Angewandte Chemie International Edition in English

Cover image for Vol. 33 Issue 18

September 30, 1994

Volume 33, Issue 18

Pages 1789–1894

Currently known as: Angewandte Chemie International Edition

    1. Cover Picture (Angew. Chem. Int. Ed. Engl. 18/1994)

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.199417871

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      The cover picture shows a complex composed of 16 Pb2+ ions (in blue) and two 16-fold deprotonated γ-cyclodextrin tori (O atoms in red), in which each alkoxide O atom bridges two Pb atoms. An eight-point star of P2+ ions results; the diolate residues face each other, and the inner Pb2+ ions have 4 + 2 coordination. The complex is formed in the presence of a substoichiometric amount of Pb2+, which hints at a cooperative mechanism of formation. P. Klüfers and J. Schuhmacher report more on this attractive first member of a long-neglected class of compounds on p. 1863 ff.

  1. Reviews

    1. Top of page
    2. Reviews
    3. Highlights
    4. Communications
    5. Book Reviews
    1. Ligand Effects on the Chemoselectivity of Transition Metal Catalyzed Reactions of α-Diazo Carbonyl Compounds (pages 1797–1815)

      Prof. Albert Padwa and Dr. David J. Austin

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.199417971

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      Dirhodium(II) complexes, in particular, catalyze the reactions of α-diazo carbonyl compounds (e.g. 1). The rhodium(II) carbenoids formed as intermediates can undergo reactions such as cyclopropanation and insertion into C[BOND]H bonds (for instance, formation of 2 or 3; cap = caprolactamate, pfb = perfluorobutyrate). Mechanistic interpretations account for the results of the rich chemistry.

    2. Recycling in the Earth's Atmosphere: The OH Radical—Its Importance for the Chemistry of the Atmosphere and the Determination of Its Concentration (pages 1816–1826)

      Prof. Dr. Franz Josef Comes

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.199418161

      An ideal probe for testing models of the atmosphere, the OH radical is produced primarily by the photolysis of ozone. Some of its subsequent reactions are cyclic processes involving CO, CH4, and NOx, in which OH radicals are regenerated. For this reason the OH concentration is a sensitive measure of the composition of the atmosphere; however, its determination is also a significant challenge for analytical chemists.

  2. Highlights

    1. Top of page
    2. Reviews
    3. Highlights
    4. Communications
    5. Book Reviews
    1. Specific Binding of Antibodies to DNA through Combinatorial Antibody Libraries (pages 1827–1829)

      Dr. Michael Famulok and Dipl.-Chem. Dirk Faulhammer

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.199418271

      A much broader range of applications for antibody techniques should result from a new method that allows the production of a large quantity of diverse antibodies without the immunization of animals. Expression on phage surfaces is used to produce antibodies that recognize double-stranded DNA with specificity. This is but the latest demonstration of the tremendous potential of antibody methods.

    2. Subvalent Aluminum Halides as Examples of High-Temperature Species in Inorganic Syntheses (pages 1830–1832)

      Priv.-Doz. Dr. Jörg J. Schneider

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.199418301

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      Chemistry under extreme conditions makes the synthesis of 1 and 2 possible. AlBr is formed by cocondensation of Al atoms and HBr and trapped with different reagents and at different temperatures to yield the first donor-stabilized aluminum(I) and aluminum(II) halides isolable at room temperature.

    3. The Search for Selective, Neutral Anion Receptors (pages 1832–1834)

      Prof. Dr. Dieter E. Kaufmann and Dr. A. Otten

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.199418321

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      Difficult, but not impossible! Though anions are large and coordinatively saturated—and therefore slow to form adducts—they do form complexes selectively and efficiently with the novel coronands and cryptands specially tailored to be large enough and to contain ionic, Lewis acidic, or dipolar groups. These host molecules can be, for instance, modified carboranes and crown ethers or tricyclic borane–amine adducts (as in the formation of 1).

  3. Communications

    1. Top of page
    2. Reviews
    3. Highlights
    4. Communications
    5. Book Reviews
    1. First Resolution of a Free Fluorophosphane Chiral at Phosphorus (pages 1835–1837)

      Dr. Michael Pabel, Dr. Anthony C. Willis and Dr. S. Bruce Wild

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.199418351

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      Optically pure (SP)-(−)-1 ([α]math image = −210) can be liberated from a configurationally homogeneous palladium(II) complex containing the phosphane and ortho-metalated (R)-(−)-[1-(dimethylamino)-ethyljnaphthalene]. The phosphane racemizes over 6 h at 20°C without significant disproportionation.

    2. Spectroscopic Studies of Anhydroretinol, an Endogenous Mammalian and Insect retro-Retinoid (pages 1837–1839)

      Dr. Fadila Derguini, Prof. Koji Nakanishi, Dr. Jochen Buck, Dr. Ulrich Hämmerling and Dr. Felix Grün

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.199418371

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      A prevalent metabolite and antagonist of retinol, all-trans-anhydroretinol 1 is found in the liver and lung cells of mammals and in cultivated insect cell lines. This compound is particularly important owing to its reversible inhibition of the growth and proliferation of immune cells. The characterization of 1 isolated from Drosophila cell line S2M3, and several of its synthetic isomers is described.

    3. Oxygen Evolution by Oxidation of Water with Manganese Porphyrin Dimers (pages 1839–1841)

      Dr. Yoshinori Naruta, Masa-aki Sasayama and Takao Sasaki

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.199418391

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      A functional model for the tetranuclear manganese cluster in the photosystem II of higher plants and cyanobacteria is now provided by binuclear dicationic manganese complexes such as 1. In the anodic oxidation of aqueous acetonitrile containing these complexes water is oxidized to oxygen by a four-electron process. An example of Ar is 4-tBuC6H4; counterion ClOmath image.

    4. [(C6H5)4P]math image[Cu3I4]—The First Compound with a Helical Chain of Face-Sharing Tetrahedra as a Structural Element (pages 1841–1842)

      Prof. Dr. Hans Hartl and Dr. Farbod Mahdjour-Hassan-Abadi

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.199418411

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      Face-sharing tetrahedra arranged in a helix (idealized form shown below) mark the structure of the iodocuprate 1, which was obtained from Ph4PI, I2, and Cu. Five Cu positions were identified at room temperature; at lower temperatures only three (slow cooling) or four (rapid cooling) are occupied.

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    5. Asymmetric Synthesis of Biaryls by Intramolecular Oxidative Couplings of Cyanocuprate Intermediates (pages 1842–1844)

      Prof. Bruce H. Lipshutz, Dr. Frank Kayser and Dr. Zi-Ping Liu

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.199418421

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      With a judicious choice of tether from the “chiral pool”, coupling of the two aryl rings in nonracemic 1 yields only one of the two possible diastereomers of biaryl 2. G [DOUBLE BOND] C or O substituent; R, R′ [DOUBLE BOND] H, 3OMe. This method is expected to be widely applicable.

    6. The Trehalase Inhibitor Salbostatin, a Novel Metabolite from Streptomyces albus, ATCC21838 (pages 1844–1846)

      Dr. László Vértesy, Dr. Hans-Wolfram Fehlhaber and Dr. Arno Schulz

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.199418441

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      A new lead structure for the synthesis of trehalase inhibitors, salbostatin (1), is described. In one of the few systematic investigations into microorganism cultures, this pseudodisaccharide and a second metabolite 2 were isolated from the culture supernatant of a long-term fermentation. Trehalase inhibitors such as 1 are important compounds in the area of plant protection.

    7. Bis(2,4,6-tri-tert-butylphenyl)stannanediyl: A DiaryIstannylene without Donor Stabilization (pages 1846–1848)

      Prof. Dr. Manfred Weidenbruch, Dipl.-Chem. Josephin Schlaefke, Dr. Annemarie Schäfer, Dr. Karl Peters, Dr. Hans Georg von Schnering and Prof. Dr. Heinrich Marsmann

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.199418461

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      The first diarylstannylene monomeric in the solid state and not stabilized by donor ligands is 1. The dark red compound forms in good yields from Sn[N(SiMe3)2]2 and RLi (R = 2,4,6-tBu3C6H2). In solution 1 apparently isomerizes to give the sterically less encumbered stannylene RR′Sn: (R′ [DOUBLE BOND] CH2C(Me)2 −3,5-tBu2C6H3).

    8. Optically Active Lactones from a Baeyer–Villiger-Type Metal-Catalyzed Oxidation with Molecular Oxygen (pages 1848–1849)

      Prof. Dr. Carsten Bolm, Dipl.-Chem. Gunther Schlingloff and Dr. Konrad Weickhardt

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.199418481

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      Simple, mild, and enantioselective! Oxygen reacts with ketone 1 in the presence of pivalaldehyde (R [DOUBLE BOND] tBu) and a chiral copper complex (cat.*) to give lactone 2 in 47% yield and 69% ee. Other enantioselective Baeyer—Villiger-type oxidations had previously only been achieved with the help of enzymes.

    9. Unexpected Reactions of Acetylenedicarboxylates with Zirconocene Complexes (pages 1850–1852)

      Prof. Dr. Uwe Rosenthal, Dipl.-Chem. Andreas Ohff, Dr. Wolfgang Baumann, Dr. Rhett Kempe, Dr. Annegret Tillack and Dr. Vladimir V. Burlakov

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.199418501

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      An O [RIGHTWARDS ARROW] C silyl group migration is the surprising result of the reaction of the Cp2Zr precursor 1 with the bis(trimethylsilyl) acetylenedicarboxylate to give 2. In contrast, with the analogous di-tert-butyl ester, a zirconadihydrofuran forms under alkyne dimerization. The participation of CO groups should be taken into consideration in the application of the metal-locene-induced cyclization of alkenes and alkynes.

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    10. A Postulated Carrier of Gold in Hydrothermal Ore Solutions: Synthesis and Crystal Structure of [(Ph3P)2N][Au(SH)2], the First Homoleptic Hydrogensulfido Complex (pages 1852–1853)

      Prof. Dr. José Vicente, Dipl.-Chem. María-Teresa Chicote, Pablo González-Herrero, Prof. Dr. Peter G. Jones and Birte Ahrens

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.199418521

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      Not an insoluble sulfide, but the homoleptic gold complex 1, which is stable without any auxiliary ligands, is formed in the reaction of bis(acetylacetonato)gold(I) with hydrogen sulfide [Eq. (a)]. Complexes of this type are of interest as intermediates in the catalytic hydrodesulfuration of organosulfur compounds. Counterion: [(Ph3P)2N]+.

    11. Structures of 2-(Me2NCH2)C6H4-Substituted Oligosilanes (pages 1854–1855)

      Dr. Johannes Belzner, Nicola Detomi, Dipl.-Chem. Heiko Ihmels and Dr. Matthias Noltemeyer

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.199418541

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      The three-membered ring of cyclotrisilane 1 is almost undistorted. This is a result of the only moderate steric bulk of the 2-(dimethylaminomethyl)phenyl ligand, which also dictates the unexpected synperiplanar conformation of disilene 2.

    12. Asymmetric Diels—Alder Reactions Catalyzed by a Chiral Iron Lewis Acid (pages 1856–1858)

      Prof. Dr. Ernst Peter Kündig, Bernadette Bourdin and Dr. Gérald Bernardinelli

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.199418561

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      A substitute for the CO ligand in the form of an electron-poor, chiral phosphorus ligand can be used to synthesize efficient transition-metal catalysts for asymmetric Diels—Alder reactions. In the presence of 2, for example, α-bromoacrolein reacts with cyclohexadiene to form 1 in > 99% ee.

    13. Synthesis and Structure of [WOTe3]2− (pages 1859–1860)

      Donna R. Gardner, Dr. James C. Fettinger and Prof. Bryan W. Eichhorn

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.199418591

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      Three terminal tellurido ligands in one complex—this is the closest approach to homoleptic [MTe4]n ions to date. The telluridotungsten(VI) complex 1 was obtained from the reaction of [W2(O2CC3H7)4] with K2Te2. The prospects for [MTe4]n complexes are not so bad after all.

    14. Synthesis and Selective Radical Cleavage of C-4′-Modified Oligonucleotides (pages 1861–1863)

      Prof. Dr. Bernd Giese, Adrian Dussy, Dr. Cornelius Elie, Peter Erdmann and Urs Schwitter

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.199418611

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      Fragments 3 and 4 are formed selectively upon irradiation of 2 in aqueous solution. This proves that sites of DNA strand scission can be designated by incorporation of 1 in oligonucleotides.

    15. Sixteenfold Deprotonated γ-Cyclodextrin Tori as Anions in a Hexadecanuclear Lead(II) Alkoxide (pages 1863–1865)

      Prof. Dr. Peter Klüfers and Dipl.-Chem. Jörg Schuhmacher

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.199418631

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      Even in neutral, aqueous solution, carbohydrates are deprotonated in the presence of appropriate metal ions. The particularly attractive structure of 1 (right; the lines represent diolato bridges and the circle the cyclodextrin torus) illustrates this principle, which has hitherto escaped attention most probably because the initial precipitates were mistaken for the metal hydroxides.

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    16. On the Mechanism of Fullerene Formation (pages 1866–1869)

      Dipl.-Chem. Thilo Belz, Dipl.-Chem. Harald Werner, Dr. Friedrich Zemlin, Ursula Klengler, Michael Wesemann, Dr. Bernd Tesche, Prof. Dr. Elmar Zeitler, Prof. Dr. Armin Reller and Prof. Dr. Robert Schlögl

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.199418661

      A tangle of threadlike carbon polymers, which do not form two-dimensional layers, was observed in the transmission electron micrograph of the fullerene black produced in an electric arc. Curved polycyclic layer structures were also formed. Both of the suggested mechanisms for fullerene formation—via small rings, which then condense, or via macrocycles, which then isomerize—thus seem possible. Which of the two dominates depends on the reaction conditions.

    17. Synthesis of Very Highly Ordered Liquid Crystalline Phases by Complex Formation of Polyacrylic Acid with Cationic Surfactants (pages 1869–1870)

      Prof. Dr. Markus Antonietti and J. Conrad

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.199418691

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      Amphotropic interactions and favorable steric conditions result in the formation of liquid crystalline phases from complexes of polyacrylic acid with cationic surfactants. In these phases, the polymer chains are intertwined into a multichain structure (shown below). These complexes form by self-organization, and have interesting optical and mechanical properties.

    18. On the Nature of the Active Site in a CoAPO-18 Solid Acid Catalyst (pages 1871–1873)

      Prof. Sir. John Meurig Thomas, Prof. G. Neville Greaves, Dr. Gopinathan Sankar, Dr. Paul A. Wright, Dr. Jiesheng Chen, Dr. Andrew J. Dent and Dr. Leonardo Marchese

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.199418711

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      Combined in situ fluorescence X-ray absorption and X-ray diffraction have enabled the characterization of active centers of a Co-doped aluminum phosphate catalyst under near-operational conditions. Normally the characterization is carried out under rather artificial conditions, with the catalyst in either an expired (postmortem) or precursor (prenatal) state. Thus, structure A was determined for the local Co environment of the active catalyst.

    19. A Multiple Five-Membered-Ring-Selective Williamson Reaction as a Key Step in the Stereoselective Construction of 2,5-Linked Oligo(tetrahydrofuran)s (pages 1873–1875)

      Dipl.-Chem. Holger Wagner and Dr. Ulrich Koert

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.199418731

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      Four tetrahydrofuran rings in one step can be constructed with the multiple five-mem-bered-ring-selective Williamson reaction (1 [RIGHTWARDS ARROW] 2). The tetratosylate 1 is obtained from the corresponding dialkyne by a reagent-controlled, diastereoselective dihy-droxylation. This reaction sequence opens up an efficient route to enantiomerically pure oligo(tetrahydrofuran)s.

    20. [{Sb2(Ncy)4}2Cu4]: A Mixed-Metal Antimony(III)/Copper(I) Complex Containing a Cu4 Square Plane (pages 1875–1876)

      Dr. Donald Barr, Dr. Andrew J. Edwards, Samantha Pullen, Michael A. Paver, Dr. Paul R. Raithby, Moira-Ann Rennie, Christopher A. Russell and Dr. Dominic S. Wright

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.199418751

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      Polyamidoantimony anions are durable and effective ligands. as illustrated by the synthesis of 1 from 2 and CuCl. The Cu4 framework of 1 is essentially square planar. The cyclohexyl (cy) substituents have been omitted from the picture shown on the right.

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    21. CrIII and FeIII Complexes with η3-1,3,5-Triazacyclohexane Ligands (pages 1877–1878)

      Dr. Randolf D. Köhn and Dr. Gabriele Kociok-Köhn

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.199418771

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      Ring strain does not destabilize FeIII (1) and CrIII complexes with η3-bound triazacyclohexane ligands. In the CrIII complex with isopropyl substituents on the nitrogen atoms, two chloro ligands were readily exchanged for CH2SiMe3 groups. Thus, the easily accessible triazacyclohexanes may serve as sterically less demanding alternatives for triazacyclononane ligands.

    22. 5,10,15,20-Tetra-tert-butylporphyrin and Its Remarkable Reactivity in the 5- and 15-Positions (pages 1879–1881)

      Tadashi Ema, Dr. Mathias O. Senge, Nora Y. Nelson, Prof. Dr. Hisanobu Ogoshi and Prof. Dr. Kevin M. Smith

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.199418791

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      Owing to the steric bulk of the tert-butyl groups, the reactivity of the novel porphyrin 1, which has a nonplanar macrocyclic framework, deviates distinctly from that of any other known porphyrin. For example, prolonged treatment of 1 in HClO4/MeOH leads to formation of 5,15-dihydroporphyrin (“porphodi-methene”) 2.

    23. [{Rh2Cpmath image(μ-CH2)2}2(μ-S4)]2+: A Novel Tetranuclear Cationic Complex with a Rectangular S4 Unit (pages 1882–1883)

      Prof. Kiyoshi Isobe, Dr. Yoshiki Ozawa, Prof. Amelio Vázquez de Miguel, Prof. Tian-Wei Zhu, Prof. Kui-Ming Zhao, Takanori Nishioka, Dr. Takashi Ogura and Prof. Teizo Kitagawa

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.199418821

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      A novel centrosymmetric chairlike conformation of the central Rh4S4 framework (shown on the right) is present in the title compound. The D2h-symmetric S4 ligand shows the bonding characteristics of cyclobutadiene, but its structure resembles that calculated for the free neutral S4 molecule. This ligand is stabilized by the two Rh[BOND]Rh bonds.

    24. Electron Delocalization in Ethynyl-Bridged Binuclear Ruthenium(II) Polypyridine Complexes (pages 1884–1885)

      Dr. Andrew C. Benniston, Vincent Grosshenny, Prof. Anthony Harriman and Dr. Raymond Ziessel

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.199418841

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      The triplet lifetimes of the ethynyl-bridged binuclear RuII complexes 1 (m = 0, 1; n = 1, 2) are significantly longer than that of the parent mononuclear complex, despite much lower triplet energies. This effect, which arises from electron delocalization over an extended π* orbital, decreases upon removal of the second RuII cation or if phenyl rings are incorporated into the π-electron system. Counterion: PFmath image.

    25. A Model for α-Keto Acid Dependent Nonheme Iron Enzymes: Structure and Reactivity of [Femath image(Me2hdp)2(bf)](ClO4) (pages 1886–1888)

      Yu-Min Chiou and Prof. Lawrence Que Jr.

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.199418861

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      The bis(μ-phenolato)diiron(II) complex 1 is a model compound for nonheme iron enzymes that use α-keto acids as cofactors. Complex 1 undergoes immediate oxidative decarboxylation upon exposure to dioxygen at a rate which is three to four orders of magnitude faster than those observed for other compounds of this type. The formula of the ligand is given under that of 1.

    26. Catalytic Enantioselective Protonation of Enolates (pages 1888–1889)

      Dr. Charles Fehr and José Galindo

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.199418881

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      “A textbook example for stereoselective synthesis”—that is how one of the referees described the title reaction. With only 0.2 equivalents of a chiral proton donor, prochiral enolates such as 1 are protonated to give 2.

  4. Book Reviews

    1. Top of page
    2. Reviews
    3. Highlights
    4. Communications
    5. Book Reviews