Angewandte Chemie International Edition

Cover image for Vol. 47 Issue 25

June 9, 2008

Volume 47, Issue 25

Pages 4609–4759

  1. Cover Picture

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    3. Inside Cover
    4. Graphical Abstract
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    6. Book Review
    7. Highlights
    8. Review
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    1. Cover Picture: Multiplexing Sensory Molecules Map Protons Near Micellar Membranes (Angew. Chem. Int. Ed. 25/2008) (page 4609)

      Seiichi Uchiyama, Kaoru Iwai and A. Prasanna de Silva

      Article first published online: 3 JUN 2008 | DOI: 10.1002/anie.200890117

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      Like mapping other worlds In their Communication on page 4667 ff., A. P. de Silva et al. describe proton concentration maps of detergent micelles obtained by the fluorescent multiplexing sensors (space-filling model). These sensors can change their positions and report information comprised of pKa values and emission wavelengths. These sensors serve as nanosized robot vehicles, as they send detailed data from humanly inaccessible environments.

  2. Inside Cover

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    1. Inside Cover: Toroidal Nanoobjects from Rosette Assemblies of Melamine-Linked Oligo(p-phenyleneethynylene)s and Cyanurates (Angew. Chem. Int. Ed. 25/2008) (page 4610)

      Shiki Yagai, Sankarapillai Mahesh, Yoshihiro Kikkawa, Kanako Unoike, Takashi Karatsu, Akihide Kitamura and Ayyappanpillai Ajayaghosh

      Article first published online: 3 JUN 2008 | DOI: 10.1002/anie.200890118

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      Nanodonuts form from hierarchical self-organization of a melamine featuring π-conjugated oligo(para-phenyleneethynylene)s with a cyanurate. The toroidal nanostructures, with a diameter of 40 nm (see AFM image), form in decane under dilute conditions. S. Yagai, A. Ajayaghosh et al. propose in their Communication on page 4691 ff. that a hydrogen-bonded rosette is an essential intermediate supramolecular species for such a hierarchical self-organization process. The background picture shows a “bubble ring” made by a scuba diver.

  3. Graphical Abstract

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    6. Book Review
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  4. News

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  5. Book Review

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  6. Highlights

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    1. Organocatalytic Reactions with Acetaldehyde (pages 4632–4634)

      Benito Alcaide and Pedro Almendros

      Article first published online: 15 MAY 2008 | DOI: 10.1002/anie.200801231

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      Big step, small molecule: Although acetaldehyde is the simplest of enolizable carbonyl compounds, and low-molecular-weight enamine/iminium-ion organocatalysis is the more elegant and most economical way to introduce chirality into a molecule, the first reports of the direct catalytic asymmetric reactions of acetaldehyde with electrophiles have just recently appeared (see scheme; Boc=tert-butyloxycarbonyl). Elaboration of the obtained adducts provides precursors for the synthesis of pharmaceuticals.

    2. Postsynthetic Covalent Modification of Metal–Organic Framework (MOF) Materials (pages 4635–4637)

      Yu-Fei Song and Leroy Cronin

      Article first published online: 19 MAY 2008 | DOI: 10.1002/anie.200801631

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      MOF Tuning: Recent progress on postsynthetic covalent modification of MOF (metal–organic framework) materials has led to the discovery of exciting new porous inorganic materials. These results involve transformation of the organic groups of MOFs without altering the three-dimensional structure.

  7. Review

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    1. Asymmetric Organocatalysis: From Infancy to Adolescence (pages 4638–4660)

      Alessandro Dondoni and Alessandro Massi

      Article first published online: 17 APR 2008 | DOI: 10.1002/anie.200704684

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      As Bernini's David, in the prime of adolescence, fought Goliath armed only with a sling and a stone, organocatalysis uses simple organic molecules to address some fundamental issues of organic synthesis. Important questions concern the chemical efficiency of such processes and the development of viable and simple routes to natural products and drug candidates.

  8. Communications

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    1. Supramolecular Capsules with Gated Pores from an Amphiphilic Rod Assembly (pages 4662–4666)

      Jung-Keun Kim, Eunji Lee, Yong-beom Lim and Myongsoo Lee

      Article first published online: 16 MAY 2008 | DOI: 10.1002/anie.200705863

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      Please release me: Dumbbell-shaped rod amphiphiles self-assemble into hollow spheres (see picture) with gated nanopores in the shell. These pores undergo reversible transitions from the open state to the closed state upon heating, and are capable of entrapping the cargos with preservation of their hollow spherical structure, in a manner similar to viral capsids.

    2. Multiplexing Sensory Molecules Map Protons Near Micellar Membranes (pages 4667–4669)

      Seiichi Uchiyama, Kaoru Iwai and A. Prasanna de Silva

      Article first published online: 21 MAY 2008 | DOI: 10.1002/anie.200801516

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      Hi-fi mapping: Multiplexing fluorescent sensors that simultaneously target proton concentration and polarity move to micellar nanospaces, self-regulate their positions, and report their pKa values and wavelengths, which are controlled by their local environments. Such sensory functions enable maps of proton gradients near micellar membranes to be drawn.

    3. Chiral Bis(pyridylimino)isoindoles: A Highly Modular Class of Pincer Ligands for Enantioselective Catalysis (pages 4670–4674)

      Björn K. Langlotz, Hubert Wadepohl and Lutz H. Gade

      Article first published online: 14 MAY 2008 | DOI: 10.1002/anie.200801150

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      Protect your back: Chiral wedges (red, see scheme) at the wingtips of bis(2-pyridylimino)isoindole (bpi) pincer ligands with an appropriate protective hedge (green), to block the metal center from backside attack, in the backbone represent a new class of efficient 3d-metal catalysts. These catalysts gave excellent enantioselectivities in the iron-catalyzed hydrosilylation of arylketones and in the cobalt-catalyzed cyclopropanation of alkenes.

    4. H2O2 Generation by Decamethylferrocene at a Liquid|Liquid Interface (pages 4675–4678)

      Bin Su, Raheleh Partovi Nia, Fei Li, Mohamad Hojeij, Michel Prudent, Clémence Corminboeuf, Zdenek Samec and Hubert H. Girault

      Article first published online: 16 MAY 2008 | DOI: 10.1002/anie.200801004

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      Hydrogen peroxide generation at a liquid|liquid interface occurs with a yield of 20 % with respect to the concentration of reducing agent (decamethylferrocene). The liquid|liquid interface supplies electrons from the reducing agent and protons from the aqueous phase to drive the reduction of O2 into H2O2, which is extracted into the aqueous phase during the course of reaction (see picture; DCE=1,2-dichloroethane).

    5. Small-Molecule Inhibitors of Islet Amyloid Polypeptide Fibril Formation (pages 4679–4682)

      Rajesh Mishra, Bruno Bulic, Daniel Sellin, Suman Jha, Herbert Waldmann and Roland Winter

      Article first published online: 9 MAY 2008 | DOI: 10.1002/anie.200705372

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      Small and effective: The pathological aggregation of amylin (IAPP), which leads to type II diabetes mellitus, is effectively inhibited by small-molecule rhodanine-based inhibitors at nanomolar concentrations. The prevention of aggregation by treatment with the inhibitor is demonstrated by AFM (see image).

    6. Scaling Relationships for Adsorption Energies on Transition Metal Oxide, Sulfide, and Nitride Surfaces (pages 4683–4686)

      Eva M. Fernández, Poul G. Moses, Anja Toftelund, Heine A. Hansen, José I. Martínez, Frank Abild-Pedersen, Jesper Kleis, Berit Hinnemann, Jan Rossmeisl, Thomas Bligaard and Jens K. Nørskov

      Article first published online: 16 MAY 2008 | DOI: 10.1002/anie.200705739

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      Getting on top of things: DFT calculations have been used to study the adsorption energies of O, OH, S, SH, N, NH, and NH2 on transition metal oxide, sulfide, and nitride surfaces. A scaling relationship was found between the adsorption energies of the intermediates and the adsorption energies of the atoms which is independent of the metal and depends only on the number of H atoms in the molecule (see graph).

    7. Organocatalytic Asymmetric Synthesis of Versatile γ-Lactams (pages 4687–4690)

      Thomas B. Poulsen, Gustav Dickmeiss, Jacob Overgaard and Karl Anker Jørgensen

      Article first published online: 14 MAY 2008 | DOI: 10.1002/anie.200800329

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      A good starting point: Optically pure γ-lactams have been prepared by organocatalytic enantioselective vinylic substitution. The parent lactam structure allows logical and systematic introduction of functionality around the periphery to access new derivatives of this important class of molecules. Bn=benzyl, PG=protecting group.

    8. Toroidal Nanoobjects from Rosette Assemblies of Melamine-Linked Oligo(p-phenyleneethynylene)s and Cyanurates (pages 4691–4694)

      Shiki Yagai, Sankarapillai Mahesh, Yoshihiro Kikkawa, Kanako Unoike, Takashi Karatsu, Akihide Kitamura and Ayyappanpillai Ajayaghosh

      Article first published online: 21 MAY 2008 | DOI: 10.1002/anie.200800417

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      Nanodonuts! A hydrogen-bonded cyclic assembly (rosette, left) of a melamine featuring π-conjugated oligo(p-phenyleneethynylene) hierarchically self-organizes with a cyanurate in decane under dilute conditions to form toroidal nanostructures (right) with a diameter of 40 nm.

    9. A General and Efficient Method for the Suzuki–Miyaura Coupling of 2-Pyridyl Nucleophiles (pages 4695–4698)

      Kelvin L. Billingsley and Stephen L. Buchwald

      Article first published online: 19 MAY 2008 | DOI: 10.1002/anie.200801465

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      One of the most general systems for the cross-coupling of aryl and heteroaryl bromides and chlorides with 2-pyridyl-derived nucleophiles has been developed, for which catalysts comprising [Pd2(dba)3] and either diaryl (1) or dialkyl phosphine oxide (2) supporting ligands were found to be ideal (see scheme).

    10. Tandem Modification of Metal–Organic Frameworks by a Postsynthetic Approach (pages 4699–4702)

      Zhenqiang Wang and Seth M. Cohen

      Article first published online: 29 APR 2008 | DOI: 10.1002/anie.200800686

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      More than a one-trick pony: Postsynthetic modification of metal–organic frameworks (MOFs) permits stepwise, “tandem” modification of the lattice. An MOF bearing reactive functional groups can be subjected to a controllable, heterogeneous transformation sequence while retaining its structural integrity and microporosity. This approach allows the synthesis of MOFs bearing multiple functional groups (represented in the scheme by green and pink spheres).

    11. A Study of BF3-Promoted ortho Lithiation of Anilines and DFT Calculations on the Role of Fluorine–Lithium Interactions (pages 4703–4706)

      Satinder V. Kessar, Paramjit Singh, Kamal N. Singh, Prasad V. Bharatam, Arvind K. Sharma, Sneh Lata and Amarjit Kaur

      Article first published online: 16 MAY 2008 | DOI: 10.1002/anie.200705967

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      Director's cut: The poor directing ability of the dimethylamino group in directed ortho metalation is altered by complexation to BF3, which makes it more strongly activating than methoxy and chloro groups. DFT calculations of simplified lithiated intermediates reveal a small role of the inductive effect, but a distinctive F⋅⋅⋅Li interaction that leads to a F–Li distance which is remarkably similar to the C–Li distance.

    12. From Native to Non-Native Two-Dimensional Protein Lattices through Underlying Hydrophilic/Hydrophobic Nanoprotrusions (pages 4707–4710)

      Susana Moreno-Flores, Amal Kasry, Hans-Juergen Butt, Chandrasekhar Vavilala, Michael Schmittel, Dietmar Pum, Uwe Bernd Sleytr and Jose Luis Toca-Herrera

      Article first published online: 16 MAY 2008 | DOI: 10.1002/anie.200800151

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      Tuning to the terminals: Controlled tuning of protein–substrate interactions induces a transition from native to non-native protein crystals (see AFM images) as—depending on m, the chain-length difference, which determines whether surface protrusions are hydroxy or methyl functionalized—the underlying non-ion-mediated interactions are gradually transformed from mainly associative (H-bonding) to hydrophobic.

    13. Palladium-Catalyzed Tandem Heck Reaction/C[BOND]H Functionalization—Preparation of Spiro-Indane-Oxindoles (pages 4711–4714)

      Rebecca T. Ruck, Mark A. Huffman, Mary M. Kim, Michael Shevlin, Wynne V. Kandur and Ian W. Davies

      Article first published online: 19 MAY 2008 | DOI: 10.1002/anie.200800549

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      Tied up nicely: A novel tandem reaction involving an intramolecular Heck reaction with subsequent functionalization of an unactivated C[BOND]H bond to generate spiro-fused indane-oxindoles is described (see scheme; PMB=p-methoxybenzyl).

    14. Four-Electron Oxidative Formation of Aryl Diazenes Using a Tantalum Redox-Active Ligand Complex (pages 4715–4718)

      Ryan A. Zarkesh, Joseph W. Ziller and Alan F. Heyduk

      Article first published online: 16 MAY 2008 | DOI: 10.1002/anie.200800812

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      The active ingredient: The bis(μ-imido) tantalum dimer {[ONOred]Ta(μ-N-p-tolyl)(py)}2 releases the aryl diazene (p-tolyl)N[DOUBLE BOND]N(p-tolyl) upon four-electron oxidation with PhICl2 (see scheme; py=pyridine). Studies suggest that the redox-active [ONOred]3− ligands act to collect single-electron oxidation equivalents for the multielectron reaction.

    15. Catalytic Asymmetric Michael Reactions of Acetaldehyde (pages 4719–4721)

      Patricia García-García, Arnaud Ladépêche, Rajkumar Halder and Benjamin List

      Article first published online: 28 APR 2008 | DOI: 10.1002/anie.200800847

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      Acetaldehyde, now a big contender: A silyl prolinol derivative was found to catalyze the first Michael addition of acetaldehyde with both aromatic and aliphatic nitroolefins in excellent enantioselectivities (see scheme, TMS=trimethylsilyl). The utility of the reaction is illustrated in the synthesis of three current pharmaceuticals and in the synthesis of an enantiopure 3-monosubstituted pyrrolidine.

    16. Asymmetric Michael Reaction of Acetaldehyde Catalyzed by Diphenylprolinol Silyl Ether (pages 4722–4724)

      Yujiro Hayashi, Takahiko Itoh, Masahiro Ohkubo and Hayato Ishikawa

      Article first published online: 25 APR 2008 | DOI: 10.1002/anie.200801130

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      An acetaldehyde breakthrough: The catalytic asymmetric Michael addition reaction of acetaldehyde and various nitroalkenes in the presence of a chiral diphenylprolinol silyl ether organocatalyst is described (see scheme; TMS=trimethylsilyl). The desired 1,4-addition products, α-unsubstituted γ-nitro aldehydes, were obtained in good yields with excellent enantioselectivities.

    17. Patterning the Surface of Colloidal Microspheres and Fabrication of Nonspherical Particles (pages 4725–4728)

      Likui Wang, Linhua Xia, Gang Li, Serge Ravaine and X. S. Zhao

      Article first published online: 13 MAY 2008 | DOI: 10.1002/anie.200801061

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      One seed for two: Microspheres with patterned surfaces were obtained by modifying the surface of microspheres of a self-assembled colloidal crystal and redispersion of the colloidal crystal into individual particles. With these surface-patterned spheres as seeds, two types of nonspherical particles were fabricated by the seeded particle growth method.

    18. Ligand-Free Pd-Catalyzed Highly Selective Arylation of Allylic Esters with Retention of the Traditional Leaving Group (pages 4729–4732)

      Delin Pan, Anjun Chen, Yijin Su, Wang Zhou, Si Li, Wei Jia, Juan Xiao, Qingjian Liu, Liangren Zhang and Ning Jiao

      Article first published online: 19 MAY 2008 | DOI: 10.1002/anie.200800966

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      What leaving group? Organic halides and allylic esters undergo efficient Pd-catalyzed Heck reactions under mild conditions in air to form a new C[BOND]C bond without elimination of the β-OAc group in the intermediate palladium complex. Instead a highly regioselective β-H elimination takes place to provide substituted derivatives of allylic alcohols (see scheme).

    19. Palladium-Catalyzed Intermolecular Aerobic Oxidative Amination of Terminal Alkenes: Efficient Synthesis of Linear Allylamine Derivatives (pages 4733–4736)

      Guosheng Liu, Guoyin Yin and Liang Wu

      Article first published online: 16 MAY 2008 | DOI: 10.1002/anie.200801009

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      O2-coupled allylic C[BOND]H amination: A first general palladium-mediated intermolecular aerobic oxidative allylic amination was developed to synthesize linear (E)-allylimides with high regioselectivity (see scheme; MA=maleic anhydride). The proposed mechanism involves an allylic C[BOND]H activation with subsequent nitrogen nucleophile substitution. The catalytic system allows efficient dioxygen-coupled turnover without additional cocatalysts.

    20. Total Synthesis of (+)-Neopeltolide (pages 4737–4739)

      Haruhiko Fuwa, Shinya Naito, Tomomi Goto and Makoto Sasaki

      Article first published online: 19 MAY 2008 | DOI: 10.1002/anie.200801399

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      Rapid elaboration: (+)-Neopeltolide, a novel marine metabolite with potent cytotoxicity against several cancer cell lines, was the target of an efficient total synthesis (see scheme). The construction of the 2,4,6-trisubstituted tetrahydropyran substructure is based on a Suzuki–Miyaura coupling/ring-closing metathesis sequence. BOM=benzyloxymethyl, MPM=4-methoxyphenylmethyl, TIPS=triisopropylsilyl.

    21. Stable Five- and Six-Coordinate Cobalt(III) Complexes with a Pentadentate Bispidine Ligand (pages 4740–4743)

      Peter Comba, Marion Kerscher, Geoffrey A. Lawrance, Bodo Martin, Hubert Wadepohl and Steffen Wunderlich

      Article first published online: 16 MAY 2008 | DOI: 10.1002/anie.200800515

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      I am ligand: A pentadentate bispidine ligand with two tertiary amine and three pyridine donors stabilizes the uncommon intermediate-spin electronic configuration of CoIII (S=1; see picture: C gray, N blue, O red, Co violet). Dissociation of the monodentate coligand yields a catalytically active pentacoordinate complex.

    22. Metal-Free Conversion of Methane and Cycloalkanes to Amines and Amides by Employing a Borylnitrene (pages 4744–4747)

      Holger F. Bettinger, Matthias Filthaus, Holger Bornemann and Iris M. Oppel

      Article first published online: 16 MAY 2008 | DOI: 10.1002/anie.200705936

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      C[BOND]H insertion: Borylnitrenes, which are generated in situ by photoylsis of azides, convert unactivated alkanes by intermolecular C[BOND]H insertion into aminoboranes (see scheme), which in turn can be reacted further to give amines or amides. The boryl group serves two purposes: it converts the nitrene into a highly reactive BN vinylidene analogue, and it is easily cleaved from the product.

    23. dsRNA-Functionalized Multifunctional γ-Fe2O3 Nanocrystals: A Tool for Targeting Cell Surface Receptors (pages 4748–4752)

      Mohammed Ibrahim Shukoor, Filipe Natalio, Nadine Metz, Natalie Glube, Muhammad Nawaz Tahir, Helen Annal Therese, Vadim Ksenofontov, Patrick Theato, Peter Langguth, Jean-Paul Boissel, Heinz C. Schröder, Werner E. G. Müller and Wolfgang Tremel

      Article first published online: 15 MAY 2008 | DOI: 10.1002/anie.200704735

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      Specific cell recognition: Magnetic γ-Fe2O3 nanoparticles (MNPs) functionalized with a fluorescently labeled polymer and polyinosinic-polycytidylic acid [poly(I:C)] allow the specific visualizion of the TLR3 receptors on the the surface of Caki-1 cells. The expression of TLR3 on the Caki-1 cells was demonstrated independently by RT-PCR and immunostaining techniques.

    24. Chromophore Heterogeneity and Photoconversion in Phytochrome Crystals and Solution Studied by Resonance Raman Spectroscopy (pages 4753–4755)

      David von Stetten, Mina Günther, Patrick Scheerer, Daniel H. Murgida, Maria Andrea Mroginski, Norbert Krauß, Tilman Lamparter, Junrui Zhang, David M. Anstrom, Richard D. Vierstra, Katrina T. Forest and Peter Hildebrandt

      Article first published online: 16 MAY 2008 | DOI: 10.1002/anie.200705716

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      Crystals of the photoreceptor phytochrome were studied nondestructively by resonance Raman spectroscopy. The spectra of the chromophore-binding domains (CBD) of phytochrome from Deinococcus radiodurans, from which three-dimensional structures have been determined, demonstrate the same chromophore structure in the parent Pr state as in solution. Unlike CBD, crystals of phytochrome from Agrobacterium tumefaciens including the CBD and the PHY domain can be photoconverted to a Meta-Rc-like state.

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    3. Inside Cover
    4. Graphical Abstract
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    6. Book Review
    7. Highlights
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      Article first published online: 3 JUN 2008 | DOI: 10.1002/anie.200890121

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