
An Azobenzene Unit Embedded in a Cyclopeptide as a Type-Specific and Spatially Directed Switch

By embedding an azobenzene unit into a chiral scaffold, switching of azobenzene from the trans-(P) isomer to the cis-(P) isomer and back was achieved (black arrows in picture). The embedding leads to a flipping process in which the phenyl rings can only move directly towards one another in the switching process.

Electrochemistry

Why Silver Deposition is so Fast: Solving the Enigma of Metal Deposition

  • Pages: 7883-7885
  • First Published: 20 June 2013
Why Silver Deposition is so Fast: Solving the Enigma of Metal Deposition

A perfect match: Silver deposition is one of the fastest electrochemical reactions, even though the Ag+ ion loses more than 5 eV solvation energy in the process. This phenomenon, an example of the enigma of metal deposition, was investigated by a combination of MD simulations, DFT, and specially developed theory. At the surface, the Ag+ ion experiences a strong interaction with the sp band of silver, which catalyzes the reaction.