Library

X
feed icon rss

Your email was sent successfully. Check your inbox.

An error occurred while sending the email. Please try again.

Proceed reservation?

Export
  • 1
    Electronic Resource
    Electronic Resource
    (-)-(M,7S)-Colchicine and (-)-(M,7S)-10-Ethylthiocolchicide/Alkyne Cycloaddition Reactions: Synthesis of Novel Colchicine Derivatives by Consecutive [4+2] and [3+2] Cycloadditions (1998)
    Weinheim : Wiley-Blackwell
    Liebigs Annalen 1998 (1998), S. 2451-2460 
    Details
    ISSN: 1434-193X
    Keywords: Colchicine ; 10-Ethylthiocolchicide, diene properties of ; π-Facial diastereoselectivity ; Consecutive [4+2],[3+2] cycloadditions ; Atropisomerism ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Cycloaddition reactions of the facially dissymmetric diene moiety of (-)-(M,7S)-colchicine (5) and (-)-(M,7S)-10-ethylthiocolchicide (9) to various alkynes have been studied. With 5 and the dienophilic benzyne (3), dimethyl acetylenedicarboxylate (DMAD) (4) and cyclooctyne (6) as starting materials all cycloadditions could be realized with high regioselectivity at the 8,12-positions of the alkaloid. The approach of the dienophiles preferentially occurred toward the syn π-face of the diene. In contrast to the cycloaddition mode of 5 the ethylthiocolchicide 9 surprisingly reacted in a different manner. With benzyne as starting material a novel [3+2] cycloaddition of the thioenol ether moiety of 9 towards the dipolarophilic benzyne is supposed, affording the unexpected colchicide 10 after [1,5]H shift of the primarily formed cycloadduct followed by cleavage of the C-S linkage. With DMAD (4) and cyclooctyne (6) the reaction course is more complex. In a consecutive [4+2]/[3+2] cycloaddition (or vice versa) followed by a thermally induced cycloreversion of a not identified intermediate DMAD (4) gives rise to the polycyclic thiophene derivative 13 and the novel allocolchicinoid 14. In a similar way cyclooctyne (6) yielded three products, the thiophene-annulated homobarrelenones 18 and 19 and the tetracyclic allocolchicinoid 21. The structures of the novel colchicine derivatives were assigned on the basis of spectral data, those of the cycloadducts 1 and 19 were verified by X-ray crystallography. For the unprecedented formation of the various allocolchicinoids by consecutive [4+2]/[3+2] cycloadditions plausible reaction pathways are suggested, as far as possible. In addition the inhibitory effects on the tubulin polymerization reaction in vitro of 10, 14, and 21 are reported.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
    BibTip Others were also interested in ...
    Paper (German National Licenses)
  • 2
    Electronic Resource
    Electronic Resource
    [4+ + 2] Cycloadditions with an N-Methyl-4H-pyrazolium cation as electron-deficient diazadiene systemDedicated to Prof. Dr. Hans Möhrle on the occasion of his 65th birthday. (1995)
    Weinheim : Wiley-Blackwell
    Liebigs Annalen 1995 (1995), S. 1313-1318 
    Details
    ISSN: 0947-3440
    Keywords: 4H-Pyrazole synthesis ; Dimethoxycarbene ; Diels-Alder reactions, „inverse“ ; Isopyrazolium ketal cations ; Phthalazinecarboxylates ; Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: 3,6-Diphenyl-1,2,4,5-tetrazine (6) reacts with dimethoxycarbene (7), generated from the 1,3,4-oxadiazoline 8, to yield the 4H-pyrazole 10. This is alkylated to the N-methyl-4H-pyrazolium tetrafluoroborate 12 in high yield. The alkylated, cationic azine system of 12 serves as electron-deficient diene in a [4+ + 2] cycloaddition with inverse electron demand and reacts diastereoselectively with several cyclic olefins as electron-rich dienophiles. The initially formed cationic [4+ + 2] adduct, e.g. 15, is unstable and rearranges probably via 16 to a racemic phthalazinecarboxylic ester of type 17. The crystal structures of the epoxyphthalazinecarboxylic ester 25 and of the trans-annulated cycloocta[d]pyridazine 27 were determined by X-ray diffraction. In contrast to the cyclic olefins, cyclooctyne (28) reacts with the pyrazolium cation 12 to yield the cyclooctapyridiazinium tetrafluoroborate 30 via the cycloadduct 29.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/jlac.1995199507174
    Library Location Call Number Volume/Issue/Year Availability
    BibTip Others were also interested in ...
    Paper (German National Licenses)
    Fulltext
  • 3
    Electronic Resource
    Electronic Resource
    Positional and Facial Selectivity in Diels-Alder Reactions of (-)-(aS,7S)-Colchicine: Synthesis of Novel Analogues of the Alkaloid (1997)
    Weinheim : Wiley-Blackwell
    Liebigs Annalen 1997 (1997), S. 851-857 
    Details
    ISSN: 0947-3440
    Keywords: Colchicine, diene properties of ; Positional selectivity ; Stabilized exciplex through hydrogen bonding ; π-Facial diastereoselectivity ; Photooxygenation ; Solvent effects ; Cycloadditions ; Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Positional and facial selectivity in Diels-Alder reactions of several hetero- and carbodienophiles with (-)-(aS,7S)-colchicine (1) has been examined. In all cases, cycloaddition occurred with high positional selectivity at the 8,12-positions of the alkaloid and preferentially from the diene face syn to the allylic substituent at the stereogenic center C-7. The observed high π-facial diastereoselectivity is independent of the polarity of the solvent used and is therefore probably a consequence of steric factors. The structures of the Diels Alder-adducts of 1 with singlet oxygen, N-phenyl-1,2,4-triazolinedione (PTAD) and trans-cyclooctene, 4,5, and 15, respectively, were assigned on the basis of spectral data and verified by X-ray crystallography.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/jlac.199719970510
    Library Location Call Number Volume/Issue/Year Availability
    BibTip Others were also interested in ...
    Paper (German National Licenses)
    Fulltext
  • 4
    Electronic Resource
    Electronic Resource
    Pericyclic Domino reactions with 3,6-Bis(trifluoromethyl)-1,2,4,5-tetrazine: A convenient entry into azo cage compounds (1997)
    New York, NY : Wiley-Blackwell
    Journal für Praktische Chemie/Chemiker-Zeitung 339 (1997), S. 623-632 
    Details
    ISSN: 0941-1216
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: 3,6-Bis(trifluoromethyl)-1,2,4,5-tetrazine (1) characterized by a highly reactive, electron deficient diazdiene system reacted with several cyclic and acyclic bis-dienophiles to yield the cage compounds 11, 19a, b, 31a, b and 41 in a pericyclic homo-domino reaction in good yields. The first step of the domino reactions is an inverse electron demand inter-molecular Diels-Alder addition followed by elimination of nitrogen to give 4,5-dihydropyridazines which then undergo a terminal ring closure to yield the cage compounds. The solvent employed and the reaction temperature is of crucial importance. Whereas in nitromethane and at elevated temperatures the main products are the cage compounds, at lower temperature and in dichloromethane as solvent the initially formed 4,5-dihydropyridazines are frequently converted to 1,4-dihydropyridazines by a 1,3-H-shift. Treatment of the tetrazine 1 with cyclooctatriene 23 did not lead to a cage compound in any case; instead via valence tautomeric species octa-1,3,5,7-tetraene 23a and bicyclo[4.2.0]octa-2,4-diene 23b the twofold pyridazine-substituted butadienes 24 and 26 together with the tricyclic cyclobuta[f]phthalazine 25 were formed.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/prac.199733901111
    Library Location Call Number Volume/Issue/Year Availability
    BibTip Others were also interested in ...
    Paper (German National Licenses)
    Fulltext
  • 5
    Electronic Resource
    Electronic Resource
    Dihydrocolchicine 8,12-Endoperoxide: A Novel Starting Material for Convenient Syntheses of the Allocolchicinoids N-Acetylcolchinol O-Methyl Ether and Androbiphenyline (1997)
    Weinheim : Wiley-Blackwell
    Liebigs Annalen 1997 (1997), S. 2275-2279 
    Details
    ISSN: 0947-3440
    Keywords: Semisynthetic colchicine analogues ; Endoperoxide transformations ; Colchicine-allocolchicine rearrangement ; Axial chirality ; Biaryls ; Alkaloids ; Colchicum autumnale ; Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Optically pure dihydrocolchicine-8,12-endoperoxide 2 is used as the starting material for the synthesis of some bioactive allocolchicinoids. Depending on the reaction conditions and reagents employed, different modifications of the C ring of colchicine (1) are achieved. Triphenylphosphane deoxygenation of 2 leads to the well known N-acetylcolchinol O-methyl ether (NCME, 6, 40% yield from 1). Treatment of the endoperoxide 2 with CH3OH/CH2Cl2/silica gel provides the plant alkaloid androbiphenyline (11) in a yield of 60% from 1. Triethylamine-catalysed transformation of 2 yields (-)-colchicine-8,12-dione (12) (17% yield), together with a mixture of interconverting tetracyclic hemiketals 8a and 8b. For the formation of the allo colchicinoids 6 and 11 plausible reaction pathways are suggested. In contrast to what is found in the literature, the assignment of the absolute configuration of natural (-)-colchicine (1), and the allo-congeners 6 and 11, should be (M,7S) or (aR,7S) instead of (aS,7S).
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/jlac.199719971115
    Library Location Call Number Volume/Issue/Year Availability
    BibTip Others were also interested in ...
    Paper (German National Licenses)
    Fulltext
  • 6
    Electronic Resource
    Electronic Resource
    A Novel Cycloocta[d]-/Barreleno[d]pyridazine RearrangementDedicated to Prof. Dr. Dr. h.c. F. Eiden on the occasion of his 70th birthday. (1995)
    Weinheim : Wiley-Blackwell
    Liebigs Annalen 1995 (1995), S. 661-666 
    Details
    ISSN: 0947-3440
    Keywords: Cyclooctatetraene-bicyclooctatriene valence tautomerism ; [4+2] Cycloadditions, inverse ; Cycloocta[d]pyridazine ⇛ barreleno[d]pyridazine rearrangement ; [1, 3]-Carbon migration ; Catalysis, 1,3-tautomerization with 2-hydroxypyridine ; Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: As part of the valence tautomeric system cyclooctatetraene (2) bicyclo[4.2.0]octa-2,4,7-triene (3), the monocyclic polyene (2) reacts as a dienophile with the diazadiene 3,6-bis(trifluoromethyl)-1,2,4,5-tetrazine (1) to form after N2-elimination two products: The 1 : 1-adduct 6, a cycloocta[d]pyridazine, and the tetracyclic bis-Diels-Alder cycloadduct 9. Depending on solvent polarity and temperature, compound 6 displays interesting novel rearrangements. On refluxing in nonpolar solvents like toluene, compound 6 yields the barreleno[d]pyridazine 13 in high yield. Compound 13 can be oxidized with 4-phenyltriazolinedione 14 to the barreleno[d]pyridazine 15. When the more polar nitromethane is used as a solvent, heating of 6 at 90° 2°C surprisingly leads to the dihydrocycloocta[d]pyridazine 18 in a multistep reaction including proton-shift tautomerism and [1, 5]-sigmatropic rearrangement. The structures of the compounds 15 and 18 were assigned by the spectral data and verified by X-ray crystallography.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/jlac.199519950493
    Library Location Call Number Volume/Issue/Year Availability
    BibTip Others were also interested in ...
    Paper (German National Licenses)
    Fulltext
Close ⊗
This website uses cookies and the analysis tool Matomo. More information can be found here...