Angewandte Chemie International Edition

Cover image for Angewandte Chemie International Edition

March 15, 2002

Volume 41, Issue 6

Pages 875–1078

    1. Cover Picture: Angew. Chem. Int. Ed. 6/2002 (page 875)

      Warren G. Lewis, Luke G. Green, Flavio Grynszpan, Zoran Radić, Paul R. Carlier, Palmer Taylor, M. G. Finn and K. Barry Sharpless

      Version of Record online: 15 MAR 2002 | DOI: 10.1002/1521-3773(20020315)41:6<875::AID-ANIE875>3.0.CO;2-Y

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      Editorial: Through the Wire: Online Submission of Manuscripts (page 877)

      Version of Record online: 15 MAR 2002 | DOI: 10.1002/1521-3773(20020315)41:6<877::AID-ANIE877>3.0.CO;2-Q

    3. Graphical Abstract: Angew. Chem. Int. Ed. 6/2002 (pages 878–888)

      Version of Record online: 15 MAR 2002 | DOI: 10.1002/1521-3773(20020315)41:6<878::AID-ANIE878>3.0.CO;2-M

    4. Dynamic Covalent Chemistry (pages 898–952)

      Stuart J. Rowan, Stuart J. Cantrill, Graham R. L. Cousins, Jeremy K. M. Sanders and J. Fraser Stoddart

      Version of Record online: 15 MAR 2002 | DOI: 10.1002/1521-3773(20020315)41:6<898::AID-ANIE898>3.0.CO;2-E

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      Supramolecular chemistry at the covalent level! That is the mouthwatering prospect that dynamic covalent chemistry offers the chemist. Covalent synthesis under thermodynamic control can either result in the self-assembly of a single molecular architecture (see scheme, top), if the monomer is rigid and correctly predisposed, or the formation of adaptable libraries (bottom), if the monomer contains some flexibility programmed into it.

    5. Palladium-Catalyzed α-Arylation of Esters: Ideal New Methodology for Discovery Chemistry (pages 953–956)

      Guy C. Lloyd-Jones

      Version of Record online: 15 MAR 2002 | DOI: 10.1002/1521-3773(20020315)41:6<953::AID-ANIE953>3.0.CO;2-9

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      Fine tuning for fine chemicals: Two complimentary and yet intimately related methods for the palladium-catalyzed arylation of esters and their derivatives have emerged. The careful choice of ligand and base proved to be decisive; the scheme shows one variation of one of the methods, which leads to amino esters. These results confirm, yet again, that the repertoire of palladium catalysis continues to expand at an astonishing pace.

    6. 1,1′-Ferrocenedi(amido) Chelate Ligands in Titanium and Zirconium Complexes (pages 956–958)

      Max Herberhold

      Version of Record online: 15 MAR 2002 | DOI: 10.1002/1521-3773(20020315)41:6<956::AID-ANIE956>3.0.CO;2-Y

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      The search for catalysts for olefin polymerization has brought complexes into the limelight that contain anionic 1,1′-ferrocenedi(amido) chelate ligands. The stabilization of cationic titanium centers by such a chelate ligand may lead to the formation of a dative Fe[RIGHTWARDS ARROW]Ti heterodimetallic bond, as in the cation of the salt 1.

    7. Sensitized Luminescence of Trivalent Europium by Three-Dimensionally Arranged Anatase Nanocrystals in Mesostructured Titania Thin Films (pages 959–962)

      Karen L. Frindell, Michael H. Bartl, Alois Popitsch and Galen D. Stucky

      Version of Record online: 15 MAR 2002 | DOI: 10.1002/1521-3773(20020315)41:6<959::AID-ANIE959>3.0.CO;2-M

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      The well-ordered array of pores and walls made up of nanocrystallites in a mesoporous titania thin film can be doped with high concentrations of Eu3+ (up to 8 mol %) to create a bright red photoluminescent material (see picture). The photoluminescence arises from energy transfer through excitation of the titania nanocrystallites in their band gap to the crystal field states of the europium ions; photoluminescence concentration quenching is prevented because of the high surface area and nanocrystalline structure of the material.

    8. Multiple Emissions from 1,3-Diphenyl-5-pyrenyl-2-pyrazoline Nanoparticles: Evolution from Molecular to Nanoscale to Bulk Materials (pages 962–965)

      Hongbing Fu, B. H. Loo, Debao Xiao, Ruiming Xie, Xuehai Ji, Jiannian Yao, Baowen Zhang and Lianqi Zhang

      Version of Record online: 15 MAR 2002 | DOI: 10.1002/1521-3773(20020315)41:6<962::AID-ANIE962>3.0.CO;2-9

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      Tunable, multiple emission is exhibited by nanoparticles of 1,3-diphenyl-5-pyrenyl-2-pyrazoline (DPP; see picture), which ranges from near-UV to green. Tuning could be effected by alteration of either the excitation wavelength or the nanoparticle size. In contrast, DPP in dilute solution only showed the emission characteristics of the pyrene chromophore. In bulk crystals, only the emission characteristics of the pyrazoline chromophore were exhibited.

    9. Template Effects, Asymmetry, and Twinning in Helical Inclusion Compounds (pages 965–969)

      Mark D. Hollingsworth, Michael E. Brown, Michael Dudley, Hua Chung, Matthew L. Peterson and Andrew C. Hillier

      Version of Record online: 15 MAR 2002 | DOI: 10.1002/1521-3773(20020315)41:6<965::AID-ANIE965>3.0.CO;2-Y

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      Previously unrecognized chiral and rotational twinning were revealed by optical microscopy, synchrotron white beam X-ray topography, and crystallography in the crystal structure of the inclusion compound of 2,12-tridecanedione/urea (see picture), which was otherwise intractable.

    10. Structural Analysis of C60 Trimers by Direct Observation with Scanning Tunneling Microscopy (pages 969–972)

      Masashi Kunitake, Shinobu Uemura, Osamu Ito, Koichi Fujiwara, Yasujiro Murata and Koichi Komatsu

      Version of Record online: 15 MAR 2002 | DOI: 10.1002/1521-3773(20020315)41:6<969::AID-ANIE969>3.0.CO;2-I

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      Isomeric fullerene trimers have been prepared by using a high speed vibration milling technique, and Langmuir films of the isomers observed on Au(111) surfaces by scanning tunneling microscopy (STM). Each isomer exhibited a different surface morphology. The observed distribution of isomers supports molecular orbital calculations of isomer stability. STM may be used to distinguish the individual isomers (see image), which is difficult to achieve by spectroscopy.

    11. Computational Prediction of the Phase Transformation of Two As-Synthesized Oxyfluorinated Compounds into the Zeotype CHA Forms (pages 972–975)

      Stéphanie Girard, Alain Tuel, Caroline Mellot-Draznieks and Gérard Férey

      Version of Record online: 15 MAR 2002 | DOI: 10.1002/1521-3773(20020315)41:6<972::AID-ANIE972>3.0.CO;2-5

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      Computer calcination: The phase transformation of two as-synthesized fluorinated inorganic compounds into their related microporous structures upon calcination (see scheme) is predicted by using lattice energy minimizations, successfully capturing in one step dehydration, defluorination, and template elimination.

    12. Assembly of a Face-to-Face Tetranuclear Copper(I) Complex as a Host for an Anthracene Guest (pages 975–979)

      Raymond Ziessel, Loïc Charbonnière, Michèle Cesario, Thierry Prangé and Hélène Nierengarten

      Version of Record online: 15 MAR 2002 | DOI: 10.1002/1521-3773(20020315)41:6<975::AID-ANIE975>3.0.CO;2-U

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      Anthracene in a bucket: Coordination-driven assembly of a ditopic ligand with copper salts leads to two stable tetranuclear complexes. The major complex, characterized by X-ray crystallography (see picture), displays a face-to-face arrangement of the phenanthroline subunits, and the inclusion of an anthracene molecule can be demonstrated by both proton NMR spectroscopy and cyclic voltammetry. The minor species has a plaited structure and does not exhibit significant interaction with the anthracene guest.

    13. The Mechanism of Catalytic Enantioselective Fluorination: Computational and Experimental Studies (pages 979–982)

      Stefano Piana, Ingrid Devillers, Antonio Togni and Ursula Rothlisberger

      Version of Record online: 15 MAR 2002 | DOI: 10.1002/1521-3773(20020315)41:6<979::AID-ANIE979>3.0.CO;2-E

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      A parallel orientation between the coordinated substrate enolate and a face-on naphthyl group of the TADDOL ligand (see picture; Ti dark gray, O red, Cl green, F orange, N violet) control the stereochemical outcome of the Ti-catalyzed asymmetric fluorination of 1,3-dicarbonyl compounds with 1-chloromethyl-4-fluoro-1,4-diazoniabicyclo[2.2.2]octanetriethylenediamine (F-TEDA; its approach is also shown the in picture). Density functional theory based quantum-mechanical molecular mechanical calculations also disclose the fluorine-transfer step as occurring by a single-electron transfer.

    14. Molecular Dynamic Computer Simulations of Phase Behavior of Non-Ionic Surfactants (pages 983–986)

      Ekaterina Ryjkina, Hubert Kuhn, Heinz Rehage, Felix Müller and Jörg Peggau

      Version of Record online: 15 MAR 2002 | DOI: 10.1002/1521-3773(20020315)41:6<983::AID-ANIE983>3.0.CO;2-Y

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      Aggregation without aggravation: A rapid and accurate estimation of the phase structure of amphiphilic molecules is made possible with a new computer simulation technique that excellently reproduces the aggregation behavior of such compounds. For dodecyldimethylamine oxide it is demonstrated how the micellar, hexagonal (see picture for isodensity profile), and lamella surfactant mesostructures can be calculated.

    15. A Highly Efficient Catalyst for the Telomerization of 1,3-Dienes with Alcohols: First Synthesis of a Monocarbenepalladium(0)–Olefin Complex (pages 986–989)

      Ralf Jackstell, Mario Gómez Andreu, Anja Frisch, Kumaravel Selvakumar, Alexander Zapf, Holger Klein, Anke Spannenberg, Dirk Röttger, Oliver Briel, Ralf Karch and Matthias Beller

      Version of Record online: 15 MAR 2002 | DOI: 10.1002/1521-3773(20020315)41:6<986::AID-ANIE986>3.0.CO;2-M

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      Industrial reaction improved: The first monocarbenepalladium(0)–olefin complex has been isolated and characterized (see structure; Pd orange, N green, S yellow, O blue). The complex exhibited unprecedented high catalyst productivity and selectivity for industrially important telomerization reactions (the dimerization of 1,3-dienes in the presence of a nucleophile, in this case an alcohol).

    16. Simple Synthesis of Oligosilyl-α,ω-dipotassium Compounds (pages 989–992)

      Christian Kayser, Guido Kickelbick and Christoph Marschner

      Version of Record online: 15 MAR 2002 | DOI: 10.1002/1521-3773(20020315)41:6<989::AID-ANIE989>3.0.CO;2-A

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      Multiply metalated oligosilanes: Treatment of bridged bis[tris(trimethylsilyl)silyl] compounds with two equivalents of potassium tert-butoxide leads to the formation of 1,3- and 1,4-dipotassium silanes [Eq. (1)]. Reaction of the latter with zirconocene dichloride and hafnocene dichloride, respectively, gives the corresponding metallacyclopentasilanes.

    17. Modulation of the Reactivity Profile of IBX by Ligand Complexation: Ambient Temperature Dehydrogenation of Aldehydes and Ketones to α,β-Unsaturated Carbonyl Compounds (pages 993–996)

      K. C. Nicolaou, Tamsyn Montagnon and Phil S. Baran

      Version of Record online: 15 MAR 2002 | DOI: 10.1002/1521-3773(20020315)41:6<993::AID-ANIE993>3.0.CO;2-U

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      The reactivity profile of IBX can be altered by complexation with various ligands (e.g. 14). A new complex, IBX⋅MPO, is a remarkably effective oxidant and allows the room-temperature dehydrogenation of carbonyl compounds, for example, the formation of cyclooctenones 6 and 7 from cyclooctanone 5. IBX = iodoxybenzoic acid; MPO = 4-methoxypyridine-N-oxide.

    18. Oxidation of Silyl Enol Ethers by Using IBX and IBX⋅N-Oxide Complexes: A Mild and Selective Reaction for the Synthesis of Enones (pages 996–1000)

      K. C. Nicolaou, David L. F. Gray, Tamsyn Montagnon and Scott T. Harrison

      Version of Record online: 15 MAR 2002 | DOI: 10.1002/1521-3773(20020315)41:6<996::AID-ANIE996>3.0.CO;2-I

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      α,β-Unsaturated carbonyl compounds can be prepared by the oxidation of trimethylsilyl enol ethers with IBX (1) or IBX⋅MPO (2). A diverse set of carbonyl compounds can be dehydrogenated with ease by using this method. Trimethylsilyl enol ethers such as 4, which are formed in situ by the addition of an organometallic species to an enone, can be dehydrogenated with 1 or 2 to give a functionalized enone (e.g. 3[RIGHTWARDS ARROW]5). IBX = iodoxybenzoic acid; MPO = 4-methoxypyridine-N-oxide.

    19. One-Step Preparation of Block Copolymer Vesicles with Preferentially Segregated Acidic and Basic Corona Chains (pages 1001–1004)

      Laibin Luo and Adi Eisenberg

      Version of Record online: 15 MAR 2002 | DOI: 10.1002/1521-3773(20020315)41:6<1001::AID-ANIE1001>3.0.CO;2-Q

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      By varying the hydrophilic block lengths in polystyrene diblock copolymers containing both polystyrene-b-poly(acrylic acid) (PS-b-PAA) and polystyrene-b-poly(4-vinylpyridine) (PS-b-P(4-VP)), vesicles can be prepared (see transmission electron micrograph) in which the PAA and P(4-VP) chains can be preferentially segregated on the inside and outside of the vesicles.

    20. A Method To Identify and Screen Libraries of Guests That Complex to a Synthetic Host (pages 1004–1008)

      Menno R. de Jong, Ronald M. A. Knegtel, Peter D. J. Grootenhuis, Jurriaan Huskens and David N. Reinhoudt

      Version of Record online: 15 MAR 2002 | DOI: 10.1002/1521-3773(20020315)41:6<1004::AID-ANIE1004>3.0.CO;2-8

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      Molecular docking with a large number of guests, followed by experimental verification, was used to determine the selectivity of a synthetic host molecule and resulted in a hit rate of 30 % (see schematic outline of procedure). The identification of ligands for a given receptor by means of screening may represent a paradigm shift in supramolecular host–guest chemistry.

    21. Aluminum-Catalyzed Asymmetric Addition of TMSCN to Aromatic and Aliphatic Ketones Promoted by an Easily Accessible and Recyclable Peptide Ligand (pages 1009–1012)

      Hongbo Deng, Markus P. Isler, Marc L. Snapper and Amir H. Hoveyda

      Version of Record online: 15 MAR 2002 | DOI: 10.1002/1521-3773(20020315)41:6<1009::AID-ANIE1009>3.0.CO;2-F

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      Easily prepared peptide-based ligands efficiently promote the Al-catalyzed enantioselective addition of trimethylsilyl cyanide (TMSCN) to aromatic, aliphatic, cyclic, and acyclic ketones (see scheme for an example). The chiral ligands can be readily recovered and reused without loss of activity or selectivity.

    22. Unprecedented Regiocontrol Using An Aldolase I Antibody (pages 1012–1014)

      Virginie Maggiotti, Marina Resmini and Véronique Gouverneur

      Version of Record online: 15 MAR 2002 | DOI: 10.1002/1521-3773(20020315)41:6<1012::AID-ANIE1012>3.0.CO;2-I

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      Direct asymmetric aldol reactions at the less substituted carbon atom of unmodified unsymmetrical ketones are achieved in the presence of the commercially available aldolase I antibody 84G3 [Eq. (1)]. All the reactions proceeded with enantiomeric excesses greater than 94 %. Both enantiomers are accessible by using either an aldol or a retro-aldol reaction.

    23. Biocatalytic Asymmetric Hydrogen Transfer (pages 1014–1017)

      Wolfgang Stampfer, Birgit Kosjek, Christian Moitzi, Wolfgang Kroutil and Kurt Faber

      Version of Record online: 15 MAR 2002 | DOI: 10.1002/1521-3773(20020315)41:6<1014::AID-ANIE1014>3.0.CO;2-6

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      Celling chemistry: Ketones (secondary alcohols) can be biocatalytically reduced (oxidized) at a substrate concentration of up to 1.8 mol L−1 in an asymmetric fashion by employing a novel secondary alcohol dehydrogenase from Rhodococcus ruber DSM 44541 (see scheme). Furthermore, the enzyme is exceptionally stable at high cosubstrate concentrations, that is, 2-propanol (50 % v/v) for reduction and acetone (20 % v/v) for oxidation, respectively.

    24. Compartmentalization of a Gadolinium Complex in the Apoferritin Cavity: A Route To Obtain High Relaxivity Contrast Agents for Magnetic Resonance Imaging (pages 1017–1019)

      Silvio Aime, Luca Frullano and Simonetta Geninatti Crich

      Version of Record online: 15 MAR 2002 | DOI: 10.1002/1521-3773(20020315)41:6<1017::AID-ANIE1017>3.0.CO;2-P

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      A remarkably high relaxation enhancement of water protons has been observed for solutions containing apoferritin loaded with GdHPDO3A (see schematic representation). The entrapment of the complex within apoferritin (internal diameter: 7.5 nm, external diameter: 12.5 nm) allows an increased number of dipolar interactions with water molecules and exchangeable protons in the protein cavity.

    25. The Asymmetric Meerwein–Schmidt–Ponndorf–Verley Reduction of Prochiral Ketones with iPrOH Catalyzed by Al Catalysts (pages 1020–1022)

      E. Joseph Campbell, Hongying Zhou and SonBinh T. Nguyen

      Version of Record online: 15 MAR 2002 | DOI: 10.1002/1521-3773(20020315)41:6<1020::AID-ANIE1020>3.0.CO;2-S

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      Efficient and practical: An aluminum-based catalyst system for the asymmetric Meerwein–Schmidt–Ponndorf–Verley reduction of aromatic ketones is reported. By using iPrOH as the achiral hydride source and BINOL-type chiral ligands (see scheme), chiral secondary aromatic alcohols (up to 83 % ee) can be obtained in good yields.

    26. Highly Efficient Stereocontrolled Total Synthesis of the Polyfunctional Carotenoid Peridinin (pages 1023–1026)

      Noriyuki Furuichi, Hirokazu Hara, Takashi Osaki, Hajime Mori and Shigeo Katsumura

      Version of Record online: 15 MAR 2002 | DOI: 10.1002/1521-3773(20020315)41:6<1023::AID-ANIE1023>3.0.CO;2-A

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      The convergent, highly stereoselective synthesis of the nor carotenoid peridinin (1) is based on the following key steps: a) a Sharpless asymmetric epoxidation, b) reaction with a silylfuran-Wittig reagent and oxidation with 1O2, c) a Pd-catalyzed three-step one-pot procedure for the formation of the ylidene butenolide segment), and d) a modified Julia olefination. This provides a new method for the synthesis of carotenoids.

    27. Dynamics and Energetics of Hole Trapping in DNA by 7-Deazaguanine (pages 1026–1028)

      Frederick D. Lewis, Jianqin Liu, Xiaoyang Liu, Xiaobing Zuo, Ryan T. Hayes and Michael R. Wasielewski

      Version of Record online: 15 MAR 2002 | DOI: 10.1002/1521-3773(20020315)41:6<1026::AID-ANIE1026>3.0.CO;2-T

      A deep hole trap is 7-deazaguanine (Z)—according to time-resolved transient absorption spectroscopy and kinetic modeling—for hole transport in DNA from a guanine (G) to a Z base across one or two intervening adenine–thymine base pairs. The Gibbs energy for hole transport from G to Z was determined to be −0.19 eV, much larger than values for GG or GGG sites. Thus Z effectively prevents charge migration in DNA.

    28. Hydroxylation of N-Heterocycle Ligands Observed in Two Unusual Mixed-Valence CuI/CuII Complexes (pages 1029–1031)

      Xian-Ming Zhang, Ming-Liang Tong and Xiao-Ming Chen

      Version of Record online: 15 MAR 2002 | DOI: 10.1002/1521-3773(20020315)41:6<1029::AID-ANIE1029>3.0.CO;2-B

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      Structural evidence for the Gillard mechanism of covalent hydrates is provided by two mixed-valence CuI/CuII complexes containing 2,2′-bipyridine (see picture) or 1,10-phenanthroline ligands, in which a hydroxy group is added to a carbon atom adjacent to a nitrogen atom. These complexes are synthesized by hydrothermal treatment of Cu(NO3)2, the respective N,N ligand, and terephthalic acid.

    29. Diastereoselective Asymmetric Nitro-Aldol Reaction of α-Amino Aldehydes under High Pressure without Catalyst (pages 1031–1033)

      Yukihiro Misumi and Kiyoshi Matsumoto

      Version of Record online: 15 MAR 2002 | DOI: 10.1002/1521-3773(20020315)41:6<1031::AID-ANIE1031>3.0.CO;2-K

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      Under pressure, the nitro-aldol reaction of (S)-N,N-dibenzylphenylalaninal and related compounds with nitroalkanes was highly stereoselective (see scheme; R1, R2 = Me, H; R = Ph, Me, iPr, iBu). This reaction is very convenient, as it only requires high pressure and no catalyst.

    30. Sigmatropic Shiftamers: Fluxionality in Broken Ladderane Polymers (pages 1033–1036)

      Dean J. Tantillo and Roald Hoffmann

      Version of Record online: 15 MAR 2002 | DOI: 10.1002/1521-3773(20020315)41:6<1033::AID-ANIE1033>3.0.CO;2-8

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      A new (and so far hypothetical) class of molecules is described—the “sigmatropic shiftamers.” These are polymers that contain local “defects”—single or double bonds—which propagate by sigmatropic rearrangements (see scheme).

    31. Ultrastable and Highly Acidic, Zeolite-Coated Mesoporous Aluminosilicates (pages 1036–1040)

      Do Trong On and Serge Kaliaguine

      Version of Record online: 15 MAR 2002 | DOI: 10.1002/1521-3773(20020315)41:6<1036::AID-ANIE1036>3.0.CO;2-R

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      A uniform pore size with a highly ordered structure is still observed for zeolite (ZSM-5)-coated mesoporous aluminosilicates (ZCMesoAS) even after the coating procedure (see transmission electron micrograph). These ZCMesoAS, which are hydrothermally ultrastable and highly acidic owing to the nanocrystalline zeolitic nature of their pore wall surface, are produced from diluted clear solutions containing primary zeolite units. The novel features of ZCMesoAS open new possibilities for their use as acid catalysts.

    32. Diffusion-Limited, Aggregation-Based, Mesoscopic Assembly of Roughened Core–Shell Bimetallic Nanoparticles into Fractal Networks at the Air–Water Interface (pages 1040–1044)

      Yongdong Jin and Shaojun Dong

      Version of Record online: 15 MAR 2002 | DOI: 10.1002/1521-3773(20020315)41:6<1040::AID-ANIE1040>3.0.CO;2-O

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      The concentration of the plating solution enables control over the fine-tuning of fractal patterns and also drastically affects the crystal growth of Ag/Au core–shell roughened nanoparticles through diffusion-limited aggregation. At low concentrations there are more open spaces in the well-ramified fractal pattern than at higher concentrations, and the whisker-linked nanoparticles align almost one-by-one (see transmission electron micrograph).

    33. The First Water-Soluble Copper(I) Calix[6]arene Complex Presenting a Hydrophobic Ligand Binding Pocket: A Remarkable Model for Active Sites in Metalloenzymes (pages 1044–1046)

      Yannick Rondelez, Gildas Bertho and Olivia Reinaud

      Version of Record online: 15 MAR 2002 | DOI: 10.1002/1521-3773(20020315)41:6<1044::AID-ANIE1044>3.0.CO;2-0

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      Remarkable stabilization of a copper(i) center is evident in the tris(sulfonated) calixarene-based complex shown. This complex is truly biomimetic as it is soluble in water and also has a free valence where CO can bind. Thus it imitates the first coordination sphere encountered in copper enzymes and the hydrophobic microenvironment of the active site.

    34. Self-Complementary Metal Complexes Containing a DNA Base Pair (pages 1047–1049)

      Clayton Price, Benjamin R. Horrocks, Annabelle Mayeux, Mark R. J. Elsegood, William Clegg and Andrew Houlton

      Version of Record online: 15 MAR 2002 | DOI: 10.1002/1521-3773(20020315)41:6<1047::AID-ANIE1047>3.0.CO;2-J

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      Hoogsteen base pairing between coordinated adenine (A) and pendant thymine (T) residues of the Pt complex of a dithioether ligand bearing A and T groups results in the formation of infinite chains in the solid state (see picture). The chains are further involved in π–π stacking interactions.

    35. Dearomatizing Disrotatory Electrocyclic Ring Closure of Lithiated N-Benzoyloxazolidines (pages 1049–1051)

      Jonathan Clayden, Savroop Purewal, Madeleine Helliwell and Simon J. Mantell

      Version of Record online: 15 MAR 2002 | DOI: 10.1002/1521-3773(20020315)41:6<1049::AID-ANIE1049>3.0.CO;2-7

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      Loss of aromaticity ensues when N-benzoyl oxazolidines are lithiated and undergo a 6π disrotatory electrocyclization (see scheme). The stereochemistry of the cyclization shows it to be a new example of an electrocyclic ring closure. The cis-tricyclic products epimerize to their more stable trans diastereoisomers in aqueous acid.

    36. Click Chemistry In Situ: Acetylcholinesterase as a Reaction Vessel for the Selective Assembly of a Femtomolar Inhibitor from an Array of Building Blocks (pages 1053–1057)

      Warren G. Lewis, Luke G. Green, Flavio Grynszpan, Zoran Radić, Paul R. Carlier, Palmer Taylor, M. G. Finn and K. Barry Sharpless

      Version of Record online: 15 MAR 2002 | DOI: 10.1002/1521-3773(20020315)41:6<1053::AID-ANIE1053>3.0.CO;2-4

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      Form-fitting chemistry in a protein mold is enabled by the use of the 1,3-dipolar cycloaddition of azides and alkynes. The enzyme acetylcholinesterase preferentially assembles one pair of these reactants, each of which bears a group that binds to adjacent positions on the protein structure (see picture), into a 1,2,3-triazole adduct that is the most potent noncovalent inhibitor of the enzyme yet developed.

    37. Highly Enantioselective Desymmetrization of Anhydrides by Carbon Nucleophiles: Reactions of Grignard Reagents in the Presence of (−)-Sparteine (pages 1057–1059)

      Ryo Shintani and Gregory C. Fu

      Version of Record online: 15 MAR 2002 | DOI: 10.1002/1521-3773(20020315)41:6<1057::AID-ANIE1057>3.0.CO;2-H

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      Where other common chiral ligands failed, (−)-sparteine can be employed to form complexes with Grignard reagents. These chirally modified reagents desymmetrize a range of anhydrides with good enantioselectivity (up to 92 % ee; see scheme). Whereas (−)-sparteine is well known to form complexes with organolithium reagents and to induce excellent enantioselection in their reactions with electrophiles, (−)-sparteine-controlled asymmetric processes that involve Grignard reagents are rare.

    38. A Stereospecific Ruthenium-Catalyzed Allylic Alkylation (pages 1059–1061)

      Barry M. Trost, Pierre L. Fraisse and Zachary T. Ball

      Version of Record online: 15 MAR 2002 | DOI: 10.1002/1521-3773(20020315)41:6<1059::AID-ANIE1059>3.0.CO;2-5

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      Good regioselectivity and chirality transfer for aryl-substituted allyl units is achieved in allylic alkylations with a wide range of nucleophiles by using the highly active ruthenium catalyst 1. This method provides a route to antidepressants such as (−)-fluoxetine from (S)-ephedrine (see scheme; Cp*=η5-C5Me5, TBAT=tetrabutylammonium triphenyldifluorosilicate).

    39. Enantioselective Synthesis of Kedarcidin Chromophore Aglycon in Differentially Protected Form (pages 1062–1067)

      Andrew G. Myers, Philip C. Hogan, Alexander R. Hurd and Steven D. Goldberg

      Version of Record online: 15 MAR 2002 | DOI: 10.1002/1521-3773(20020315)41:6<1062::AID-ANIE1062>3.0.CO;2-8

      Thumbnail image of graphical abstract

      Four components, each prepared in multigram amounts, have been assembled in the convergent (25 steps in the longest linear sequence), enantioselective synthesis of the differentially protected kedarcidin chromophore aglycon (1). In addition to the enantioselective synthesis of each of the four components, the route features a transannular anionic cyclization to form the bicyclo[7.3.0]dodecadienediyne core in the presence of an ansa-bridged macrolactone. MOM=methoxymethyl, TIPS=triisopropylsilyl, TES=triethylsilyl.

    40. Book Review: Voodoo Science. The Road from Foolishness to Fraud. Edited by Robert L. Park (pages 1069–1071)

      Nicholas J. Turro

      Version of Record online: 15 MAR 2002 | DOI: 10.1002/1521-3773(20020315)41:6<1069::AID-ANIE1069>3.0.CO;2-3

    41. Book Review: Quantum-Mechanical Prediction of Thermochemical Data. Edited by Jerzy Cioslowski (pages 1071–1072)

      Detlef Schröder

      Version of Record online: 15 MAR 2002 | DOI: 10.1002/1521-3773(20020315)41:6<1071::AID-ANIE11111071>3.0.CO;2-4

    42. Book Review: Electrochemistry of Nanomaterials. Edited by Gary Hodes (pages 1072–1073)

      Laurence Peter

      Version of Record online: 15 MAR 2002 | DOI: 10.1002/1521-3773(20020315)41:6<1072::AID-ANIE1072>3.0.CO;2-6

    43. Book Review: Combinatorial Library Design and Evaluation. Edited by Arup K. Ghose and Vellarkad N. Viswanadhan (pages 1073–1074)

      Gisbert Schneider

      Version of Record online: 15 MAR 2002 | DOI: 10.1002/1521-3773(20020315)41:6<1073::AID-ANIE1073>3.0.CO;2-0

    44. Book Review: Quaternary Ammonium Salts. Their Use in Phase-Transfer Catalysis. By R. Allen Jones (page 1074)

      Barry Lygo

      Version of Record online: 15 MAR 2002 | DOI: 10.1002/1521-3773(20020315)41:6<1074::AID-ANIE1074>3.0.CO;2-V

    45. Web Site: The Protein Information Resource (page 1075)

      Daniel Hoffmann

      Version of Record online: 15 MAR 2002 | DOI: 10.1002/1521-3773(20020315)41:6<1075::AID-ANIE1075>3.0.CO;2-P

    46. Preview: Angew. Chem. Int. Ed. 6/2002 (page 1078)

      Version of Record online: 15 MAR 2002 | DOI: 10.1002/1521-3773(20020315)41:6<1078::AID-ANIE1078>3.0.CO;2-7