From Hamamelitannin Synthesis to the Study of Enzymatic Acylations of D-Hamamelose
The bioactive natural substance, hamamelitannin, was effectively synthesized in two ways. The chemical acylation of 2,3-<i>O</i>-isopropylidene-α,β-D-hamamelofuranose promoted by Bu<sub>2</sub>SnO using 3,4,5-tri-<i>O</i>-acetylgalloyl chloride, followed by the de...
| Main Authors: | , |
|---|---|
| Format: | Article |
| Language: | English |
| Published: |
MDPI AG
2023-03-01
|
| Series: | Biomolecules |
| Subjects: | |
| Online Access: | https://www.mdpi.com/2218-273X/13/3/519 |
| _version_ | 1797613225977577472 |
|---|---|
| author | Mária Mastihubová Vladimír Mastihuba |
| author_facet | Mária Mastihubová Vladimír Mastihuba |
| author_sort | Mária Mastihubová |
| collection | DOAJ |
| description | The bioactive natural substance, hamamelitannin, was effectively synthesized in two ways. The chemical acylation of 2,3-<i>O</i>-isopropylidene-α,β-D-hamamelofuranose promoted by Bu<sub>2</sub>SnO using 3,4,5-tri-<i>O</i>-acetylgalloyl chloride, followed by the deprotection provided hamamelitannin in 79%. Pilot enzymatic benzoylation of D-hamamelose using vinyl benzoate (4 equiv.) and Lipozyme TL IM as a biocatalyst in <i>t</i>-butyl methyl ether (<i>t</i>-BuMeO) gave mainly benzoylated furanoses (89%), of which tribenzoates reached (52%). Enzymatic galloylation of 2,3-<i>O</i>-isopropylidene-α,β-D-hamamelofuranose with vinyl gallate under the catalysis of Lipozyme TL IM in <i>t</i>-butyl alcohol (<i>t</i>-BuOH) or <i>t</i>-BuMeO provided only the 5-<i>O</i>-galloylated product. The reaction in <i>t</i>-BuMeO proceeded in a shorter reaction time (61 h) and higher yield (82%). The more hydrophobic vinyl 3,4,5-tri-<i>O</i>-acetylgallate in the same reactions gave large amounts of acetylated products. Vinyl gallate and triacetylgallate in the enzymatic acylation of D-hamamelose with Lipozyme TL IM in <i>t</i>-BuMeO yielded 2′,5-diacylated hamamelofuranoses in a yield below 20%. The use of other vinyl gallates hydrophobized by methylation or benzylation provided 2′,5-diacylated hamamelofuranoses in good yields (65–84%). The reaction with silylated vinyl gallate did not proceed. The best results were obtained with vinyl 2,3,5-tri-<i>O</i>-benzyl gallate, and the only product, 2′,5-diacylated hamamelofuranoside precipitated from the reaction mixture (84% in 96 h). After debenzylation, hamamelitannin was obtained an 82% yield from hamamelose in two steps. This synthesis is preparatively undemanding and opens the way to multigram preparations of bioactive hamamelitannin and its analogues. |
| first_indexed | 2024-03-11T06:52:52Z |
| format | Article |
| id | doaj.art-b7286aca382340afb4db8e471f31d87d |
| institution | Directory Open Access Journal |
| issn | 2218-273X |
| language | English |
| last_indexed | 2024-03-11T06:52:52Z |
| publishDate | 2023-03-01 |
| publisher | MDPI AG |
| record_format | Article |
| series | Biomolecules |
| spelling | doaj.art-b7286aca382340afb4db8e471f31d87d2023-11-17T09:52:27ZengMDPI AGBiomolecules2218-273X2023-03-0113351910.3390/biom13030519From Hamamelitannin Synthesis to the Study of Enzymatic Acylations of D-HamameloseMária Mastihubová0Vladimír Mastihuba1Institute of Chemistry, Slovak Academy of Sciences, Dúbravská Cesta 9, 845 38 Bratislava, SlovakiaInstitute of Chemistry, Slovak Academy of Sciences, Dúbravská Cesta 9, 845 38 Bratislava, SlovakiaThe bioactive natural substance, hamamelitannin, was effectively synthesized in two ways. The chemical acylation of 2,3-<i>O</i>-isopropylidene-α,β-D-hamamelofuranose promoted by Bu<sub>2</sub>SnO using 3,4,5-tri-<i>O</i>-acetylgalloyl chloride, followed by the deprotection provided hamamelitannin in 79%. Pilot enzymatic benzoylation of D-hamamelose using vinyl benzoate (4 equiv.) and Lipozyme TL IM as a biocatalyst in <i>t</i>-butyl methyl ether (<i>t</i>-BuMeO) gave mainly benzoylated furanoses (89%), of which tribenzoates reached (52%). Enzymatic galloylation of 2,3-<i>O</i>-isopropylidene-α,β-D-hamamelofuranose with vinyl gallate under the catalysis of Lipozyme TL IM in <i>t</i>-butyl alcohol (<i>t</i>-BuOH) or <i>t</i>-BuMeO provided only the 5-<i>O</i>-galloylated product. The reaction in <i>t</i>-BuMeO proceeded in a shorter reaction time (61 h) and higher yield (82%). The more hydrophobic vinyl 3,4,5-tri-<i>O</i>-acetylgallate in the same reactions gave large amounts of acetylated products. Vinyl gallate and triacetylgallate in the enzymatic acylation of D-hamamelose with Lipozyme TL IM in <i>t</i>-BuMeO yielded 2′,5-diacylated hamamelofuranoses in a yield below 20%. The use of other vinyl gallates hydrophobized by methylation or benzylation provided 2′,5-diacylated hamamelofuranoses in good yields (65–84%). The reaction with silylated vinyl gallate did not proceed. The best results were obtained with vinyl 2,3,5-tri-<i>O</i>-benzyl gallate, and the only product, 2′,5-diacylated hamamelofuranoside precipitated from the reaction mixture (84% in 96 h). After debenzylation, hamamelitannin was obtained an 82% yield from hamamelose in two steps. This synthesis is preparatively undemanding and opens the way to multigram preparations of bioactive hamamelitannin and its analogues.https://www.mdpi.com/2218-273X/13/3/519hamamelitanninD-hamameloseregioselective acylationhydrophobized gallatesenzymatic galloylationLipozyme TL IM |
| spellingShingle | Mária Mastihubová Vladimír Mastihuba From Hamamelitannin Synthesis to the Study of Enzymatic Acylations of D-Hamamelose Biomolecules hamamelitannin D-hamamelose regioselective acylation hydrophobized gallates enzymatic galloylation Lipozyme TL IM |
| title | From Hamamelitannin Synthesis to the Study of Enzymatic Acylations of D-Hamamelose |
| title_full | From Hamamelitannin Synthesis to the Study of Enzymatic Acylations of D-Hamamelose |
| title_fullStr | From Hamamelitannin Synthesis to the Study of Enzymatic Acylations of D-Hamamelose |
| title_full_unstemmed | From Hamamelitannin Synthesis to the Study of Enzymatic Acylations of D-Hamamelose |
| title_short | From Hamamelitannin Synthesis to the Study of Enzymatic Acylations of D-Hamamelose |
| title_sort | from hamamelitannin synthesis to the study of enzymatic acylations of d hamamelose |
| topic | hamamelitannin D-hamamelose regioselective acylation hydrophobized gallates enzymatic galloylation Lipozyme TL IM |
| url | https://www.mdpi.com/2218-273X/13/3/519 |
| work_keys_str_mv | AT mariamastihubova fromhamamelitanninsynthesistothestudyofenzymaticacylationsofdhamamelose AT vladimirmastihuba fromhamamelitanninsynthesistothestudyofenzymaticacylationsofdhamamelose |