Regioselectivity of glycosylation reactions of galactose acceptors: an experimental and theoretical study
Regioselective glycosylations allow planning simpler strategies for the synthesis of oligosaccharides, and thus reducing the need of using protecting groups. With the idea of gaining further understanding of such regioselectivity, we analyzed the relative reactivity of the OH-3 and OH-4 groups of 2,...
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| Format: | Article |
| Language: | English |
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Beilstein-Institut
2019-12-01
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| Series: | Beilstein Journal of Organic Chemistry |
| Subjects: | |
| Online Access: | https://doi.org/10.3762/bjoc.15.294 |
| _version_ | 1824033621562884096 |
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| author | Enrique A. Del Vigo Carlos A. Stortz Carla Marino |
| author_facet | Enrique A. Del Vigo Carlos A. Stortz Carla Marino |
| author_sort | Enrique A. Del Vigo |
| collection | DOAJ |
| description | Regioselective glycosylations allow planning simpler strategies for the synthesis of oligosaccharides, and thus reducing the need of using protecting groups. With the idea of gaining further understanding of such regioselectivity, we analyzed the relative reactivity of the OH-3 and OH-4 groups of 2,6-diprotected methyl α- and β-galactopyranoside derivatives in glycosylation reactions. The glycosyl acceptors were efficiently prepared by simple methodologies, and glycosyl donors with different reactivities were assessed. High regioselectivities were achieved in favor of the 1→3 products due to the equatorial orientation of the OH-3 group. A molecular modeling approach endorsed this general trend of favoring O-3 substitution, although it showed some failures to explain subtler factors governing the difference in regioselectivity between some of the acceptors. However, the Galp-(β1→3)-Galp linkage could be regioselectively installed by using some of the acceptors assayed herein. |
| first_indexed | 2024-12-22T06:59:12Z |
| format | Article |
| id | doaj.art-9b0c98710ff144b7825efc31a4175c9e |
| institution | Directory Open Access Journal |
| issn | 1860-5397 |
| language | English |
| last_indexed | 2024-12-22T06:59:12Z |
| publishDate | 2019-12-01 |
| publisher | Beilstein-Institut |
| record_format | Article |
| series | Beilstein Journal of Organic Chemistry |
| spelling | doaj.art-9b0c98710ff144b7825efc31a4175c9e2022-12-21T18:34:51ZengBeilstein-InstitutBeilstein Journal of Organic Chemistry1860-53972019-12-011512982298910.3762/bjoc.15.2941860-5397-15-294Regioselectivity of glycosylation reactions of galactose acceptors: an experimental and theoretical studyEnrique A. Del Vigo0Carlos A. Stortz1Carla Marino2Universidad de Buenos Aires, Facultad de Ciencias Exactas y Naturales, Consejo Nacional de Investigaciones Científicas y Técnicas, Centro de Investigaciones en Hidratos de Carbono (CIHIDECAR), Departamento de Química Orgánica, Pab. 2, Ciudad Universitaria, 1428 Buenos Aires, ArgentinaUniversidad de Buenos Aires, Facultad de Ciencias Exactas y Naturales, Consejo Nacional de Investigaciones Científicas y Técnicas, Centro de Investigaciones en Hidratos de Carbono (CIHIDECAR), Departamento de Química Orgánica, Pab. 2, Ciudad Universitaria, 1428 Buenos Aires, ArgentinaUniversidad de Buenos Aires, Facultad de Ciencias Exactas y Naturales, Consejo Nacional de Investigaciones Científicas y Técnicas, Centro de Investigaciones en Hidratos de Carbono (CIHIDECAR), Departamento de Química Orgánica, Pab. 2, Ciudad Universitaria, 1428 Buenos Aires, ArgentinaRegioselective glycosylations allow planning simpler strategies for the synthesis of oligosaccharides, and thus reducing the need of using protecting groups. With the idea of gaining further understanding of such regioselectivity, we analyzed the relative reactivity of the OH-3 and OH-4 groups of 2,6-diprotected methyl α- and β-galactopyranoside derivatives in glycosylation reactions. The glycosyl acceptors were efficiently prepared by simple methodologies, and glycosyl donors with different reactivities were assessed. High regioselectivities were achieved in favor of the 1→3 products due to the equatorial orientation of the OH-3 group. A molecular modeling approach endorsed this general trend of favoring O-3 substitution, although it showed some failures to explain subtler factors governing the difference in regioselectivity between some of the acceptors. However, the Galp-(β1→3)-Galp linkage could be regioselectively installed by using some of the acceptors assayed herein.https://doi.org/10.3762/bjoc.15.294fukui indexesgalactopyranosyl acceptorsgalactose donorsmolecular modelingregioselectivity |
| spellingShingle | Enrique A. Del Vigo Carlos A. Stortz Carla Marino Regioselectivity of glycosylation reactions of galactose acceptors: an experimental and theoretical study Beilstein Journal of Organic Chemistry fukui indexes galactopyranosyl acceptors galactose donors molecular modeling regioselectivity |
| title | Regioselectivity of glycosylation reactions of galactose acceptors: an experimental and theoretical study |
| title_full | Regioselectivity of glycosylation reactions of galactose acceptors: an experimental and theoretical study |
| title_fullStr | Regioselectivity of glycosylation reactions of galactose acceptors: an experimental and theoretical study |
| title_full_unstemmed | Regioselectivity of glycosylation reactions of galactose acceptors: an experimental and theoretical study |
| title_short | Regioselectivity of glycosylation reactions of galactose acceptors: an experimental and theoretical study |
| title_sort | regioselectivity of glycosylation reactions of galactose acceptors an experimental and theoretical study |
| topic | fukui indexes galactopyranosyl acceptors galactose donors molecular modeling regioselectivity |
| url | https://doi.org/10.3762/bjoc.15.294 |
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