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Synthesis and transformations of some N-substituted (1R,4S)-3-aminomethylidene-1,7,7-trimethylbicyclo[2.2.1]-heptan-2-ones
Grošelj, Uroš (Author), Rečnik, Simon (Author), Meden, Anton (Author), Stanovnik, Branko (Author), Svete, Jurij (Author)

URLURL - Presentation file, Visit http://acta.chem-soc.si/53/53-3-245.pdf This link opens in a new window

Abstract
Acid-catalysed reactions of (1R,3E,4S)-3-[(dimethylamino)methylidene]-1,7,7-trimethylbicyclo[2.2.1]hept an-2 -one (2) with amino acid derivatives 3a-d and pyrazolidin-3-ones 5a-e gave the substitution products 4/4a-d and 6a-e, respectively, in 40-83% yields. Compound 4a was transformed with Bredereckćs reagent into the 3-(dimethylamino)propenoate 7/7. Treatment of 1-{[(1R,3Z,4S)-1,7,7-trimethyl-2-oxobicyclo-[2.2.1]hept-3-ylide-ne]methyl}p yrazolidin-3-ones 6a and 6b with dimethyl acetylenedicarboxylate in refluxing anisole furnished the corresponding cycloadducts as mixtures of four diastereomers, the major endo-isomers 10/11a,b and the minor exo-isomers 12/13a,b with moderate endo-selectivity. Chromatographic separation of 10/11/12/13a,b afforded the endo/exo-pairs of diastereomers, 10/13a,b and 11/12a,b. The structures of compounds 4/4, 6, 7/7, and 10/11/12/13were determined by NMR and by X-ray diffraction.

Language:English
Keywords:organska kemija, sinteza, stereoselektivne sinteze, kondenzacija, NMR spektroskopija, rentgenska strukturna analiza, rentgenska difrakcija, heterociklične spojine, heterociklični sistemi, heterocikli, kafra, enaminoni, derivati pirazola, pirazolidin-3-oni, pirazolo[1, 2-a]pirazoli, camphor, enaminones, condensations, pyrazolidin-3-ones, pyrazolo[1, 2-a]pyrazoles
Work type:Not categorized (r6)
Tipology:1.01 - Original Scientific Article
Organization:FKKT - Faculty of Chemistry and Chemical Technology
Year:2006
Publisher:Slovensko kemijsko društvo
Number of pages:str. 245-256
Numbering:Vol. 53, no. 3
UDC:547.599.6:547.77.022.057:543.442.3
ISSN on article:1318-0207
COBISS.SI-ID:27954437 Link is opened in a new window
Views:367
Downloads:174
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Record is a part of a journal

Title:Acta chimica slovenica
Shortened title:Acta chim. slov.
Publisher:Slovensko kemijsko društvo, =Slovenian Chemical Society
ISSN:1318-0207
COBISS.SI-ID:14086149 This link opens in a new window

Secondary language

Language:English
Abstract:
Pri kislinsko kataliziranih reakcijah (1R,3E,4S)-3-[(dimetilamino)metiliden]-1,7,7-trimetilbiciklo-[2.2.1]heptan- 2-on a (2) z .-aminokislinskimi derivati 3a-d in pirazolidin-3-oni 5a-e poteče izmenjava dimetilaminske skupine, ki vodi do nastanka ustreznih N-substituiranih (1R,4S)-3-aminometiliden-1,7,7-trimetilbiciklo[2.2.1]heptan-2-onov4/4a-d in 6a-e. Izmenjave dimetilaminske skupine z .-aminokislinskimi derivati 3a-d so vodile do zmesi večinskih (3E)-izomerov 4a-d in manjšinskih (3Z)-izomerov 4a-d, medtem ko so bile pretvorbe enaminona 2 s pirazolidinoni 5a-e stereoselektivne saj so nastali izključno ustrezni (3Z)-izomeri 6a-e. Pretvorba spojine 4a z bis(dimetilamino)-terc-butoksimetanom (Bredereckovim reagentom) je vodila do 3-(dimetilamino)propenoata 7/7. Izvedli smo tudi pretvorbi 1-{[(1R,3Z,4S)-1,7,7-trimetil-2-oksobiciklo[2.2.1]hept-3-iliden]metil}piraz olid in-3-onov 6a and 6b z dimetil acetilendikarboksilatom (DMAD). V obeh primerih sta nastali ustrezni zmesi štirih diastereomernih spojin, 10/11/12/13a in 10/11/12/13b, z večinskima endo-izomeroma 10 in 11 ter manjšinskima ekso-izomeroma 12 in 13. S preparativno tekočinsko kromatografijo (MPLC) smo zmesi štirih izomerov 10/11, 12/13 uspeli ločiti na dva endo/ekso-para izomerov, 10/13 in 11/12. Strukture produktov so bile potrjene z NMR spektroskopijo in z rentgensko strukturno analizo.


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