Angewandte Chemie International Edition

Cover image for Vol. 43 Issue 44

November 12, 2004

Volume 43, Issue 44

Pages 5863–6007

    1. Cover Picture: Crystal Structure of Tricolorin A: Molecular Rationale for the Biological Properties of Resin Glycosides Found in Some Mexican Herbal Remedies (Angew. Chem. Int. Ed. 44/2004) (page 5863)

      Anna Rencurosi, Edward P. Mitchell, Gianluca Cioci, Serge Pérez, Rogelio Pereda-Miranda and Anne Imberty

      Version of Record online: 10 NOV 2004 | DOI: 10.1002/anie.200490153

      In traditional Mexican farming the morning glory “heavenly blue” (Ipomea tricolor Cav.) is used as a cover crop. The structure of tricolorin A, one of several phytotoxic resin glycosides present in this plant, has now been determined crystallographically. The lipopolysaccharide contains one macrolactone ring and forms channel structures, which could be responsible for the biological activity of this compound, as reported by R. Pereda-Miranda, A. Imberty, and co-workers in their Communication on page 5918 ff.

    2. Hierarchical Zeolites: A Proven Strategy to Combine Shape Selectivity with Efficient Mass Transport (pages 5880–5882)

      Martin Hartmann

      Version of Record online: 8 OCT 2004 | DOI: 10.1002/anie.200460644

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      Pores for effect: Hierarchical zeolites combine the high activity, shape selectivity, and hydrothermal stability of conventional zeolites with the efficient mass transport that is typically achieved in mesoporous materials. The mesopores can be templated with carbon during zeolite synthesis (see scheme).

    3. Enantioselective Catalysis with Chiral Phosphine Oxide Preligands (pages 5883–5886)

      Natalia V. Dubrovina and Armin Börner

      Version of Record online: 21 OCT 2004 | DOI: 10.1002/anie.200460848

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      Primed! Secondary phosphine oxides are able to tautomerize in situ to phosphinous acids and then coordinate to soft transition metals through the trivalent phosphorus atom (see scheme). The presence of a chiral backbone allows this reaction to run stereoselectively and be used for the generation of highly enantioselective homogeneous catalysts.

    4. The Road to Chemical Names and Eponyms: Discovery, Priority, and Credit (pages 5888–5894)

      Pedro Cintas

      Version of Record online: 16 SEP 2004 | DOI: 10.1002/anie.200330074

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      Discovery is a two-step process—finding and comprehending (see scheme). The history of chemistry contains incorrect attributions, mistakes, and problems created by conflicting interpretations. But retrospective analyses can set matters straight and give credit where credit is due. Language and naming also convey a fascinating human side to research and illustrate that chemical discovery is multifaceted, evolutionary, and very much alive.

    5. When and How Do Diaminocarbenes Dimerize? (pages 5896–5911)

      Roger W. Alder, Michael E. Blake, Leila Chaker, Jeremy N. Harvey, François Paolini and Jan Schütz

      Version of Record online: 29 SEP 2004 | DOI: 10.1002/anie.200400654

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      It's amazing what a little help can do: Simple diaminocarbenes, such as (Et2N)2C, do not dimerize at room temperature in THF, even though thermodynamics favor the dimer. Dimerization occurs rapidly in the presence of proton sources, however (see scheme), and the possibility of catalysis by Li+ is discussed. DFT calculations give a good account of the thermodynamics and kinetics of dimer formation.

    6. Assembly of an Oxo–Zirconium(IV) Cluster in a Protein Cleft (pages 5914–5918)

      Weiqing Zhong, Dmitriy Alexeev, Ian Harvey, Maolin Guo, Dominic J. B. Hunter, Haizhong Zhu, Dominic J. Campopiano and Peter J. Sadler

      Version of Record online: 7 OCT 2004 | DOI: 10.1002/anie.200460806

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      Filling a gap: A trinuclear oxo–zirconium(IV) cluster readily assembles in the “venus fly trap” binding cleft of bacterial transferrin (see picture; cluster: Zr green, O red, P yellow; protein: β sheets cyan, Tyr pink, Arg dark blue). Its structure was determined by EXAFS and X-ray crystallography.

    7. Crystal Structure of Tricolorin A: Molecular Rationale for the Biological Properties of Resin Glycosides Found in Some Mexican Herbal Remedies (pages 5918–5922)

      Anna Rencurosi, Edward P. Mitchell, Gianluca Cioci, Serge Pérez, Rogelio Pereda-Miranda and Anne Imberty

      Version of Record online: 21 SEP 2004 | DOI: 10.1002/anie.200460327

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      A water channel was observed in the first crystallographically determined structure of a natural resin glycoside (see figure). Tricolorin A displays amphipathic features, which have been correlated with its significant mammalian and plant toxicity. The architecture of tricolorin A in the solid state suggests that the cytotoxicity of this class of compounds may be the result of their pore-forming ability.

    8. Supramolecular, Bifurcated N-H⋅⋅⋅OC-M Bonding Explains Unusually Low νCO Frequencies in Metal Carbonyl Compounds: A Case Study (pages 5922–5925)

      Pierre Braunstein, Jean-philippe Taquet, Olivier Siri and Richard Welter

      Version of Record online: 10 NOV 2004 | DOI: 10.1002/anie.200461175

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      New tricks for an old dog: The solid-state structure of cis-[W(CO)4(piperidine)2] reveals an intermolecular, bifurcated H-bonding network involving the N-H protons and the two CO ligands trans to the piperidine ligands (see X-ray crystal structure; C gray, H green, N blue, O red, W magenta). Such an arrangement accounts for νCO absorptions as low as 1768 cm−1!

    9. Individual Molecules of Dye-Labeled DNA Act as a Reversible Two-Color Switch upon Application of an Electric Field (pages 5926–5930)

      Samuel S. White, Liming Ying, Shankar Balasubramanian and David Klenerman

      Version of Record online: 10 NOV 2004 | DOI: 10.1002/anie.200460323

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      Reversible switching of the fluorescence of an individual dye-labeled DNA molecule is possible by utilizing an electric field applied in the tip of a nanopipette (see picture; FRET=fluorescence resonance energy transfer). The electric field appears to alter the conformation of the acceptor dye only, resulting in a significant change in its quantum yield.

    10. Self-Construction of Hollow SnO2 Octahedra Based on Two-Dimensional Aggregation of Nanocrystallites (pages 5930–5933)

      Hua Gui Yang and Hua Chun Zeng

      Version of Record online: 10 NOV 2004 | DOI: 10.1002/anie.200461129

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      0D[RIGHTWARDS ARROW]2D[RIGHTWARDS ARROW]3D oriented attachment has been exploited to prepare octahedra of rutile-like SnO2 with a central cavity by a template-free hydrothermal route. The synthesis is based on the two-dimensional attachment of nanocrystallites and stabilization of a family of {111}-like crystal planes in 2-propanol/water in the presence of ethylenediamine. In TEM images of the octahedron (see picture), the central cavity is evidenced by lighter regions.

    11. Quaternary Ammonium Groups in Silica-Associated Proteins (pages 5933–5936)

      Stephan Wenzl, Rainer Deutzmann, Robert Hett, Eduard Hochmuth and Manfred Sumper

      Version of Record online: 10 NOV 2004 | DOI: 10.1002/anie.200461236

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      Mother Nature knows best! Silaffins (silica-associated proteins) from the diatom Eucampia zodiacus (see picture) were found to contain novel lysine modifications that carry quaternary ammonium groups. It appears that the very special interaction between quaternary ammonium groups and silica is exploited in the natural biomineralization of silica.

    12. A Palladium(II)-Clipped Aromatic Sandwich (pages 5936–5940)

      Kazuhisa Kumazawa, Yoshinori Yamanoi, Michito Yoshizawa, Takahiro Kusukawa and Makoto Fujita

      Version of Record online: 10 NOV 2004 | DOI: 10.1002/anie.200460868

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      A filling that makes the sandwich: Large aromatic molecules are sandwiched by two π-conjugated ligands (L) that are joined together by six {(en)Pd}2+ units (M; en=1,2-ethanediamine; see picture; guest red, {(en)Pd}2+ yellow, ligand blue). This host has an M6L2 composition and is distorted by the concave shape of the ligand. Without a guest, it releases the distortion by forming the dimeric M12L4 in a reversible fashion.

    13. [(Tp)8(H2O)6CuII6FeIII8(CN)24]4+: A Cyanide-Bridged Face-Centered-Cubic Cluster with Single-Molecule-Magnet Behavior (pages 5940–5943)

      Shi Wang, Jing-Lin Zuo, Hong-Cai Zhou, Hye Jin Choi, Yanxiong Ke, Jeffrey R. Long and Xiao-Zeng You

      Version of Record online: 10 NOV 2004 | DOI: 10.1002/anie.200461515

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      A box of magnetic tricks: By using the anionic precursor [(Tp)Fe(CN)3] (Tp=hydrotris(pyrazolyl)borate), the title compound, which is a new face-centered-cubic cluster, has been synthesized (see structure; red Fe, turquoise Cu, orange B, gray C, blue N, dark red O). Magnetic studies show that it exhibits single-molecule-magnet behavior with substantial axial magnetic anisotropy (D=−0.16 cm−1).

    14. Surface-Cap-Mediated Host–Guest Chemistry of Semiconductor CdS: Intercalative Cation Accumulation around a Phenyl-Capped CdS Cluster and Its Notable Effects on the Cluster Photoluminescence (pages 5943–5946)

      Takayuki Hiratani and Katsuaki Konishi

      Version of Record online: 10 NOV 2004 | DOI: 10.1002/anie.200461190

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      Turning on the light: Remarkable photoluminescence enhancement is observed upon intercalation of cetyltrimethylammonium cations (CTA+) among the surface aromatic groups of a complex formed from the phenyl-capped semiconductor CdS cluster molecule [Cd10S4(SPh)12] (1) and tetraoctylammonium bromide (TOAB) (see scheme).

    15. Stereochemical Assignment in Acyclic Lipids Across Long Distance by Circular Dichroism: Absolute Stereochemistry of the Aglycone of Caminoside A (pages 5946–5951)

      John B. MacMillan, Roger G. Linington, Raymond J. Andersen and Tadeusz F. Molinski

      Version of Record online: 10 NOV 2004 | DOI: 10.1002/anie.200461158

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      Information technology: The configuration at C10-OH of the caminoside aglycone (see formula) was shown to be R by interpretation of exciton coupling in the circular dichroism (CD) spectrum of the tetraphenylporphyrin carboxylate diester of (2R,10R)-2,10-nonadecanediol. This compound is derived from the title compound and was embedded in highly uniform nanometric liposomes for the CD measurements.

    16. Enantioselective Total Synthesis of (+)-Milnamide A and Evidence of Its Autoxidation to (+)-Milnamide D (pages 5951–5954)

      Chaomin Liu, Makoto N. Masuno, John B. MacMillan and Tadeusz F. Molinski

      Version of Record online: 10 NOV 2004 | DOI: 10.1002/anie.200461245

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      Spontaneous oxidation of the marine-sponge-derived peptide (+)-milnamide A (1) to (+)-milnamide D (2), which is also a natural product, was observed during the total synthesis of 1. The absolute configurations of the structures were determined and are also reported.

    17. Biofunctionalization of Fluorescent Rare-Earth-Doped Lanthanum Phosphate Colloidal Nanoparticles (pages 5954–5957)

      Felix Meiser, Christina Cortez and Frank Caruso

      Version of Record online: 10 NOV 2004 | DOI: 10.1002/anie.200460856

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      Approximately eight avidin molecules are conjugated to each Ce/Tb-doped lanthanum phosphate nanoparticle (NP) through the formation of amide bonds (see scheme). This biofunctionalization process comprises modification of the LaPO4 NPs with 6-aminohexanoic acid (AHA) to confer colloidal stability, activation of the AHA carboxy groups by 1-ethyl-3-[3-dimethylaminopropyl]carbodiimide, and avidin conjugation.

    18. Two- and Three-Dimensional Mesoporous Iron Oxides with Microporous Walls (pages 5958–5961)

      Feng Jiao and Peter G. Bruce

      Version of Record online: 20 AUG 2004 | DOI: 10.1002/anie.200460826

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      Age concern: Alkyl amine templates act as bifunctional surfactants which can template mesostructures with microporous walls. Ordered two-dimensional hexagonal mesoporous iron oxide with P6mm symmetry and three-dimensional cubic mesoporous iron oxide with Fm3m symmetry (see TEM image) have been prepared by using decylamine as the template, iron(III) ethoxide as the precursor, and different aging conditions.

    19. Self-Oxidation of a Phenolate Complex to a Bimetallic Stilbene Quinone (pages 5961–5963)

      Milko E. van der Boom, Tatiana Zubkov, Atindra D. Shukla, Boris Rybtchinski, Linda J. W Shimon, Haim Rozenberg, Yehoshoa Ben-David and David Milstein

      Version of Record online: 10 NOV 2004 | DOI: 10.1002/anie.200460360

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      Do-it-yourself oxidation: The RhIII complex 1 undergoes a self-oxidative coupling process, in which the phenolate oxygen atom serves as the oxidant, to give 2 and the hydride complex 3 (2:3=1:3). This reaction involves cleavage of a strong aryl–oxygen bond. X-ray analysis of 2 reveals that the two quinonoid C[DOUBLE BOND]O bonds are η2-coordinated to the metal centers.

    20. α,α-Difluoro-H-phosphinates: Useful Intermediates for a Variety of Phosphate Isosteres (pages 5963–5967)

      Arnaud Gautier, Goulnara Garipova, Carmen Salcedo, Sébastien Balieu and Serge R. Piettre

      Version of Record online: 10 NOV 2004 | DOI: 10.1002/anie.200460519

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      Addition of the radical generated from the sodium salt of hypophosphorous acid to difluoroalkenes results in the formation of α,α-difluoro-H-phosphinates. These intermediates can be transformed into different phosphorus-centered isosteres, such as difluorophosphonates, difluorophosphonothioates, and difluorophosphinates (see scheme).

    21. A Simple, One-Step Procedure for the Formation of Chiral Metallamacrocycles (pages 5967–5971)

      Katie Campbell, Charles A. Johnson II, Robert McDonald, Michael J. Ferguson, Michael M. Haley and Rik R. Tykwinski

      Version of Record online: 10 NOV 2004 | DOI: 10.1002/anie.200461139

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      A twist in the final stage: Chiral, conjugated metallamacrocycles can be formed in excellent yield in a single step from achiral precursors by ligand exchange between (R,R)- or (S,S)-chiraphos and trans platinum acetylide complexes (see scheme).

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      Readily Available Biaryl P,N Ligands for Asymmetric Catalysis (pages 5971–5973)

      Thomas F. Knöpfel, Patrick Aschwanden, Takashi Ichikawa, Takumi Watanabe and Erick M. Carreira

      Version of Record online: 10 NOV 2004 | DOI: 10.1002/anie.200461286

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      A short and modular synthesis of novel P,N ligands (pinap; see scheme; X=O or NH) is presented. A covalently bound chiral group allows the separation of the atropisomeric diastereomers, thus avoiding resolution involving chiral Pd–amine complexes. The utility of the ligands is demonstrated for three reactions catalyzed by different transition metals; in each case products are obtained with high enantiomeric excess (up to 99 % ee).

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      Profiling Kinase Activities by Using a Peptide Chip and Mass Spectrometry (pages 5973–5977)

      Dal-Hee Min, Jing Su and Milan Mrksich

      Version of Record online: 10 NOV 2004 | DOI: 10.1002/anie.200461061

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      Weighing in: Multiple kinases can be assayed simultaneously by using a method that combines peptide chips and MALDI-TOF mass spectrometry (MS). The method uses self-assembled monolayers that present a set of peptides that are each selective for a kinase. The kinase phosphorylates the peptide, changing its mass. MS analysis of the surface resolves each peptide and gives the activity of each kinase.

    24. A Highly Stereoselective Addition of the Anion Derived from α-Diazoacetamide to Aromatic N-Tosylimines (pages 5977–5980)

      Yonghua Zhao, Zhihua Ma, Xiaomei Zhang, Yaping Zou, Xianglin Jin and Jianbo Wang

      Version of Record online: 10 NOV 2004 | DOI: 10.1002/anie.200460730

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      In the presence of an Evans oxazolidinone as the chiral auxiliary, the anion derived from α-diazoacetamide adds to aromatic N-tosylimines with high stereoselectivity (see scheme). The addition products can be used in a concise and stereoselective synthesis of syn- and anti-α-hydroxy-β-amino acid derivatives.

    25. Highly Ordered Mesoporous Bioactive Glasses with Superior In Vitro Bone-Forming Bioactivities (pages 5980–5984)

      Xiaoxia Yan, Chengzhong Yu, Xufeng Zhou, Jiawei Tang and Dongyuan Zhao

      Version of Record online: 10 NOV 2004 | DOI: 10.1002/anie.200460598

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      Large pore volumes and highly accessible mesopore surface areas are present in highly ordered mesoporous bioactive glasses (MBGs) prepared by a block copolymer templating approach under non-aqueous conditions. These glasses have a high bone-forming bioactivity in vitro, as shown by immersing them in simulated body fluid (SBF) and monitoring the formation of hydroxycarbonate apatite (HCA) on the surface (see electron micrographs).

    26. C1-Symmetric Sulfoximines as Ligands in Copper-Catalyzed Asymmetric Mukaiyama-Type Aldol Reactions (pages 5984–5987)

      Martin Langner and Carsten Bolm

      Version of Record online: 10 NOV 2004 | DOI: 10.1002/anie.200460953

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      Aldol products with quarternary centers have been obtained with up to 99 % ee in high yields by using copper(II) catalysts bearing C1-symmetric aminosulfoximines as ligands (see scheme). In terms of ee values and yield the new catalysts compare well with established systems based on metal complexes with bis(oxazoline) and pyridylbis(oxazoline) ligands.

    27. A Mesoporous/Crystalline Composite Material Containing Tin Phosphate for Use as the Anode in Lithium-Ion Batteries (pages 5987–5990)

      Eunjin Kim, Dongyeon Son, Tae-Gon Kim, Jaephil Cho, Byungwoo Park, Kwang-Sun Ryu and Soon-Ho Chang

      Version of Record online: 10 NOV 2004 | DOI: 10.1002/anie.200454080

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      Packed to capacity: The incorporation of mesoporous structures as a buffer layer enhances the structural stability of tin phosphate and alleviates the volume expansion of the tin phosphate anode during Li alloying/dealloying (see TEM image). The mesoporous tin phosphate/Sn2P2O7 composite anode shows a large initial capacity (721 mA h g−1) and excellent cyclability (587 mA h g−1 at the 30th cycle).

    28. Enantioselective Total Synthesis of the Highly Oxygenated 1,10-seco-Eudesmanolides Eriolanin and Eriolangin (pages 5991–5994)

      Jörn Merten, Roland Fröhlich and Peter Metz

      Version of Record online: 10 NOV 2004 | DOI: 10.1002/anie.200460936

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      Sultones of swing: A sultone served as the key intermediate in the first enantioselective total syntheses of the bioactive title compounds (see scheme), the absolute configuration of which is now established. Starting from 2-bromo-1-(2-furyl)ethanone, 24 steps were required to generate the common basic structure, and in each case two additional steps yielded the natural products.

    29. [Yb3N(dpa)6][Yb(dpa)3]: A Molecular Nitride of a Rare-Earth Metal with a Yb3N Unit (pages 5994–5996)

      Catharina C. Quitmann and Klaus Müller-Buschbaum

      Version of Record online: 10 NOV 2004 | DOI: 10.1002/anie.200460478

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      Centered by a nitride ion: The oxidation of ytterbium with 2,2′-dipyridylamine in liquid ammonia at low temperatures leads to the novel compound [Yb3N(dpa)6][Yb(dpa)3], which is unique among homoleptic dipyridylamides of the rare-earth metals. The complete deprotonation of NH3 provides the first molecular nitride of a rare-earth metal with a Yb3N unit (see picture; C blue, N green, Yb silver).

    30. Novel Three-Component Reactions Based on a Heck Carbopalladation/Cyclization Domino Reaction (pages 5997–6000)

      Christoph J. Kressierer and Thomas J. J. Müller

      Version of Record online: 10 NOV 2004 | DOI: 10.1002/anie.200461134

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      In one fell swoop: the reaction of alkynylallyl alcohols with aryl halides in the presence of [Pd(PPh3)2Cl2] under Heck reaction conditions provides cyclic γ,δ-enals (see scheme). This reaction serves as the starting sequence for the one-pot synthesis of diene esters and β-amino-substituted tetrahydrofurans.

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