Angewandte Chemie International Edition

Cover image for Vol. 44 Issue 47

December 2, 2005

Volume 44, Issue 47

Pages 7649–7809

    1. Cover Picture: Ruthenium-Catalyzed Asymmetric Propargylic Substitution Reactions of Propargylic Alcohols with Acetone (Angew. Chem. Int. Ed. 47/2005) (page 7649)

      Youichi Inada, Yoshiaki Nishibayashi and Sakae Uemura

      Version of Record online: 28 NOV 2005 | DOI: 10.1002/anie.200590156

      Diruthenium complexes with optically active thiolate-bridged ligands promote the catalytic propargylic substitution of propargylic alcohols with acetone as the nucleophile. The use of novel chiral ligands bearing a phenyl ring that can engage in a π–π interaction with a phenyl ring of the ruthenium–allenylidene moiety lead to high enantioselectivities in these processes. For more details, see the Communication by Y. Nishibayashi and co-workers on page 7715 ff.

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      Highly Diastereoselective Alkylation of Aziridine-2-carboxylate Esters: Enantioselective Synthesis of LFA-1 Antagonist BIRT-377 (page 7661)

      Aniruddha P. Patwardhan, V. Reddy Pulgam, Yu Zhang and William D. Wulff

      Version of Record online: 28 NOV 2005 | DOI: 10.1002/anie.200590158

      This article corrects:
    3. All the Rave in Microwaves (pages 7666–7669)

      C. Oliver Kappe and Mats Larhed

      Version of Record online: 28 NOV 2005 | DOI: 10.1002/anie.200503543

    4. Stephacidin B, The Avrainvillamide Dimer: A Formidable Synthetic Challenge (pages 7670–7673)

      Carmen Escolano

      Version of Record online: 27 OCT 2005 | DOI: 10.1002/anie.200502383

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      Rising to the challenge: Stephacidin B is an antitumor antibiotic isolated from the fungi Aspergillus ochraceus (see picture). Recently, two elegant approaches to the enantioselective synthesis of this dimeric N-hydroxyindole alkaloid were reported that pave the way to a series of medicinally attractive stephacidin analogues.

    5. Organosulfur Compounds: Electrophilic Reagents in Transition-Metal-Catalyzed Carbon–Carbon Bond-Forming Reactions (pages 7674–7684)

      Srinivas Reddy Dubbaka and Pierre Vogel

      Version of Record online: 15 NOV 2005 | DOI: 10.1002/anie.200463007

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      Inexpensive and easily prepared organosulfur compounds, such as sulfonyl chlorides, thiol esters, thioethers, sulfonium ions, sulfoxides, sulfoximines, sulfones, sulfonates and sulfonamides, are good electrophilic partners in C[BOND]C cross-coupling reactions and arylations catalyzed by transition metals (see scheme).

    6. Soft Nanotechnology with Soft Nanoparticles (pages 7686–7708)

      Satish Nayak and L. Andrew Lyon

      Version of Record online: 11 NOV 2005 | DOI: 10.1002/anie.200501321

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      A swell idea: Research on hydrogel nanoparticles confirms the huge application potential of soft nanomaterials. Such nanoparticles can be made to swell and contract in response to changes in their environment. They could find uses as bioresponsive sensors, drug-delivery systems, implantable biomaterials, biotesting, and targetable chemotherapy agents. The picture shows HeLa cells containing core–shell nanoparticles as fluorescent markers.

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      Lithium Alkoxide {Li4O4} Cubanes Bridged by Rhodium–Quinonoid Organometalloligands (pages 7710–7715)

      Seung Uk Son, Jeffrey A. Reingold, Sang Bok Kim, Gene B. Carpenter and Dwight A. Sweigart

      Version of Record online: 8 NOV 2005 | DOI: 10.1002/anie.200503050

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      Joining the cubes: The linking of lithium {Li4O4} cubanes by the bifunctional organometalloligand [(η4-quinone)Rh(cod)] (cod=cyclooctadiene) results in an unprecedented doubly bridged motif. The dimeric assembly features cubane units that are connected by a transition-metal complex and that incorporate a quinone oxygen atom at one of the corners.

    8. Ruthenium-Catalyzed Asymmetric Propargylic Substitution Reactions of Propargylic Alcohols with Acetone (pages 7715–7717)

      Youichi Inada, Yoshiaki Nishibayashi and Sakae Uemura

      Version of Record online: 27 OCT 2005 | DOI: 10.1002/anie.200502981

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      Enantioselective propargylic substitution reactions of propargylic alcohols with acetone catalyzed by a diruthenium complex gives the propargylic alkylated products in good yields with up to 82 % ee. A π–π interaction of phenyl rings between the ligand and allenylidene moieties is considered to play a crucial role in achieving such a high selectivity (see scheme; Cp*=pentamethylcyclopentadiene).

      Corrected by:

      Corrigendum: Ruthenium-Catalyzed Asymmetric Propargylic Substitution Reactions of Propargylic Alcohols with Acetone

      Vol. 45, Issue 4, 533, Version of Record online: 11 JAN 2006

    9. Oxindole Synthesis through Intramolecular Nucleophilic Addition of Vinylpalladiums to Aryl Isocyanates (pages 7718–7721)

      Shin Kamijo, Yuya Sasaki, Chikashi Kanazawa, Thomas Schüßeler and Yoshinori Yamamoto

      Version of Record online: 8 NOV 2005 | DOI: 10.1002/anie.200502252

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      Ringing the changes for organopalladium catalysts. A new nucleophilic reactivity of organopalladium species has been revealed. The reaction between aryl isocyanates and terminal alkynes in the presence of a palladium catalyst produces oxindoles through the intramolecular vinylpalladation of isocyanates (see scheme; dppe=1,2-bis(diphenylphosphanyl)ethane).

    10. Tetraphenylborate as a Novel Bridging Ligand in a Zwitterionic Nickel(I) Dimer (pages 7721–7725)

      Yaofeng Chen, Christine Sui-Seng and Davit Zargarian

      Version of Record online: 8 NOV 2005 | DOI: 10.1002/anie.200502905

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      An uncommon interaction characterizes the NiI–NiI zwitterionic complex presented here. The μ-Ph moiety of the tetraphenylborate ligand coordinates synfacially to the two Ni centers (see picture) and provides two pairs of electrons through an η2(C2,C3):η2(C5,C6) interaction that is strengthened as a result of the electrostatic attractions between the anion and the formally cationic Ni2 fragment.

    11. Thiooligosaccharide Conjugate Vaccines Evoke Antibodies Specific for Native Antigens (pages 7725–7729)

      David R. Bundle, Jamie R. Rich, Sandra Jacques, Henry N. Yu, Mark Nitz and Chang-Chun Ling

      Version of Record online: 8 NOV 2005 | DOI: 10.1002/anie.200502179

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      When S is SO much better: Conjugate vaccines that contain S-glycosides induce carbohydrate-specific antibodies that cross react with the corresponding O-glycosides and vice versa. Four distinct systems have been examined, in each of which the antigen-specific response to S-glycosides is either comparable or superior to the response to O-glycosides.

    12. Tl2[Aryl2P4]: A Thallium Complexed Diaryltetraphosphabutadienediide and its Two-Electron Oxidation to a Diaryltetraphosphabicyclobutane, Aryl2P4 (pages 7729–7733)

      Alexander R. Fox, Robert J. Wright, Eric Rivard and Philip P. Power

      Version of Record online: 9 NOV 2005 | DOI: 10.1002/anie.200502865

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      An analogue with P: Reaction of the “dithallene” (TlArmath image)2 (1; Armath image=C6H3-2,6-(C6H2-2,6-iPr2)2) with P4 afforded Tl2[P4(Armath image)2] (2), a thallium complexed diaryltetraphosphabutadienediide. The negative charge in the anion of 2 is delocalized over the P4 array to afford an average P[BOND]P bond order of approximately 1.33.

    13. Ba8CoNb6O24: A d0 Dielectric Oxide Host Containing Ordered d7 Cation Layers 1.88 nm Apart (pages 7733–7736)

      Phillip M. Mallinson, Mathieu M. B. Allix, John B. Claridge, Richard M. Ibberson, David M. Iddles, Tim Price and Matthew J. Rosseinsky

      Version of Record online: 7 NOV 2005 | DOI: 10.1002/anie.200500135

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      Following orders: The cobalt and niobium ions in Ba8CoNb6O24 are completely ordered in the seven-layer repeat of hexagonal and cubic stacking. Such site-ordered solids may find application as microwave dielectric resonators, for example, in mobile telecommunications. In the structure shown, {CoO6} and {NbO6} units are red and blue octahedra, respectively, and barium cations are black spheres.

    14. Staggered to Eclipsed Conformational Rearrangement of [Co2(CO)6(PPh3)2] in the Solid State: An X-ray Diffraction Study at High Pressure and Low Temperature (pages 7736–7739)

      Nicola Casati, Piero Macchi and Angelo Sironi

      Version of Record online: 9 NOV 2005 | DOI: 10.1002/anie.200502241

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      Under pressure: characterization of the high-pressure phase of crystalline [Co2(CO)6(PPh3)2] has provided the first structural evidence for the transformation from a staggered to eclipsed arrangement of the equatorial carbonyl ligands in a dimeric transition-metal complex (see picture). A comparison with the same phenomenon observed at low temperature (though arrested in the very early stages) is presented.

    15. The Effects of Triplet Sensitizers' Energies on the Photoreactivity of β,γ-Unsaturated Methyl Ketones (pages 7739–7741)

      Diego Armesto, Maria J. Ortiz, Antonia R. Agarrabeitia and Noureddin El-Boulifi

      Version of Record online: 3 NOV 2005 | DOI: 10.1002/anie.200502619

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      Triplet determines reactivity: β,γ-Unsaturated ketones 1 do not undergo the oxa-di-π-methane (ODPM) rearrangement in the presence of acetophenone or 3-methoxyacetophenone as a triplet sensitizer. However, they afford the ODPM products 2 when using triplet sensitizers with triplet energies slightly higher than those of the alkene triplets. When the triplet energies of the sensitizers are slightly lower than those of the alkene groups in 1, ODPM rearrangement occurs along with 1,3-acyl migration to form enones 3 (see scheme).

    16. [MnIII(salen)]6[FeIII(bpmb)(CN)2]6⋅7 H2O: A Cyanide-Bridged Nanosized Molecular Wheel (pages 7742–7745)

      Zhong-Hai Ni, Hui-Zhong Kou, Li-Fang Zhang, Chunhua Ge, Ai-Li Cui, Ru-Ji Wang, Yadong Li and Osamu Sato

      Version of Record online: 3 NOV 2005 | DOI: 10.1002/anie.200502699

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      Heterometallic wheel: A cyanide-bridged heterometallic dodecanuclear complex featuring a nanosized molecular wheel has been synthesized based on magnetically anisotropic [Mn(salen)]+ and [Fe(bpmb)(CN)2] building blocks. Magnetic studies reveal that the complex exhibits overall ferromagnetic intramolecular coupling (see picture) and frequency-dependent ac magnetic susceptibility. H2bpmb=1,2-bis(pyridine-2-carboxamido)-4-methylbenzene.

    17. Characterization of a Complex Comprising a {Cu2(S2)2}2+ Core: Bis(μ-S22−)dicopper(III) or Bis(μ-S2.)dicopper(II)? (pages 7745–7748)

      John T. York, Eric C. Brown and William B. Tolman

      Version of Record online: 3 NOV 2005 | DOI: 10.1002/anie.200503134

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      Cores for thought: Structural and spectroscopic studies show that the {Cu2(S2)2}2+ core of [Cu2(tmeda)2(μ-S2)2](OTf)2 (tmeda=N,N,N′,N′-tetramethylethylenediamine; OTf=trifluoromethanesulfonate) is best described as a bis(μ-disulfido(.1−))dicopper(II) complex rather than a bis(μ-disulfido(2−))dicopper(III) complex. This complex represents a new motif in the copper–sulfur chemistry of biologically relevant, synthetic model systems.

    18. Structural Transition and Tuning of tert-Butylamine Hydrate (pages 7749–7752)

      Do-Youn Kim, Jong-won Lee, Yu-Taek Seo, John A. Ripmeester and Huen Lee

      Version of Record online: 27 OCT 2005 | DOI: 10.1002/anie.200502376

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      An unconventional hydrate promoter, tBuNH2 , forms a double hydrate upon reacting with CH4 (see picture). This double hydrate shows different storage capacities for CH4 depending on the concentration of tBuNH2. Based on this phenomenon, a tuning concept for determining the optimum initial concentration of tBuNH2 is proposed.

    19. Nucleobases in Molecular Recognition: Molecular Adducts of Adenine and Cytosine with COOH Functional Groups (pages 7752–7757)

      Sathyanarayana Reddy Perumalla, E. Suresh and Venkateswara Rao Pedireddi

      Version of Record online: 7 NOV 2005 | DOI: 10.1002/anie.200502434

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      Covering the bases: Nucleobases and aromatic carboxylic acids possessing complementary functional groups have been used in the synthesis of molecular adducts with exotic architectures. The architectures obtained with cytosine as the nucleobase lead to the production of several different supramolecular structures (see picture).

    20. Porous Capsules Allow Pore Opening and Closing That Results in Cation Uptake (pages 7757–7761)

      Achim Müller, Liviu Toma, Hartmut Bögge, Christian Schäffer and Anja Stammler

      Version of Record online: 8 NOV 2005 | DOI: 10.1002/anie.200502202

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      Popping corks: The protonated urea ions (C black, N/O green) that cork the pores of a polyoxomolybdate capsule (Mo blue, O red) can be reversibly removed allowing the entry of Ca2+ ions (pink) into the capsule. This process resembles the functioning of gated calcium channels in cell membranes.

    21. Enantiospecific Chemisorption of Small Molecules on Intrinsically Chiral Cu Surfaces (pages 7761–7764)

      Bhawna Bhatia and David S. Sholl

      Version of Record online: 9 NOV 2005 | DOI: 10.1002/anie.200501655

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      Stepping up: Density functional calculations indicate that small molecules, such as propylene oxide, chemisorb in an enantiospecific manner on intrinsically chiral, stepped Cu surfaces. As an example, the preferential adsorption configurations for the (S)- (right) and (R)-amino(fluoro)methoxy species (left) on Cu(874)S are shown.

    22. Tailoring the Active Site of Chemzymes by Using a Chemogenetic-Optimization Procedure: Towards Substrate-Specific Artificial Hydrogenases Based on the Biotin–Avidin Technology (pages 7764–7767)

      Gérard Klein, Nicolas Humbert, Julieta Gradinaru, Anita Ivanova, François Gilardoni, Untung E. Rusbandi and Thomas R. Ward

      Version of Record online: 8 NOV 2005 | DOI: 10.1002/anie.200502000

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      The combination of chemical- with genetic-optimization strategies (i.e. chemogenetic) allows the production of artificial hydrogenases based on the biotin–avidin technology. In the spirit of enzymes, second-coordination-sphere interactions between the host protein (streptavidin) and the substrate (an olefin) allow fine-tuning of the selectivity to produce either R or S hydrogenation products.

    23. Decoration of Microspheres with Gold Nanodots—Giving Colloidal Spheres Valences (pages 7767–7770)

      Gang Zhang, Dayang Wang and Helmuth Möhwald

      Version of Record online: 8 NOV 2005 | DOI: 10.1002/anie.200502117

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      Giving directions: Microspheres are decorated with a defined number of Au nanodots by using O2-plasma-etched colloidal crystals as masks for the deposition of Au vapor (see picture). The Au nanodots deposited on the spheres might be considered as nanoscale analogues of sp-hybridized atomic orbitals, which may be used to spatially direct the association of spheres to generate hierarchical “supraparticles”.

    24. Finely Tuning Metallic Nanogap Size with Electrodeposition by Utilizing High-Frequency Impedance in Feedback (pages 7771–7775)

      Quan Qing, Fang Chen, Peigang Li, Weihua Tang, Zhongyun Wu and Zhongfan Liu

      Version of Record online: 3 NOV 2005 | DOI: 10.1002/anie.200502680

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      Positive feedback: Relatively large gaps can be reproducibly fabricated by utilizing the change in impedance arising from the high electric field between the electrodes in a feedback-controlled electrodeposition system. Furthermore, the gap size can be finely tuned down to around 1 nm by simply controlling subsequent deposition time (see SEM images).

    25. Side-Chain Orientation and Hydrogen-Bonding Imprint Supra-τc Motion on the Protein Backbone of Ubiquitin (pages 7776–7778)

      Nils A. Lakomek, Christophe Farès, Stefan Becker, Teresa Carlomagno, Jens Meiler and Christian Griesinger

      Version of Record online: 8 NOV 2005 | DOI: 10.1002/anie.200502573

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      Order parameters derived from residual dipolar couplings between NH groups reveal motion of protein backbones on a time scale slower than the correlation time τC. Less-mobile amides (blue and green) in ubiquitin, for example, are H-bonded and belong to residues with side chains pointing towards the hydrophobic core while more mobile ones (yellow, orange, and red) have solvent-exposed side chains and fewer H bonds.

    26. Photochemical Regulation of DNA-Binding Specificity of MyoD (pages 7778–7782)

      Lucia Guerrero, Oliver S. Smart, Chris J. Weston, Darcy C. Burns, G. Andrew Woolley and Rudolf K. Allemann

      Version of Record online: 9 NOV 2005 | DOI: 10.1002/anie.200502666

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      Lighting up: The conformation of the DNA-binding domain of the basic helix-loop-helix protein MyoD can be controlled through an azobenzene cross-linker in response to light flashes. The DNA binding specificity of alkylated MyoD can be modulated through the isomerization of the cross-linker to the cis conformer, which leads to significantly enhanced sequence selectivity.

    27. Molecular Mechanism of the Solid-State Fluorescence Behavior of the Organic Pigment Yellow 101 and Its Derivatives (pages 7783–7786)

      Andreas Dreuw, Jürgen Plötner, Lisa Lorenz, Josef Wachtveitl, Juste E. Djanhan, Jürgen Brüning, Thomas Metz, Michael Bolte and Martin U. Schmidt

      Version of Record online: 28 NOV 2005 | DOI: 10.1002/anie.200501781

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      Close and yet fluorescent: Derivatives of Pigment Yellow 101 can exhibit small intermolecular distances in the solid-state crystal structures. Nevertheless, these compounds show strong solid-state fluorescence. X-ray structure determinations and elaborate quantum-chemical calculations indicate that the unexpected fluorescence is a property of the individual molecules which is retained in the crystal. (Excited state energies are plotted along a CNN bending mode.)

    28. (Pr4N)4[Ag3Fe2(ECN)12]—Anionic Network Structures with Mutual Interpenetration (pages 7787–7790)

      Stefan Gerber, Henriette Gröger, Jürgen Ensling, Philipp Gütlich and Harald Krautscheid

      Version of Record online: 4 NOV 2005 | DOI: 10.1002/anie.200502287

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      Ambidextrous ligands satisfy both Ag and Fe. The three-dimensional polymeric ions [Ag3Fe2(ECN)12]4− (E=S, Se) form networks in which {Fe(1,3-μ-NCE)2Ag} units are linked to form 80-membered {Fe10Ag10}(ECNC)20 rings. The mixed-valent compound (Pr4N)4[Ag3Fe2(SeCN)12] is the first crystallographically characterized homoleptic selenocyanato complex of iron.

    29. A Triazadiphosphole (pages 7790–7793)

      Sebastian Herler, Peter Mayer, Jörn Schmedt auf der Günne, Axel Schulz, Alexander Villinger and Jan J. Weigand

      Version of Record online: 31 OCT 2005 | DOI: 10.1002/anie.200502475

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      Two GaCl3adducts of 4-bis(trimethylsilyl)amino-1,2,4,3,5-triazadiphosphole were formed in simple high-yielding reactions. The adducts were fully characterized (see structure of the monoadduct) and shown to be stable at ambient temperature. The structure, bonding, and NMR spectra of the triazadiphosphole adducts are discussed on the basis of MO, NBO, and DFT calculations.

    30. Intramolecular Hydroamination of Functionalized Alkenes and Alkynes with a Homogenous Zinc Catalyst (pages 7794–7798)

      Agustino Zulys, Maximilian Dochnahl, Dirk Hollmann, Karolin Löhnwitz, Jost-Steffen Herrmann, Peter W. Roesky and Siegfried Blechert

      Version of Record online: 4 NOV 2005 | DOI: 10.1002/anie.200502006

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      Simple and versatile: A new zinc complex catalyzes the intramolecular hydroamination of nonactivated alkynes and alkenes (see example in scheme; {(iPr)2ATI}=N-isopropyl-2-(isopropylamino)troponiminato). The catalyst is relatively robust, exhibits excellent activities, and tolerates various functional groups such as ethers, thioethers, and amides.

    31. Can Acetylenedithiolate Act as a Tetradentate Bridging Ligand? (pages 7798–7800)

      Wolfram W. Seidel, Markus Schaffrath and Tania Pape

      Version of Record online: 4 NOV 2005 | DOI: 10.1002/anie.200502489

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      Tetradentate and ambidentate: Because the four-atom acetylenedithiolate has donor electron density on all sides of the dianion, it can link and electronically couple different metal ions. The bend-back angles of the sulfur atoms in the η2-C,C′-acetylenedithiolate complex [Tp′W(CO)22-C2S2)] are sufficiently flexible to allow for a chelation of both sulfur donors to the {(η5-C5H5)Ru(PPh3)} fragment (see structure).

    32. Direct Conversion of Linoleic Acid over Silver Catalysts in the Presence of H2: An Unusual Way towards Conjugated Linoleic Acids (pages 7800–7804)

      Markus Kreich and Peter Claus

      Version of Record online: 28 NOV 2005 | DOI: 10.1002/anie.200501852

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      A silver lining: The isomerization of conjugated double bonds over silver catalysts in the presence of hydrogen are unusual and hitherto unknown. Silver catalysts control the selectivity of the extremely difficult isomerization of linoleic acid towards the physiologically important 9-cis,11-trans- and 10-trans,12-cis-unsaturated isomers, which are anticarcinogenic and antiarteriosclerotic agents (see scheme, CLA=conjugated linoleic acids).

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