Angewandte Chemie International Edition

Cover image for Vol. 43 Issue 35

September 6, 2004

Volume 43, Issue 35

Pages 4537–4673

    1. Cover Picture: Total Synthesis and Configurational Assignment of (−)-Dictyostatin, a Microtubule-Stabilizing Macrolide of Marine Sponge Origin / Total Synthesis of (−)-Dictyostatin: Confirmation of Relative and Absolute Configurations (Angew. Chem. Int. Ed. 35/2004) (page 4537)

      Ian Paterson, Robert Britton, Oscar Delgado, Arndt Meyer, Karine G. Poullennec, Youseung Shin, Jean-Hugues Fournier, Yoshikazu Fukui, Arndt M. Brückner and Dennis P. Curran

      Article first published online: 1 SEP 2004 | DOI: 10.1002/anie.200490122

      Sponging off nature is a reliable way to find promising drug leads: (−)-Dictyostatin, which was isolated from the marine sponge Corallistidae, is a novel microtubule-stabilizing agent that could be useful against multidrug-resistant tumors. In their Communications on pages 4629 ff. and 4634 ff., the groups of I. Paterson and D. P. Curran describe the total synthesis of this challenging target, thus establishing unequivocally the relative and absolute configuration of the macrolactone and opening the way to useful amounts of the drug and designed analogues. The Photo of the sponge was provided by Harbor Branch Oceanographic Institution.

    2. A Radical Show (pages 4550–4551)

      Emmanuel Lacôte

      Article first published online: 1 SEP 2004 | DOI: 10.1002/anie.200461443

    3. Organic Protein Chemistry: Drug Discovery through the Chemical Modification of Proteins (pages 4554–4556)

      Jörg Rademann

      Article first published online: 20 JUL 2004 | DOI: 10.1002/anie.200460075

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      Recent strategies used in the hunt for new active compounds employ chemically modified proteins that are formed by ligation techniques and then transformed chemically. The modified proteins have been successful both as active compounds and in the search for new ligands and binding pockets.

    4. On the TEM and AFM Evidence of Zeosil Nanoslabs Present during the Synthesis of Silicalite-1 (pages 4558–4561)

      Harikrishnan Ramanan, Efrosini Kokkoli and Michael Tsapatsis

      Article first published online: 20 AUG 2004 | DOI: 10.1002/anie.200460376

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      Nanoslabs (1): Investigations of the mechanism of formation of tetrapropylammonium (TPA)-silicalite-1 by TEM and atomic force microscopy (AFM) analysis (see picture) are not consistent with the existence of “nanoblocks” or “nanoslabs” previously proposed by J. A. Martens and co-workers

    5. Reply (pages 4562–4564)

      Christine E. A. Kirschhock, Duoduo Liang, Alexander Aerts, Caroline A. Aerts, Sebastien P. B. Kremer, Pierre A. Jacobs, Gustaaf Van Tendeloo and Johan A. Martens

      Article first published online: 20 AUG 2004 | DOI: 10.1002/anie.200460541

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      Nanoslabs (2): Small square domains of lighter contrast observed with TEM on NaCl particles are attributed to tetrapropylammonium-silicalite-1 nanoslabs carefully extracted from a nanoslab suspension (see TEM image).

    6. Towards Perfect Catalytic Asymmetric Synthesis: Dual Activation of the Electrophile and the Nucleophile (pages 4566–4583)

      Jun-An Ma and Dominique Cahard

      Article first published online: 1 SEP 2004 | DOI: 10.1002/anie.200300635

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      Twice as good: The design of new catalysts greatly benefits from the concept of dual activation (see picture) of the electrophile and the nucleophile, which has been increasingly applied in catalytic asymmetric syntheses. This Review gives some examples of spectacular developments in this area; some mechanistic models are also discussed.

    7. Ultrafast Cold Reactions in the Bipropellant Monomethylhydrazine/Nitrogen Tetroxide: CPMD Simulations (pages 4586–4589)

      Christel Nonnenberg, Irmgard Frank and Thomas M. Klapötke

      Article first published online: 9 AUG 2004 | DOI: 10.1002/anie.200454093

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      Highly reactive intermediates, such as that shown, which arise under special conditions in hypergolic mixtures of monomethylhydrazine and nitrogen tetroxide, may trigger uncontrolled reaction behavior. Car–Parrinello molecular dynamics simulations provide an insight into the complex reactions on very short timescales.

    8. Challenges in Engineering Spin Crossover: Structures and Magnetic Properties of Six Alcohol Solvates of Iron(II) Tris(2-picolylamine) Dichloride (pages 4589–4594)

      Marc Hostettler, Karl W. Törnroos, Dmitry Chernyshov, Brita Vangdal and Hans-Beat Bürgi

      Article first published online: 9 AUG 2004 | DOI: 10.1002/anie.200460736

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      So similar yet so different: The crystal structures of six alcohol solvates of the title compound (see formula) are found to be very similar at 200 K. In contrast, their spin-transition behavior and their structural phase transitions are quite different. Implications of these observations for crystal engineering are discussed.

    9. Regio- and Enantioselective Iridium-Catalyzed Allylic Alkylation with In Situ Activated P,C-Chelate Complexes (pages 4595–4597)

      Gunter Lipowsky, Nicole Miller and Günter Helmchen

      Article first published online: 1 SEP 2004 | DOI: 10.1002/anie.200460016

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      Come together: Successful cooperation of iridium and copper yielded a new catalyst system for allylic alkylation. Branched alkylation products can be obtained rapidly and with high enantioselectivity from simple linear precursors (see scheme; cod=cyclooctadiene).

    10. Total Synthesis of Apoptolidin (pages 4597–4601)

      Hermut Wehlan, Mario Dauber, M.-Teresa Mujica Fernaud, Julia Schuppan, Rainer Mahrwald, Burkhard Ziemer, M.-Elisa Juarez Garcia and Ulrich Koert

      Article first published online: 1 SEP 2004 | DOI: 10.1002/anie.200460172

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      A ring-size-selective macrolactonization and the early introduction of the saccharide portions are the main features of a total synthesis of the 20-membered macrolide apoptolidin (see formula), which induces apoptosis in rat glia cells transformed with oncogenes.

    11. Fully Metalated Silsesquioxanes: Building Blocks for the Construction of Catalyst Models (pages 4603–4606)

      Volker Lorenz, Stephan Gießmann, Yurii K. Gun'ko, Axel K. Fischer, John W. Gilje and Frank T. Edelmann

      Article first published online: 1 SEP 2004 | DOI: 10.1002/anie.200454094

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      Versatile building blocks for the construction of molecular models for heterogeneous catalysts are readily available in high yields in the form of fully metalated silsesquioxane derivatives, such as dimeric 1, by using alkali-metal silylamides as deprotonating agents.

    12. Sn-Filled Single-Crystalline Wurtzite-Type ZnS Nanotubes (pages 4606–4609)

      Junqing Hu, Yoshio Bando, Jinhua Zhan and Dmitri Golberg

      Article first published online: 1 SEP 2004 | DOI: 10.1002/anie.200454205

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      A Sn-nanorod-templated process was used for the first synthesis of single-crystalline wurtzite-type ZnS nanotubes. The as-grown ZnS nanotubes are structurally uniform single crystals and are partially filled with Sn (see picture). Most of the tubes are straight with lengths ranging from several to tens of micrometers, diameters of about 150–250 nm, and wall thicknesses of about 50–80 nm.

    13. Formation of a Stable, Lattice-Framework Disilene: A Strategy for the Construction of Bulky Substituents (pages 4610–4612)

      Shigeki Matsumoto, Shinobu Tsutsui, Eunsang Kwon and Kenkichi Sakamoto

      Article first published online: 1 SEP 2004 | DOI: 10.1002/anie.200460067

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      Bulky protectors: A one-pot reduction of tri(tert-butyl)cyclopropenyltribromosilane with potassium graphite yielded a unique lattice-framework disilene in 47 % yield (see scheme). The new polycyclic disilene is C2-symmetric and has a long Si[BOND]Si double bond (2.26 Å). Its stability is attributed to the bulky substituents, which act as protecting groups.

    14. A Combinatorial Approach to Catalytic Peptide Dendrimers (pages 4612–4615)

      Anthony Clouet, Tamis Darbre and Jean-Louis Reymond

      Article first published online: 1 SEP 2004 | DOI: 10.1002/anie.200460177

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      Exploring the structural diversity of peptide dendrimers as synthetic protein models: A 65 536-membered combinatorial peptide-dendrimer library was prepared by split-and-mix techniques on beads (see picture). The library was screened and revealed peptide dendrimers that catalyze fluorogenic ester hydrolysis and peptide dendrimers that bind to vitamin B12.

    15. Electrostatic Site Attachment of Divalent Counterions to Rodlike Ruthenium(II) Coordination Polymers Characterized by EPR Spectroscopy (pages 4616–4621)

      Dariush Hinderberger, Oliver Schmelz, Matthias Rehahn and Gunnar Jeschke

      Article first published online: 12 AUG 2004 | DOI: 10.1002/anie.200460500

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      Subnanosecond ion-pair lifetimes have been observed for the electrostatic attachment of divalent spin-carrying counterions to oppositely charged, rodlike RuII coordination polymers in solution. Continuous wave (CW) EPR and double electron-electron resonance (DEER) spectroscopy show that the spatial distribution of the divalent counterions reflects the spatial distribution of charges on the polyion (see schematic representation).

    16. Liquid Crystals with Complex Superstructures (pages 4621–4625)

      Bin Chen, Xiang Bing Zeng, Ute Baumeister, Siegmar Diele, Goran Ungar and Carsten Tschierske

      Article first published online: 19 AUG 2004 | DOI: 10.1002/anie.200460762

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      The hexagonal-channeled layer phase (ChLhex; see picture, right) is one of the new liquid-crystalline phases formed by the self-organization of the rigid rodlike alkali-metal carboxylates shown.

    17. Selective Oxidation of Methane to Methanol Catalyzed, with C[BOND]H Activation, by Homogeneous, Cationic Gold (pages 4626–4629)

      CJ Jones, Doug Taube, Vadim R. Ziatdinov, Roy A. Periana, Robert J. Nielsen, Jonas Oxgaard and William A. Goddard III

      Article first published online: 12 AUG 2004 | DOI: 10.1002/anie.200461055

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      Cationic gold catalyzes the title reaction in strong acid solvents with SeVI as the stoichiometric oxidant. At 180 oC and 27 bar of CH4 turnover numbers of about 30 and methanol concentrations of 0.6 M have been observed with selectivities >90%. DFT calculations indicate that cationic AuI and AuIII are both viable catalysts that operate by electrophilic C[BOND]H activation and oxidative functionalization (see picture).

    18. Total Synthesis and Configurational Assignment of (−)-Dictyostatin, a Microtubule-Stabilizing Macrolide of Marine Sponge Origin (pages 4629–4633)

      Ian Paterson, Robert Britton, Oscar Delgado, Arndt Meyer and Karine G. Poullennec

      Article first published online: 1 JUL 2004 | DOI: 10.1002/anie.200460589

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      A flexible and modular approach was used in the convergent and highly stereocontrolled synthesis of the antimitotic agent dictyostatin. This first total synthesis establishes its full stereochemistry and should be amenable to producing useful quantities and designed analogues of this molecule, whose conformation closely resembles that of discodermolide (see overlayed structures).

    19. Total Synthesis of (−)-Dictyostatin: Confirmation of Relative and Absolute Configurations (pages 4634–4637)

      Youseung Shin, Jean-Hugues Fournier, Yoshikazu Fukui, Arndt M. Brückner and Dennis P. Curran

      Article first published online: 1 JUL 2004 | DOI: 10.1002/anie.200460593

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      Will the real dictyostatin please stand up? There were five finalists as stereostructures for the potent anticancer agent dictyostatin; ten, if one were to include enantiomers. A total synthesis of (−)-dictyostatin (1) has ended the decade-old masquerade and identified the winner as a structure recently proposed by Paterson and Wright.

    20. Chemical Synthesis of the Second Messenger Nicotinic Acid Adenine Dinucleotide Phosphate by Total Synthesis of Nicotinamide Adenine Dinucleotide Phosphate (pages 4637–4640)

      James Dowden, Christelle Moreau, Richard S. Brown, Georgina Berridge, Antony Galione and Barry V. L. Potter

      Article first published online: 1 SEP 2004 | DOI: 10.1002/anie.200460054

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      Signaling dinucleotides: The first single-isomer synthesis of nicotinamide adenine dinucleotide phosphate (NADP) is reported. Installation and maintenance of sensitive phosphate and pyridinium functionalities were key to success. Significantly, conversion of NADP into the important mammalian second messenger NAADP was achieved. The graph shows the biological evaluation of the activity of the release of Ca2+ ions, which confirms the identity of NAADP.

    21. Enantioselective Organocatalytic Cyclopropanation via Ammonium Ylides (pages 4641–4644)

      Charles D. Papageorgiou, Maria A. Cubillo de Dios, Steven V. Ley and Matthew J. Gaunt

      Article first published online: 1 SEP 2004 | DOI: 10.1002/anie.200460234

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      Highly functionalized cyclopropanes can be produced with excellent enantioselectivity through an amine-catalyzed organocatalytic cyclopropanation process (see scheme). Catalytically generated asymmetric ammonium ylides mediate the reaction, and the cyclopropane products can be produced as either enantiomer by using quinine- or quinidine-derived catalysts.

    22. Simple Synthesis of Nodulation-Factor Analogues Exhibiting High Affinity towards a Specific Binding Protein (pages 4644–4646)

      Nathalie Grenouillat, Boris Vauzeilles, Jean-Jacques Bono, Eric Samain and Jean-Marie Beau

      Article first published online: 1 SEP 2004 | DOI: 10.1002/anie.200460275

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      A “Nod” in the right direction: Aromatic analogues of the lipooligosaccharidic nodulation (Nod) factors involved in the symbiosis of Sinorhizobium meliloti and legumes are easily assembled from very simple precursors by combining biotechnological and chemical procedures. Some of these analogues (see structure) bind tightly to a specific binding protein and form a new class of glycolipid mimics.

    23. Total Synthesis of (±)-Nominine, a Heptacyclic Hetisine-Type Aconite Alkaloid (pages 4646–4649)

      Hideaki Muratake and Mitsutaka Natsume

      Article first published online: 1 SEP 2004 | DOI: 10.1002/anie.200460332

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      The barrier has finally been lifted to the synthesis of hetisine-type alkaloids with the total synthesis of (±)-nominine (1) in 40 steps from 2-bromo-5-methoxyphenethyl iodide. Key steps in the construction of the architecturally complex polycyclic structure of this natural product were a radical cyclization of an enyne and a palladium-catalyzed intramolecular α arylation of an aldehyde.

    24. Halide Recognition through Diagnostic “Anion–π” Interactions: Molecular Complexes of Cl, Br, and I with Olefinic and Aromatic π Receptors (pages 4650–4652)

      Yaroslav S. Rosokha, Sergey V. Lindeman, Sergiy V. Rosokha and Jay K. Kochi

      Article first published online: 1 SEP 2004 | DOI: 10.1002/anie.200460337

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      Intense colorations and new charge-transfer absorption bands are observed upon addition of a halide (Cl, Br, I) to neutral organic π acceptors with electron-deficient olefinic and aromatic centers. These phenomena results from noncovalent anion–π interactions (shown schematically), which were confirmed by X-ray crystallography.

    25. An In Vitro Assay for Evaluation of Small-Molecule Inhibitors of Cholesterol Absorption (pages 4653–4656)

      Lisbet Kværnø, Tobias Ritter, Moritz Werder, Helmut Hauser and Erick M. Carreira

      Article first published online: 1 SEP 2004 | DOI: 10.1002/anie.200460348

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      Giving cholesterol the brush off: An intestinal brush border membrane vesicle assay has been devised for the convenient in vitro testing of small molecules for inhibition of cholesterol absorption. The assay was used to identify new nonhydrolyzable glycosides as potent cholesterol-absorption inhibitors and an oxazolidinone as an effective replacement of the β-lactam scaffold of ezetimibe (1).

    26. Dihydrogen Trioxide (HOOOH) Is Generated during the Thermal Reaction between Hydrogen Peroxide and Ozone (pages 4656–4659)

      Paul T. Nyffeler, Nicholas A. Boyle, Laxman Eltepu, Chi-Huey Wong, Albert Eschenmoser, Richard A. Lerner and Paul Wentworth Jr.

      Article first published online: 12 AUG 2004 | DOI: 10.1002/anie.200460457

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      Quantifiable amounts of HOOOH can be detected by 1H NMR spectroscopic analysis of the thermal reaction of O3 and HOOH (see scheme). This first experimental report of a link between these three oxidants suggests that HOOOH may be involved in oxidation reactions that span biological, atmospheric, and environmental systems.

    27. Green and Red Three-Photon Upconversion from Polymeric Lanthanide(III) Complexes (pages 4659–4662)

      Ka-Leung Wong, Wai-Ming Kwok, Wing-Tak Wong, David Lee Phillips and Kok-Wai Cheah

      Article first published online: 1 SEP 2004 | DOI: 10.1002/anie.200460576

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      Red light, green light! Emission through three-photon upconversion processes from polymeric organic–lanthanide complexes (lanthanide, Ln=Tb, Eu) was observed upon excitation of the tripodal organic ligand at 845 nm. Multiphoton absorption by the ligand followed by a transfer of energy to Ln (see picture; S=singlet state, T=triplet state) gives rise to characteristic Eu (red) or Tb (green) emission.

    28. Responsive Aligned Carbon Nanotubes (pages 4663–4666)

      Taolei Sun, Huan Liu, Wenlong Song, Xi Wang, Lei Jiang, Lin Li and Daoben Zhu

      Article first published online: 1 SEP 2004 | DOI: 10.1002/anie.200460774

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      Feeling the heat: Surface-initiated atom transfer radical polymerization was used to modify a film of aligned carbon nanotubes with poly(N-isopropylacrylamide) (see TEM image). A distinct temperature responsiveness is found for both the macroscopic (wettability) and the microscopic (the diameter and rigidity of a single carbon nanotube) properties of the resulting film.

    29. Preview: Angew. Chem. Int. Ed. 35/2004 (page 4673)

      Article first published online: 1 SEP 2004 | DOI: 10.1002/anie.200490124

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