Stereospecific synthesis of pyrrolidines with varied configurations via 1,3-dipolar cycloadditions to sugar-derived enones
Enantiomerically pure pyrrolidines have been obtained by 1,3-dipolar cycloaddition of stabilized azomethine ylides and sugar enones (dihydropyranones) derived from pentoses. Thus, the S-enone (menthyl 3,4-dideoxy-(1S)-pent-3-enopyranosid-2-ulose) was prepared from d-xylose, while the R analogue was...
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| Acceso en línea: | https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_00223263_v79_n11_p4992_Udry http://hdl.handle.net/20.500.12110/paper_00223263_v79_n11_p4992_Udry |
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paper:paper_00223263_v79_n11_p4992_Udry2023-06-08T14:49:36Z Stereospecific synthesis of pyrrolidines with varied configurations via 1,3-dipolar cycloadditions to sugar-derived enones Repetto, Evangelina Varela, Oscar José Amino acids Stereochemistry Stereoselectivity 1 ,3-dipolar cycloadditions 1 ,3-Dipolarcycloaddition Cycloaddition reaction Diastereo-selectivity Dipolar cycloadditions Optimized conditions Stereogenic centers Stereospecific synthesis Cycloaddition 3 formylpyridine alanine aldehyde anisaldehyde arabinose azomethine ylide benzaldehyde carbon ester glycine ketone derivative nitrogen pentose phenylalanine pyran derivative pyridine derivative pyrrolidine derivative sugar unclassified drug xylose article chemical structure cycloaddition dipole isomerization stereochemistry stereospecificity synthesis Enantiomerically pure pyrrolidines have been obtained by 1,3-dipolar cycloaddition of stabilized azomethine ylides and sugar enones (dihydropyranones) derived from pentoses. Thus, the S-enone (menthyl 3,4-dideoxy-(1S)-pent-3-enopyranosid-2-ulose) was prepared from d-xylose, while the R analogue was obtained from l-arabinose. The dipoles were generated in situ from α-arylimino esters of common amino acids (glycine, alanine, or phenylalanine) and aromatic aldehydes (benzaldehyde, 3-formylpyridine and 4-methoxybenzaldehyde). Under optimized conditions, the cycloaddition reactions were highly diastereo- and regioselective to yield, in most of the cases, a very major adduct of the 16 theoretically possible. The diastereoselectivity relies on the strict stereocontrol exerted by the stereogenic center of the pyranone. Thus, the (S)-enone, derived from d-xylose, gave tetrasubstituted pyrrolidines having a defined stereochemistry for the four stereocenters of the ring, while they had the opposite configuration when starting from the (R)-dihydropyranone. Furthermore, some endo-cycloadducts underwent isomerization of the carbons vicinal to the nitrogen atom to afford pyrrolidines with a rather unusual stereochemistry for the direct dipolar cycloadditions. © 2014 American Chemical Society. Fil:Repetto, E. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales; Argentina. Fil:Varela, O. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales; Argentina. 2014 https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_00223263_v79_n11_p4992_Udry http://hdl.handle.net/20.500.12110/paper_00223263_v79_n11_p4992_Udry |
| institution |
Universidad de Buenos Aires |
| institution_str |
I-28 |
| repository_str |
R-134 |
| collection |
Biblioteca Digital - Facultad de Ciencias Exactas y Naturales (UBA) |
| topic |
Amino acids Stereochemistry Stereoselectivity 1 ,3-dipolar cycloadditions 1 ,3-Dipolarcycloaddition Cycloaddition reaction Diastereo-selectivity Dipolar cycloadditions Optimized conditions Stereogenic centers Stereospecific synthesis Cycloaddition 3 formylpyridine alanine aldehyde anisaldehyde arabinose azomethine ylide benzaldehyde carbon ester glycine ketone derivative nitrogen pentose phenylalanine pyran derivative pyridine derivative pyrrolidine derivative sugar unclassified drug xylose article chemical structure cycloaddition dipole isomerization stereochemistry stereospecificity synthesis |
| spellingShingle |
Amino acids Stereochemistry Stereoselectivity 1 ,3-dipolar cycloadditions 1 ,3-Dipolarcycloaddition Cycloaddition reaction Diastereo-selectivity Dipolar cycloadditions Optimized conditions Stereogenic centers Stereospecific synthesis Cycloaddition 3 formylpyridine alanine aldehyde anisaldehyde arabinose azomethine ylide benzaldehyde carbon ester glycine ketone derivative nitrogen pentose phenylalanine pyran derivative pyridine derivative pyrrolidine derivative sugar unclassified drug xylose article chemical structure cycloaddition dipole isomerization stereochemistry stereospecificity synthesis Repetto, Evangelina Varela, Oscar José Stereospecific synthesis of pyrrolidines with varied configurations via 1,3-dipolar cycloadditions to sugar-derived enones |
| topic_facet |
Amino acids Stereochemistry Stereoselectivity 1 ,3-dipolar cycloadditions 1 ,3-Dipolarcycloaddition Cycloaddition reaction Diastereo-selectivity Dipolar cycloadditions Optimized conditions Stereogenic centers Stereospecific synthesis Cycloaddition 3 formylpyridine alanine aldehyde anisaldehyde arabinose azomethine ylide benzaldehyde carbon ester glycine ketone derivative nitrogen pentose phenylalanine pyran derivative pyridine derivative pyrrolidine derivative sugar unclassified drug xylose article chemical structure cycloaddition dipole isomerization stereochemistry stereospecificity synthesis |
| description |
Enantiomerically pure pyrrolidines have been obtained by 1,3-dipolar cycloaddition of stabilized azomethine ylides and sugar enones (dihydropyranones) derived from pentoses. Thus, the S-enone (menthyl 3,4-dideoxy-(1S)-pent-3-enopyranosid-2-ulose) was prepared from d-xylose, while the R analogue was obtained from l-arabinose. The dipoles were generated in situ from α-arylimino esters of common amino acids (glycine, alanine, or phenylalanine) and aromatic aldehydes (benzaldehyde, 3-formylpyridine and 4-methoxybenzaldehyde). Under optimized conditions, the cycloaddition reactions were highly diastereo- and regioselective to yield, in most of the cases, a very major adduct of the 16 theoretically possible. The diastereoselectivity relies on the strict stereocontrol exerted by the stereogenic center of the pyranone. Thus, the (S)-enone, derived from d-xylose, gave tetrasubstituted pyrrolidines having a defined stereochemistry for the four stereocenters of the ring, while they had the opposite configuration when starting from the (R)-dihydropyranone. Furthermore, some endo-cycloadducts underwent isomerization of the carbons vicinal to the nitrogen atom to afford pyrrolidines with a rather unusual stereochemistry for the direct dipolar cycloadditions. © 2014 American Chemical Society. |
| author |
Repetto, Evangelina Varela, Oscar José |
| author_facet |
Repetto, Evangelina Varela, Oscar José |
| author_sort |
Repetto, Evangelina |
| title |
Stereospecific synthesis of pyrrolidines with varied configurations via 1,3-dipolar cycloadditions to sugar-derived enones |
| title_short |
Stereospecific synthesis of pyrrolidines with varied configurations via 1,3-dipolar cycloadditions to sugar-derived enones |
| title_full |
Stereospecific synthesis of pyrrolidines with varied configurations via 1,3-dipolar cycloadditions to sugar-derived enones |
| title_fullStr |
Stereospecific synthesis of pyrrolidines with varied configurations via 1,3-dipolar cycloadditions to sugar-derived enones |
| title_full_unstemmed |
Stereospecific synthesis of pyrrolidines with varied configurations via 1,3-dipolar cycloadditions to sugar-derived enones |
| title_sort |
stereospecific synthesis of pyrrolidines with varied configurations via 1,3-dipolar cycloadditions to sugar-derived enones |
| publishDate |
2014 |
| url |
https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_00223263_v79_n11_p4992_Udry http://hdl.handle.net/20.500.12110/paper_00223263_v79_n11_p4992_Udry |
| work_keys_str_mv |
AT repettoevangelina stereospecificsynthesisofpyrrolidineswithvariedconfigurationsvia13dipolarcycloadditionstosugarderivedenones AT varelaoscarjose stereospecificsynthesisofpyrrolidineswithvariedconfigurationsvia13dipolarcycloadditionstosugarderivedenones |
| _version_ |
1768541644733284352 |