A New Synthetic Approach to the Carbocyclic Core of Cyclopentane-Type Glycosidase Inhibitors: Asymmetric Synthesis of Aminocyclopentitols via Free Radical Cycloisomerization of Enantiomerically Pure Alkyne- Tethered Oxime Ethers Derived from Carbohydrates

9 páginas, 7 esquemas.-- Supporting Information Available: Experimental procedures and 1H and 13C NMR spectra for compounds 21b, 21c, 22,25a 26-29, 35-44 (13 pages).

Detalhes bibliográficos
Autores: Marco-Contelles, José, Destabel, Christine, Gallego, Pilar, Chiara, José Luis, Bernabé, Manuel
Formato: artículo
Fecha de publicación:1996
País:España
Recursos:Consejo Superior de Investigaciones Científicas (CSIC)
Repositorio:DIGITAL.CSIC. Repositorio Institucional del CSIC
OAI Identifier:oai:digital.csic.es:10261/30924
Acesso em linha:http://hdl.handle.net/10261/30924
Access Level:acceso abierto
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spelling A New Synthetic Approach to the Carbocyclic Core of Cyclopentane-Type Glycosidase Inhibitors: Asymmetric Synthesis of Aminocyclopentitols via Free Radical Cycloisomerization of Enantiomerically Pure Alkyne- Tethered Oxime Ethers Derived from CarbohydratesMarco-Contelles, JoséDestabel, ChristineGallego, PilarChiara, José LuisBernabé, Manuel9 páginas, 7 esquemas.-- Supporting Information Available: Experimental procedures and 1H and 13C NMR spectra for compounds 21b, 21c, 22,25a 26-29, 35-44 (13 pages).The synthesis of compounds 6-8, derived from 2,3:5,6-bis-O-isopropylidene-d-mannofuranose (3), and the preparation of products 16 and 17, obtained from 2,3-O-isopropylidene-d-ribose (13) is reported. The first free radical cyclization of enantiomerically pure alkyne-tethered oxime ethers derived from carbohydrates (6, 8, 16, and 17) is described. These radical precursors have been submitted to cyclization with tributyl or triphenyltin hydride plus triethylborane to yield, after ring closure, the aminocyclopentitols 9−12 and 18−20, respectively. These carbocycles have been obtained as mixtures of Z and E vinyltin isomers, but with excellent diastereoselection at the new stereocenter formed during the ring closure. After protodestannylation, only one diastereoisomer was detected and isolated. The absolute configuration at the new stereocenter formed during the carbocyclization has been established by detailed 1H NMR analysis. The specific transformation of compound 19 (or 20) into aminocyclitol 24 is described. Compound 24 is an analogue of the aminocyclopentitol moiety of trehazolin (1a), a known and powerful glycosidase inhibitor of trehalase. From these results, we can conclude that a new method for the asymmetric synthesis of aminocyclitols of biological interest is now available.The authors thank DGICYT (SAF94-0818-C02-02), CICYT (CE93- 0023), Comunidad Autónoma de Madrid-Consejería de Educación y Cultura-(AE-0094/94), and EU (Human Capital and Mobility; Contract no. ERBCHRXCT 92- 0027) for generous financial support.Peer reviewedAmerican Chemical Society201120111996info:eu-repo/semantics/articlehttp://purl.org/coar/resource_type/c_6501http://hdl.handle.net/10261/30924reponame:DIGITAL.CSIC. Repositorio Institucional del CSICinstname:Consejo Superior de Investigaciones Científicas (CSIC)Ingléshttp://dx.doi.org/10.1021/jo951891info:eu-repo/semantics/openAccessoai:digital.csic.es:10261/309242026-05-22T06:33:51Z
dc.title.none.fl_str_mv A New Synthetic Approach to the Carbocyclic Core of Cyclopentane-Type Glycosidase Inhibitors: Asymmetric Synthesis of Aminocyclopentitols via Free Radical Cycloisomerization of Enantiomerically Pure Alkyne- Tethered Oxime Ethers Derived from Carbohydrates
title A New Synthetic Approach to the Carbocyclic Core of Cyclopentane-Type Glycosidase Inhibitors: Asymmetric Synthesis of Aminocyclopentitols via Free Radical Cycloisomerization of Enantiomerically Pure Alkyne- Tethered Oxime Ethers Derived from Carbohydrates
spellingShingle A New Synthetic Approach to the Carbocyclic Core of Cyclopentane-Type Glycosidase Inhibitors: Asymmetric Synthesis of Aminocyclopentitols via Free Radical Cycloisomerization of Enantiomerically Pure Alkyne- Tethered Oxime Ethers Derived from Carbohydrates
Marco-Contelles, José
title_short A New Synthetic Approach to the Carbocyclic Core of Cyclopentane-Type Glycosidase Inhibitors: Asymmetric Synthesis of Aminocyclopentitols via Free Radical Cycloisomerization of Enantiomerically Pure Alkyne- Tethered Oxime Ethers Derived from Carbohydrates
title_full A New Synthetic Approach to the Carbocyclic Core of Cyclopentane-Type Glycosidase Inhibitors: Asymmetric Synthesis of Aminocyclopentitols via Free Radical Cycloisomerization of Enantiomerically Pure Alkyne- Tethered Oxime Ethers Derived from Carbohydrates
title_fullStr A New Synthetic Approach to the Carbocyclic Core of Cyclopentane-Type Glycosidase Inhibitors: Asymmetric Synthesis of Aminocyclopentitols via Free Radical Cycloisomerization of Enantiomerically Pure Alkyne- Tethered Oxime Ethers Derived from Carbohydrates
title_full_unstemmed A New Synthetic Approach to the Carbocyclic Core of Cyclopentane-Type Glycosidase Inhibitors: Asymmetric Synthesis of Aminocyclopentitols via Free Radical Cycloisomerization of Enantiomerically Pure Alkyne- Tethered Oxime Ethers Derived from Carbohydrates
title_sort A New Synthetic Approach to the Carbocyclic Core of Cyclopentane-Type Glycosidase Inhibitors: Asymmetric Synthesis of Aminocyclopentitols via Free Radical Cycloisomerization of Enantiomerically Pure Alkyne- Tethered Oxime Ethers Derived from Carbohydrates
dc.creator.none.fl_str_mv Marco-Contelles, José
Destabel, Christine
Gallego, Pilar
Chiara, José Luis
Bernabé, Manuel
author Marco-Contelles, José
author_facet Marco-Contelles, José
Destabel, Christine
Gallego, Pilar
Chiara, José Luis
Bernabé, Manuel
author_role author
author2 Destabel, Christine
Gallego, Pilar
Chiara, José Luis
Bernabé, Manuel
author2_role author
author
author
author
description 9 páginas, 7 esquemas.-- Supporting Information Available: Experimental procedures and 1H and 13C NMR spectra for compounds 21b, 21c, 22,25a 26-29, 35-44 (13 pages).
publishDate 1996
dc.date.none.fl_str_mv 1996
2011
2011
dc.type.none.fl_str_mv info:eu-repo/semantics/article
http://purl.org/coar/resource_type/c_6501
format article
dc.identifier.none.fl_str_mv http://hdl.handle.net/10261/30924
url http://hdl.handle.net/10261/30924
dc.language.none.fl_str_mv Inglés
language_invalid_str_mv Inglés
dc.relation.none.fl_str_mv http://dx.doi.org/10.1021/jo951891
dc.rights.none.fl_str_mv info:eu-repo/semantics/openAccess
eu_rights_str_mv openAccess
dc.publisher.none.fl_str_mv American Chemical Society
publisher.none.fl_str_mv American Chemical Society
dc.source.none.fl_str_mv reponame:DIGITAL.CSIC. Repositorio Institucional del CSIC
instname:Consejo Superior de Investigaciones Científicas (CSIC)
instname_str Consejo Superior de Investigaciones Científicas (CSIC)
reponame_str DIGITAL.CSIC. Repositorio Institucional del CSIC
collection DIGITAL.CSIC. Repositorio Institucional del CSIC
repository.name.fl_str_mv
repository.mail.fl_str_mv
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score 15,811543

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