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  • Organic Chemistry  (4)
  • (Tetrahydrofuran)[tris(trimethylsilyl)cyclopentadienyl]lithium, X-ray crystal structure  (1)
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  • 1
    ISSN: 0947-3440
    Schlagwort(e): Amino alcohols ; Chiral auxiliaries ; Diastereoselective Grignard reactions ; Proline analogues ; Homogenous catalysis ; Chemistry ; Organic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: New, chiral β-sec-amino alcohols (αR,βR)-11a-13a, (αS,βR)-11b-17b, (αS,βS)-11c, 12c, 15c, 17c and (αR,βS)-11d, 12d, 15d, 17d have been synthesized from the enantiomerically pure amine (all-R)-1a via diastereomeric, N-tert-butoxycarbonyl-protected aldehydes 3. Grignard additions proceed in fair yields with a high degree of diastereofacial stereoselection (diastereomeric ratios dr up to ≥ 95:5) with non-chelation control, generally in favor of the anti-(erythro) structures. A mechanistic interpretation of the stereochemical course of this reaction is presented. The stereodifferentiating ability of selected stereoisomeric (erythro)- and (threo)-amino alcohol structures were tested in homogeneous catalysis, e.g. in two model reactions (optical purities up to 95%).
    Zusätzliches Material: 2 Ill.
    Materialart: Digitale Medien
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  • 2
    ISSN: 0947-3440
    Schlagwort(e): β-Amino alcohols ; Organophosphorus compounds ; Methoxyphosphane borane complexes ; Enantioselective borane reduction ; Chemistry ; Organic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: New, chiral 1,3,2-oxazaphospholidine-borane complexes 3a-b and 8a-d were synthesized from the β-amino alcohols 1a-b and 6a-d. The borane complexes 3, 8a, 8c, and 8d were allowed to react with different organolithium compounds and afforded the corresponding aminophosphane-borane complexes 4a-c and 9a-g. Acid methanolysis of those complexes led to the formation of the phosphinite-borane complexes 5a-c. This is a further example of the utilization of the industrial waste material (all-R)-2-azabicyclo-[3.3.0]octane-3-carboxylic acid. The catalytic efficiency of the chiral 1,3,2-oxazaphospholidine-borane complexes 3a, 3b, and 8c was examined in the enantioselective borane reduction of some ketones.
    Materialart: Digitale Medien
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  • 3
    ISSN: 0947-3440
    Schlagwort(e): Amino alcohols ; Bicyclic pyrrolidine and piperidine derivatives ; Diastereoselective ring expansion ; Chiral auxiliaries ; Waste prevention ; Chemistry ; Organic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: New, chiral bicyclic 3-hydroxypiperidines (4S)-2a-e are synthesized from the β-amino alcohols (3R)-1a-e. In an one-step reaction (4S)-2a-e are obtained by a high diastereoselective ring expansion (dr ≥ 95:5). As well, the amino alcohol (3S)-1a leads to the corresponding rearranged epimer bicyclic piperidine derivative (4R)-2a (dr ≥ 95:5). Thus, it is possible to clarify the influence of the three stereogenic centers of the parent compound regarding the diastereoselectivity of the ring expansion. After oxidation of the tert-amino sec-alcohol (4S)-2a to the corresponding α-amino ketone 4, new 3-hydroxypiperidines (4Ξ)-5a, b12 and (4RS)-6 are obtained by a diastereoselective Grignard addition. Furthermore, the achiral and the chiral reduction of 4 to the β-amino alcohols (4S)-2a and (4R)-2a is described. These are further examples of the utilization of industrial waste material (all-R)-2-azabicyclo[3.3.0]octane-3-carboxylic acid (all-R)-3.
    Zusätzliches Material: 4 Tab.
    Materialart: Digitale Medien
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  • 4
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 122 (1989), S. 1449-1456 
    ISSN: 0009-2940
    Schlagwort(e): [Tris(trimethylsilyl)cyclopentadienyl]lithium complexes ; [Bis(trimethylsilyl)cyclopentadienyl]lithium complexes ; (Di-tert-butylcyclopentadienyl)lithium complexes ; Pentagonal-pyramidal cyclopentadienyllithium complexes ; (Tetrahydrofuran)[tris(trimethylsilyl)cyclopentadienyl]lithium, X-ray crystal structure ; Chemistry ; Inorganic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Beschreibung / Inhaltsverzeichnis: Synthesis and Structure of Lithium Complexes with Pentahapto-Bonded, Substituted Cyclopentadienyl LigandsThe reaction of [tris(trimethylsilyl)cyclopentadienyl]lithium, [bis(trimethylsilyl)cyclopentadienyl]lithium, and (di-tert-butylcyclopentadienyl)lithium with Lewis bases (ethers, amines, thioethers) leads to the crystalline, air-and moisture-sensitive adducts 1a-k, 2a-c, and 3a-c, which are monomeric in the solid state, in solution, and in the gas phase. The cyclopentadienyl ligand is pentahapto-bonded to the lithium atom. In the case of [tris(trimethylsilyl)cyclopentadienyl]lithium the use of monodentate ethers results in the isolation of complexes (1a-d, 1h, 1i) with an unusual coordination of the lithium ion. Thus, the crystal structure analysis of (tetrahydrofuran)[tris(trimethylsilyl)cyclopentadienyl]-lithium, [(Me3Si)3C5H2]Li · THF (1b), shows a nearly linear arrangement between the oxygen atom of the THF molecule, the lithium atom, and the ring centroid of the cyclopentadienyl ligand (Li—O = 187 pm; Li—Cp centroid = 180 pm).
    Notizen: Die Umsetzung von [Tris(trimethylsilyl)cyclopentadienyl]lithium, [Bis(trimethylsilyl)cyclopentadienyl]lithium und (Di-tert-butylcyclopentadienyl)lithium mit Lewis-Basen (Ether, Amine, Thioether) führt zu kristallinen, sehr luft- und feuchtigkeitsempfindlichen Addukten 1a-k, 2a-c und 3a-c, die im Festkörper, in Lösung und in der Gasphase monomer vorliegen. Der Cyclopentadienylligand ist jeweils pentahapto an das Lithiumatom gebunden. Im Fall von [Tris(trimethylsilyl)cyclopentadienyl]lithium gelingt bei Verwendung von einzähnigen Ethern die Isolierung von Komplexen (1a-d, 1h, 1i) mit ungewöhnlicher Koordination des Lithum-Ions. So zeigt die Röntgenstrukturanalyse von (Tetrahydrofuran)[tris(trimethylsilyl)cyclopentadienyl]lithium, [(Me3Si)3C5H2]Li·THF (1b), eine nahezu lineare Anordnung zwischen dem Sauerstoffatom aus dem THF-Molekül, dem Lithiumatom und dem Ringzentrum des Cyclopentadienylliganden (Li—O = 187 pm; Li—Cp-Zentrum = 180 pm).
    Zusätzliches Material: 1 Ill.
    Materialart: Digitale Medien
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  • 5
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Liebigs Annalen 1991 (1991), S. 305-310 
    ISSN: 0170-2041
    Schlagwort(e): Phosphonates, 4-thiazolidine- ; Amidoalkylation, Michaelis-Arbusov-type ; Chemistry ; Organic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Synthesis and Stereochemistry of Dimethyl 4-ThiazolidinylphosphonatesDimethyl phosphite adds to the azomethine bond of 2,5-dihydrothiazoles 1 to produce dimethyl 4-thiazolidinylphosphonates 2. Depending on the reaction conditions diastereomeric mixtures 2 are formed and explained by a two-step mechanism. Assignment of configurations is proved by an X-ray structure analysis of the thermodynamically more stable stereoisomer of 2c. N-Acylated derivatives 5 could not be obtained by direct acylation of 2 but by a TiCl4-catalyzed Michaelis-Arbusov-type reaction of trimethyl phosphite with N-acyl-4-methoxythiazolidines 3. Phosphonates 5 are formed with high diastereoselectivity.
    Zusätzliches Material: 1 Ill.
    Materialart: Digitale Medien
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