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  • 21
    Digitale Medien
    Digitale Medien
    Formale Totalsynthese von (±)-Isocomen durch Anwendung der α-Alkinon-Cyclisierung (1986)
    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 69 (1986), S. 659-669 
    Details
    ISSN: 0018-019X
    Schlagwort(e): Chemistry ; Organic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Formal Total Synthesis of (±)-Isocomen by Application of the α-Alkinon CyclizationA total synthesis of the racemic form of the sesquiterpene isocomene (A) was accomplished by application of the cyclopentenone anellation B→D (Scheme 1) which includes the α-alkynone cyclization C→D, a gas-phase flow thermolytic process. Starting with the known product 2 (Scheme 3) of the anellation B→D, the elaboration of ring C of A proceeded in 9 steps to the α-alkynone 16 (Scheme 5) which was cyclized at 540° selectively to give the angularly fused triquinane 4 (77%). A two-step procedure then led to 5 (Scheme 6), a last but one intermediate in a known total synthesis of (±)-A. The conversion of 16 to 4 also demonstrated the compatibility of an acetoxy function with the anellation sequence B→D.
    Materialart: Digitale Medien
    URL: http://dx.doi.org/10.1002/hlca.19860690316
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  • 22
    Digitale Medien
    Digitale Medien
    Kurze Totalsynthesen von (±)-Sativen und (±)-cis-Sativendiol (1988)
    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 71 (1988), S. 788-807 
    Details
    ISSN: 0018-019X
    Schlagwort(e): Chemistry ; Organic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Short Total Syntheses of (±)-Sativene and (±)-cis-SativenediolOur approach to (±)-sativene (7) and (±)-cis-sdtivenediol (9) involves: (a) reaction of 3-methylbutanoyl chloride with Et3N/cyclopentadiene to give the endo-isopropyl-ketone 1 (here improved to 71%), (b) NBS bromination of 1 to a 5:1 mixture (87%) of the bromo-ketones 2 and 3, (c) NFD-reaction sequence initiated by the attack of 1,2-butadienyl titanate (complex of 15, obtained from 2-butine) on 2/3 to afford 52% of the brexenone derivative 4 (along with 8% of its epimer 16), (d) addition of dibromomethane to 4 forming 63% of the diene-alcohol 5 (along with 13% of the diene-carbaldehyde 38), and (e) carbenoid ring-expansion with MeLi applied to 5 resulting in 41% the diene-ketone 6 (along with 15% of a 1:3 mixture of the diene-ketones 32 and 33). Wolff-Kishner reduction of 6 led to 81% of (±)-sativene (7), when enough O2 was present, but to 97% of the diene 8 in the strict absence of O2. (±)-cis-Sativenediol (9) was obrained (86%) by OsO4 hydroxylation of 8. The brexenone derivatives 4 and 16 (6:1, 50%) were also produced when the NFD-reaction sequence was applied to the isomeric bromo-ketone mixture 13/13 (1:3). The latter was obtained by NBS bromination of 10, which in turn was available by base epimerization of 1, followed by destructive removal of unreacted 1 by repeated gas-flow thermolysis. An analogous (less convenient) route to (±)-sativene (7) passed through a series of dihydro compounds (the ene series) it started with the methylidene-ketone 36, which was the product (97%) of a partial hydrogenation of 4. Addition of dibromomethane to 36 led t 62% of the methylidene-alcohol 39 (along with a little tetracyclic ether 40). Carbenoid ring expansion of 39 with MeLi afforded ca. 42% of the methylidene-ketone 41 (along with 7% of the methylidene-ketone 43 or, under slightly different condition, along with 9% of the methylidene-ketone 42 and 10% of the methylidene-carabaldehyde 44). The methylidene-alcohol 39 and the methylidene-ketone 43 were also obtained by partial hydrogenation of 5 and 33, respectively. Wolff-Kisher reduction converted 41 into (±)-sativene (7 99%); the same conditons applied to 42 afforded only ca. 8% 7 (along with three other hydrocarbons, one of them (ca. 21%) probably being (±)-copacamphene (45)). In the diene series, the two succeeding reactions (4→5 and 5→6) competed with the same side reaction, a rearrangement leading to the brendene-aldehyde 38. In the ene series, the corresponding dihydro-by-product 44 was found in the reacton 39→41, but not during 36→39. These side reactons could largely be suppressed by keeping the reaction temperature low. An explanation is proposed.
    Zusätzliches Material: 1 Ill.
    Materialart: Digitale Medien
    URL: http://dx.doi.org/10.1002/hlca.19880710414
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  • 23
    Digitale Medien
    Digitale Medien
    Cyclobut-2-enones from Alkynes via Dichlorocyclobut-2-enonesIn part taken from the Ph.D. thesis of A.A.A., University of Zürich, 1986. (1987)
    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 70 (1987), S. 321-328 
    Details
    ISSN: 0018-019X
    Schlagwort(e): Chemistry ; Organic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The [2 + 2]-cycloaddition of dichloroketene (prepared in situ from CCl3COCl and Zn(Cu)) with three alkynes 1a-c to form 2,3-dimethyl-(2a), 2,3-diethyl-(2b) and 3-butyl-4,4-dichlorocyclobut-2-enone (2c) proceeds rapidly in the absence of POCl3. The primary products 2a-c rearrange in situ to the 2,4-dichlorocyclobut-2-enones 3a-c under the influence of ZnCL2 produced during the reaction. ZnCl2 converts both 2a and 3a into a 4:6 equilibrium mixture of the two; this isomerization does not occur with LiCl. The Cl-atoms of both 2a, b and 3a, band of 2c may reductively be removed with Zn(Cu) in AcOH/pyridine to afford the alkylcyclobutenones 4a-c. Without pyridine, this reduction gives ca. 1:1 mixtures of the double-bond isomers 4 and 5 in low yields. The cyclobutenones 2c and 4c may be deuterated by CD3COOD in the presence of pyridine. D-Atom is introduced into 2c at C(4) and at C(γ), and into 4c at C(2) and C(4). A mechanism for this deuteration is considered, which does not involve a cyclobutadienolate 7, but rather a cyclobutenolate of type 8. The reductions of 2 and 3 to 4 might also pass through the same type of intermediate 8.
    Zusätzliches Material: 1 Tab.
    Materialart: Digitale Medien
    URL: http://dx.doi.org/10.1002/hlca.19870700208
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  • 24
    Digitale Medien
    Digitale Medien
    Triaziridine 7. Mitteilung6. Mitteilung: [1].. Stabile pyramidale Konfigurationen an den Stickstoff-Atomen von Dialkyl-und Trialkyl-triaziridinen (1987)
    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 70 (1987), S. 381-389 
    Details
    ISSN: 0018-019X
    Schlagwort(e): Chemistry ; Organic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Stable Pyramidal configurations at the Nitrogen Atoms of Dialkyl-and Trialkyl-triaziridinesStereochemical features of the recently synthesized nine samples of di- and trialkyl-triaziridines, namely the 1,3-cyclopentylen-(series a) and the two stereoisomers of the diisopropyl derivatives (series b and c), containing as the third substituent an H-atom (2), a CH3 group (3)or a CH2OH group (4), were elaborated on the basis of the 1H-, 13C-, and 15N-NMR spectra. The three N-atoms of the saturated N3-homocycle were found to be stable to pyramidal inversion in all cases. According to their NMR spectra, 2-4 of the series a and b possess twofold symmetry (Cs), while 2-4 of series c are asymmetric. Thus, series c has the trans-configuration at N(2)/N(3) and, consequently, the cis-configuration at N(1)/N(2), while series a and b have the cis-configuration at N(2)/N(3) and -since the all-cis-arrangement is excluded-the trans-configuration at N(1)/N(2). The asymmetry of the trans-configurated 2c turned into twofold symmetry (C2), when a little CF3COOH was added. The 1H- and 13C-NMR data of series b and c of our alkyl-triaziridines exhibit a shielding effect, according to which there are two types of i-Pr groups, i-Pr(a) and i-Pr(b). They differ in the NMR signals of the H- and the C-atoms of their CH groups: the H-atoms of i-Pr(a) are more deshielded by 0.75-1.111 ppm and its C-atoms are more shielded by 10.0-160.0 ppm as compared to the corresponding atoms of i-Pr(b). i-Pr(a) is cis (on the N3-homocycle) to a large substituent (such as i-Pr, Me, CH2OH) and to a lone pair, while i-Pr(b)is cis only to a small (H) or to no substituent and to one or two lone pairs. An analogous effect appears in the NMR signals of the CH3 and CH2OH groups at N(1) of 3 and 4 in the series b and c.
    Zusätzliches Material: 2 Tab.
    Materialart: Digitale Medien
    URL: http://dx.doi.org/10.1002/hlca.19870700216
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  • 25
    Digitale Medien
    Digitale Medien
    Triaziridine. 6. Mitteilung5. Mitteilung: [1].. Substituententransformationen an TriaziridinenVorgetragen von H.H. an der Versammlung der Schweizerischen Chemischen Gesellschaft vom 10. Oktober 1986 in Bern. (1986)
    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 69 (1986), S. 2087-2097 
    Details
    ISSN: 0018-019X
    Schlagwort(e): Chemistry ; Organic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Substituent Transformations on TriaziridinesSeveral novel triaziridines were prepared by substituent transformations starting from the known dialkyl-triaziridine-carboxylates 1a-c, with the aim to study the influence of the substitution pattern on the properties of the triaziridine ring. The dialkyl-triaziridines 2a-c were obtained by (t-BuO-)-mediated demethylation and decarboxylation and the dialkyl-triaziridine-methanols 4a-c by LiAlH4 reduction. Further reduction of the tosylates of 4a, b with LiAlH4 gave the methyl-dialkyl-triaziridines 3a, b. The dialkyl-triaziridines 2a, c could not be N-methylated directly with CH3I, but the anions 10a, c, obtained from 2a, c with CH3Li, yielded 3a, c. N-Methylation of 2a with (CH3)3OBF4 did not afford 3a but rather the methyl-triaziridinium salt 11. The dialkyl-triaziridine 2c has pKa 〉 14, its protonated species 〈 2. A concept that the electron pairs on the triaziridine N-atoms are more strongly localized than on amine N-atoms explains (a) that the dialkyl-triaziridine 2c is hardly basic, (b) that the LiAlH4 reductions of the esters 1 stop at the stage of the methanols 4, and (c) that the methanols 4a, b do not cleave like aminomethanols.
    Materialart: Digitale Medien
    URL: http://dx.doi.org/10.1002/hlca.19860690833
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  • 26
    Digitale Medien
    Digitale Medien
    Synthesis of 4-(4′-Methyl-2′-oxo-cyclohex-3′-en-1′-yl)-pentanal and its Conversion into Derivatives of Spiro[4.5]decane and of 1,6,7,7a-Tetrahydro-2H-indene (1977)
    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 60 (1977), S. 964-974 
    Details
    ISSN: 0018-019X
    Schlagwort(e): Chemistry ; Organic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Synthese von 4-(4′-Methyl-2′-oxo-cyclohex-3′-en-1′-yl)-pentanal und dessen Umwandlung in Spiro[4.5]decan- und 1,6,7,7a-Tetrahydro-2H-inden-DerivateEs wird die Synthese von 4-(4′-Methyl-2′-oxo-cyclohex-3′-en-1′-yl)-pentanal als ein (1:1)-Gemisch von zwei Diastereoisomeren 10A und 10B auf folgendem Weg beschrieben: Die Umsetzung des Grignard-Reagens von 1,1-Äthylendioxy-3-brom-propan (2) mit 2-Methoxy-4-methyl-acetophenon (1) ergab 1,1-Äthylendioxy-4-hydroxy-4-(2′-methoxy-4′-methyl-phenyl)-pentan (3), welches sich mit methanolischer Salzsäure in 2-Methoxy-5-(2′-methoxy-4′-methyl-phenyl)-5-methyl-tetrahydrofuran (7A,B) umwandeln liess. Durch Birch-Reduktion von 7A,B wurde 4-(2′-Methoxy-4′-methyl-cyclohexa-1′,4′-dien-1′-yl)-pentan-1-ol (8), und danach durch milde Hydrolyse 4-(4′-Methyl-2′-oxo-cyclohex-3′-en-1′-yl)-pentan-1-ol (9A,B)2 erhalten. Oxydation von 9A,B lieferte schliesslich den erwähnten Keto-aldehyd 10A,B. Einige Produkte von Nebenreaktionen, nämlich 4, 5, 11, 12 und 13A,B, sind auch beschrieben.Der Keto-aldehyd 10A,B liess sich in ein Gemisch, bestehend aus drei Diastereo-isomeren A, B und C von 1-Hydroxy-4,8-dimethyl-spiro[4.5] dec-7-en-6-on (15) und aus zwei Diastereoisomeren A und B von 1,5-Dimethyl-1,6,7,7a-tetrahydro-2H-inden-3-carbaldehyd (14), umwandeln. Für diese aldolartigen Cyclisierungen wurden vier verschiedene Methoden verwendet: (a) Stehenlassen in Tetrachlorkohlenstoff-lösung, (b) Behandlung mit etwas Trifluoressigsäure in Chloroformlösung, (c) und (d) Schütteln einer Ätherlösung mit wässeriger Salzsäure oder Natronlauge. Oxydation von 15A und 15C lieferte eines der Diasteroisomeren von 4,8-Dimethyl-spiro[4.5]-dec-7-en-1,6-dion (16A), und Oxydation von 15B führte zum anderen (16B).
    Materialart: Digitale Medien
    URL: http://dx.doi.org/10.1002/hlca.19770600327
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  • 27
    Digitale Medien
    Digitale Medien
    Synthesis and Rearrangement of 7-Halobicyclo[3.2.0]hept-2-en-6-ols (1977)
    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 60 (1977), S. 1528-1544 
    Details
    ISSN: 0018-019X
    Schlagwort(e): Chemistry ; Organic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Synthese und Umlagerung von 7-Halo-bicyclo[3.2.0]hept-2-en-6-olenDie Reaktion von verschiedenen 7-halogen-substituierten Bicyclo[3.2.0]hept-2-en-6-onen mit komplexen Metallhydriden oder mit Methylmagnesiumiodid zu den entsprechenden 7-Halo-bicyclo[3.2.0]hept-2-en-6-olen verläuft unter Angriff des Nucleophils trans zum Halogen, um dem vicinalen Kohlenstoff-Halogen-Dipol auszuweichen. In Gegenwart von starken Basen unterliegen die Halohydrine einer Umlagerung, die je nach der durch die intramolekularen Wechselwirkungen bedingten Konformation, entweder unter Hydridverschiebung zu Bicyclo[3.2.0]hept-2-en-6-onen oder, unter Ringverengung, zu Bicyclo[3.1.0]hex-2-en-6-carbaldehyden führt.
    Zusätzliches Material: 1 Tab.
    Materialart: Digitale Medien
    URL: http://dx.doi.org/10.1002/hlca.19770600510
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  • 28
    Digitale Medien
    Digitale Medien
    The Synthesis of Stereoisomers of Arteannuin B (1980)
    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 63 (1980), S. 2455-2468 
    Details
    ISSN: 0018-019X
    Schlagwort(e): Chemistry ; Organic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Die Synthese von Stereoisomeren des Arteannuins BWir beschreiben die Synthese von drei rac-Diastereomeren 7A-7C des Sesquiterpenlaktons Arteannuin B (I) auf dem in den Schemata 2 und 3 zusammengefassten Weg. Als Schlüsselstufe für den Aufbau des Ringsystems 6 wurde eine intramolekulare Reformatsky-artige Reaktion verwendet, in der gleichzeitig ein Cyclohexanring und ein α-Methylidenbutyrolaktonring gebildet werden (Schritte 3 und 6). Die Cyclisierung von 5A bzw. 5B oder von 9/10 führte vorwiegend zur cis, cis-Verknüpfung der drei Ringe A/B/C, wie in 6A bzw. 6B. Daneben entstand aus 5B auch das trans, cis-System 6C. Die Verlängerung der Seitenkette in 1A,B unter Ausbildung der für die Reformatsky-artige Reaktion notwendigen Funktionalität (in 5 bzw. 9/10) wurde nach zwei Methoden ausgeführt, welche in den Schritten 1, 2 bzw. 5 beschrieben sind. Die Epoxydierung von 6A, 6B bzw. 6C zu 7A, 7B bzw. 7C (Schritt 4) war vollkommen regio- (an C(7′), C(8′)) und stereospezifisch. Die relative Konfiguration an den Zentren C(1′), C(4′), C(4a′) und C(8a′) der drei Diastereomeren A, B bzw. C von 6 und 7 wurde anhand der 1H-NMR-Spektren abgeleitet.
    Zusätzliches Material: 1 Tab.
    Materialart: Digitale Medien
    URL: http://dx.doi.org/10.1002/hlca.19800630840
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  • 29
    Digitale Medien
    Digitale Medien
    Azimine. V.Teil IV siehe [1].. Untersuchungen zur stereoisomerie an der N(2), N(3)-bindung von 2, 3-dialkyl-1-phthalimido-aziminenHerrn Prof. Dr. Conrad Hans Eugster zu seinem 60, Geburtstag gewidmet (1981)
    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 64 (1981), S. 1219-1233 
    Details
    ISSN: 0018-019X
    Schlagwort(e): Chemistry ; Organic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Azimines. V. Investigation on the Stereoisomerism Around the N (2), N (3) Bond in 2, 3-Dialkyl-1-phthalimido-azimines2, 3-(cis-1, 3-Cyclopentylene)-1-phthalimido-azimine (7) and isomerically pure (2 Z)- and (2 E)-2, 3-diisopropyl-1-phthalimido-azimine (9a and 9b) were prepared by the addition of phthalimido-nitrene (1) to 2, 3-diazabicyclo [2.2.1]hept-2-ene (6) and to (E)- and (Z)-1, 1′-dimethylazoethane (8a and 8b), respectively. Comparison of their UV. spectra with those of two stereoisomeric azimines of known configuration, namely (1 E, 2 Z)- and (1 Z, 2 E)-2, 3-dimethyl-1-phthalimido-azimine (5a and 5b), reveals that 2, 3-dialkyl-1-phthalimido-azimines with (2 Z)-configuration are characterized by a shoulder at about 258 nm (∊ ≈ 14,000) and those with (2 E)-configuration by a maximum at 270-278 nm (∊ ≈ 10,000). The (2 E)-azimine 9b isomerizes under acid catalysis as well as thermally and photochemically into the more stable (2 Z)-isomer 9a. Under the last two conditions the isomerization is accompanied by a slower fragmentation with loss of nitrogen into N, N′-diisopropyl-N, N′-phthaloylhydrazine (4, R = iso-C3H7). The same fragmentation was also observed on thermolysis and photolysis of the (2 Z)-isomer 9a. The kinetic parameters for the thermal isomerization of 9b (they fit first-order plots) and for the fragmentation of 9a and 9b were determined by 1H-NMR. spectroscopy in benzene, trichloromethane and acetonitrile. In the photolysis of 9a or 9b the fragmentation is accompanied by dissociation into the azo compounds 8a or 8b and the nitrene 1, the latter being subject to trapping by cyclohexene. With the azimine 7, an analogous thermal fragmentation was observed to give N, N′-(cis-1, 3-cyclo-pentylene)-N, N′-phthaloylhydrazine (15), but more energetic conditions were required than with 9. Photolysis of 7 led exclusively to dissociation into the azo compound 6 and the nitrene 1, perhaps because the fragmentation of 7 is prevented by ring strain.
    Zusätzliches Material: 4 Tab.
    Materialart: Digitale Medien
    URL: http://dx.doi.org/10.1002/hlca.19810640426
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  • 30
    Digitale Medien
    Digitale Medien
    Isolation of Four Hexaketides from Verticillium intertextum. Preliminary communication (1981)
    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 64 (1981), S. 1843-1846 
    Details
    ISSN: 0018-019X
    Schlagwort(e): Chemistry ; Organic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Aus dem Kulturmedium von Verticillium intertextum wurden vier Metabolite isoliert: Vertinolid (1) und Bisvertinochinol (2), beide bisher unbekannt, sowie das auch von Penicillium chrysogenum (= P. notatum) gebildete Sorbicillin (3) und das früher synthetisch hergestellte, aber noch nicht als Naturprodukt bekannte Dihydrosorbicillin (4). Hypothesen über gemeinsame Biosynthesewege werden erörtert.
    Materialart: Digitale Medien
    URL: http://dx.doi.org/10.1002/hlca.19810640616
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