Radical-Mediated C-H Functionalization: A strategy for access to modified Cyclodextrins
A simple and efficient radical C–H functionalization to access modified cyclodextrins (CDs) has been developed. The well-defined conformation of glycosidic and aglyconic bonds in α-, β-, and γ-CDs favors the intramolecular 1,8-hydrogen atom transfer (HAT) promoted by the 6I-O-yl radical, which abstracts regioselectively the hydrogen at C5II of the contiguous pyranose. The C5II-radical evolves by a polar crossover mechanism to a stable 1,3,5-trioxocane ring between two adjacent glucoses or alternatively triggers the inversion of one α-d-glucose into a 5-C-acetoxy-β-l-idose unit possessing a 1C4 conformation. The 6I,IV- and 6I,III-diols of α- and β-CDs behave similarly to the monoalcohols, forming mostly compounds originating from two 1,8-HAT consecutive processes. In the case of 6I,II-diols the proximity of the two 6-O-yl radicals in adjacent sugar units allows the formation of unique lactone rings within the CD framework via a 1,8-HAT−β-scission tandem mechanism. X-ray diffraction carried out on the crystalline 1,4-bis(trioxocane)-α-CD derivative shows a severe distortion toward a narrower elliptical shape for the primary face.
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American Chemical Society
2016-11-02
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Online Access: | http://hdl.handle.net/10261/183853 http://dx.doi.org/10.13039/100012000 http://dx.doi.org/10.13039/501100003329 http://dx.doi.org/10.13039/501100000921 |
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dig-ipna-es-10261-1838532020-05-26T04:30:51Z Radical-Mediated C-H Functionalization: A strategy for access to modified Cyclodextrins Álvarez-Dorta, Dimitri León, Elisa I. Kennedy, Alan R. Martín, Ángeles Pérez-Martín, Inés Suárez, Ernesto Fundación CajaCanarias Ministerio de Economía y Competitividad (España) European Cooperation in Science and Technology A simple and efficient radical C–H functionalization to access modified cyclodextrins (CDs) has been developed. The well-defined conformation of glycosidic and aglyconic bonds in α-, β-, and γ-CDs favors the intramolecular 1,8-hydrogen atom transfer (HAT) promoted by the 6I-O-yl radical, which abstracts regioselectively the hydrogen at C5II of the contiguous pyranose. The C5II-radical evolves by a polar crossover mechanism to a stable 1,3,5-trioxocane ring between two adjacent glucoses or alternatively triggers the inversion of one α-d-glucose into a 5-C-acetoxy-β-l-idose unit possessing a 1C4 conformation. The 6I,IV- and 6I,III-diols of α- and β-CDs behave similarly to the monoalcohols, forming mostly compounds originating from two 1,8-HAT consecutive processes. In the case of 6I,II-diols the proximity of the two 6-O-yl radicals in adjacent sugar units allows the formation of unique lactone rings within the CD framework via a 1,8-HAT−β-scission tandem mechanism. X-ray diffraction carried out on the crystalline 1,4-bis(trioxocane)-α-CD derivative shows a severe distortion toward a narrower elliptical shape for the primary face. Financial support by the Investigation Programs of the Ministerio de Economía y Competitividad (CTQ2010-18244), Fundación CajaCanarias (2015-BIO08) and the COST Action CM1201 “Biomimetic Radical Chemistry” is acknowledged. D.A.-D. thanks the Ministerio de Economía y Competitividad for a fellowship. Peer Reviewed 2019-06-12T09:37:13Z 2019-06-12T09:37:13Z 2016-11-02 2019-06-12T09:37:13Z artículo http://purl.org/coar/resource_type/c_6501 Journal of Organic Chemistry 81(23): 11766-11787 (2016) 0022-3263 http://hdl.handle.net/10261/183853 10.1021/acs.joc.6b02241 1520-6904 http://dx.doi.org/10.13039/100012000 http://dx.doi.org/10.13039/501100003329 http://dx.doi.org/10.13039/501100000921 https://doi.org/10.1021/acs.joc.6b02241 Sí open American Chemical Society |
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A simple and efficient radical C–H functionalization to access modified cyclodextrins (CDs) has been developed. The well-defined conformation of glycosidic and aglyconic bonds in α-, β-, and γ-CDs favors the intramolecular 1,8-hydrogen atom transfer (HAT) promoted by the 6I-O-yl radical, which abstracts regioselectively the hydrogen at C5II of the contiguous pyranose. The C5II-radical evolves by a polar crossover mechanism to a stable 1,3,5-trioxocane ring between two adjacent glucoses or alternatively triggers the inversion of one α-d-glucose into a 5-C-acetoxy-β-l-idose unit possessing a 1C4 conformation. The 6I,IV- and 6I,III-diols of α- and β-CDs behave similarly to the monoalcohols, forming mostly compounds originating from two 1,8-HAT consecutive processes. In the case of 6I,II-diols the proximity of the two 6-O-yl radicals in adjacent sugar units allows the formation of unique lactone rings within the CD framework via a 1,8-HAT−β-scission tandem mechanism. X-ray diffraction carried out on the crystalline 1,4-bis(trioxocane)-α-CD derivative shows a severe distortion toward a narrower elliptical shape for the primary face. |
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Fundación CajaCanarias |
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Fundación CajaCanarias Álvarez-Dorta, Dimitri León, Elisa I. Kennedy, Alan R. Martín, Ángeles Pérez-Martín, Inés Suárez, Ernesto |
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Álvarez-Dorta, Dimitri León, Elisa I. Kennedy, Alan R. Martín, Ángeles Pérez-Martín, Inés Suárez, Ernesto |
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Álvarez-Dorta, Dimitri León, Elisa I. Kennedy, Alan R. Martín, Ángeles Pérez-Martín, Inés Suárez, Ernesto Radical-Mediated C-H Functionalization: A strategy for access to modified Cyclodextrins |
author_sort |
Álvarez-Dorta, Dimitri |
title |
Radical-Mediated C-H Functionalization: A strategy for access to modified Cyclodextrins |
title_short |
Radical-Mediated C-H Functionalization: A strategy for access to modified Cyclodextrins |
title_full |
Radical-Mediated C-H Functionalization: A strategy for access to modified Cyclodextrins |
title_fullStr |
Radical-Mediated C-H Functionalization: A strategy for access to modified Cyclodextrins |
title_full_unstemmed |
Radical-Mediated C-H Functionalization: A strategy for access to modified Cyclodextrins |
title_sort |
radical-mediated c-h functionalization: a strategy for access to modified cyclodextrins |
publisher |
American Chemical Society |
publishDate |
2016-11-02 |
url |
http://hdl.handle.net/10261/183853 http://dx.doi.org/10.13039/100012000 http://dx.doi.org/10.13039/501100003329 http://dx.doi.org/10.13039/501100000921 |
work_keys_str_mv |
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_version_ |
1777669785744572416 |