Reductive decarboxylation of bicyclic prolinic systems: a new approach to the enantioselective synthesis of the Geissman-Waiss lactone. X-ray structure determination of a key lactone intermediate
Two concise and enantioselective syntheses of the necine base precursors (1R,5R)-N-Cbz and N-Boc-2-oxa-6-azabicyclo[3.3.0]octan-3-ones (Geissman-Waiss lactones) were carried out from two enantiomerically pure endocyclic five-membered enecarbamates with overall yields of 23% and 26%, respectively. Th...
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| Format: | Article |
| Language: | English |
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Sociedade Brasileira de Química
2003-01-01
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| Series: | Journal of the Brazilian Chemical Society |
| Subjects: | |
| Online Access: | http://www.scielo.br/scielo.php?script=sci_arttext&pid=S0103-50532003000100006 |
| _version_ | 1819241655379689472 |
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| author | Ambrósio João Carlos L. Santos Regina Helena de A. Correia Carlos R. D. |
| author_facet | Ambrósio João Carlos L. Santos Regina Helena de A. Correia Carlos R. D. |
| author_sort | Ambrósio João Carlos L. |
| collection | DOAJ |
| description | Two concise and enantioselective syntheses of the necine base precursors (1R,5R)-N-Cbz and N-Boc-2-oxa-6-azabicyclo[3.3.0]octan-3-ones (Geissman-Waiss lactones) were carried out from two enantiomerically pure endocyclic five-membered enecarbamates with overall yields of 23% and 26%, respectively. The synthetic strategy made use of a highly effective and stereoselective [2+2]cycloaddition of enantiomerically pure endocyclic enecarbamates with dichloroketene, as well as an efficient decarboxylation step of a bicyclic alpha-amino acid employing Boger's acyl selenide protocol employing tributyltin hydride. Interesting aspects concerning the regiochemical outcome of Baeyer-Villiger oxidations of bicyclic cyclobutanones are also reported, in which the usual stereoelectronic bias of Baeyer-Villiger oxidation seems to be counterbalanced by steric effects on the putative Criegee intermediate. |
| first_indexed | 2024-12-23T14:27:22Z |
| format | Article |
| id | doaj.art-e8972c969afa45aeb1571b9ee3380fa1 |
| institution | Directory Open Access Journal |
| issn | 0103-5053 |
| language | English |
| last_indexed | 2024-12-23T14:27:22Z |
| publishDate | 2003-01-01 |
| publisher | Sociedade Brasileira de Química |
| record_format | Article |
| series | Journal of the Brazilian Chemical Society |
| spelling | doaj.art-e8972c969afa45aeb1571b9ee3380fa12022-12-21T17:43:38ZengSociedade Brasileira de QuímicaJournal of the Brazilian Chemical Society0103-50532003-01-011412738Reductive decarboxylation of bicyclic prolinic systems: a new approach to the enantioselective synthesis of the Geissman-Waiss lactone. X-ray structure determination of a key lactone intermediateAmbrósio João Carlos L.Santos Regina Helena de A.Correia Carlos R. D.Two concise and enantioselective syntheses of the necine base precursors (1R,5R)-N-Cbz and N-Boc-2-oxa-6-azabicyclo[3.3.0]octan-3-ones (Geissman-Waiss lactones) were carried out from two enantiomerically pure endocyclic five-membered enecarbamates with overall yields of 23% and 26%, respectively. The synthetic strategy made use of a highly effective and stereoselective [2+2]cycloaddition of enantiomerically pure endocyclic enecarbamates with dichloroketene, as well as an efficient decarboxylation step of a bicyclic alpha-amino acid employing Boger's acyl selenide protocol employing tributyltin hydride. Interesting aspects concerning the regiochemical outcome of Baeyer-Villiger oxidations of bicyclic cyclobutanones are also reported, in which the usual stereoelectronic bias of Baeyer-Villiger oxidation seems to be counterbalanced by steric effects on the putative Criegee intermediate.http://www.scielo.br/scielo.php?script=sci_arttext&pid=S0103-50532003000100006Geissman-Waiss lactone[2+2]cycloadditionsdecarboxylationpyrrolizidine alkaloids |
| spellingShingle | Ambrósio João Carlos L. Santos Regina Helena de A. Correia Carlos R. D. Reductive decarboxylation of bicyclic prolinic systems: a new approach to the enantioselective synthesis of the Geissman-Waiss lactone. X-ray structure determination of a key lactone intermediate Journal of the Brazilian Chemical Society Geissman-Waiss lactone [2+2]cycloadditions decarboxylation pyrrolizidine alkaloids |
| title | Reductive decarboxylation of bicyclic prolinic systems: a new approach to the enantioselective synthesis of the Geissman-Waiss lactone. X-ray structure determination of a key lactone intermediate |
| title_full | Reductive decarboxylation of bicyclic prolinic systems: a new approach to the enantioselective synthesis of the Geissman-Waiss lactone. X-ray structure determination of a key lactone intermediate |
| title_fullStr | Reductive decarboxylation of bicyclic prolinic systems: a new approach to the enantioselective synthesis of the Geissman-Waiss lactone. X-ray structure determination of a key lactone intermediate |
| title_full_unstemmed | Reductive decarboxylation of bicyclic prolinic systems: a new approach to the enantioselective synthesis of the Geissman-Waiss lactone. X-ray structure determination of a key lactone intermediate |
| title_short | Reductive decarboxylation of bicyclic prolinic systems: a new approach to the enantioselective synthesis of the Geissman-Waiss lactone. X-ray structure determination of a key lactone intermediate |
| title_sort | reductive decarboxylation of bicyclic prolinic systems a new approach to the enantioselective synthesis of the geissman waiss lactone x ray structure determination of a key lactone intermediate |
| topic | Geissman-Waiss lactone [2+2]cycloadditions decarboxylation pyrrolizidine alkaloids |
| url | http://www.scielo.br/scielo.php?script=sci_arttext&pid=S0103-50532003000100006 |
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