β‐Mannosylation through O‐Alkylation of Anomeric Cesium Alkoxides: Mechanistic Studies and Synthesis of the Hexasaccharide Core of Complex Fucosylated N‐Linked Glycans
dc.contributor.author | Meng, Shuai | |
dc.contributor.author | Bhetuwal, Bishwa Raj | |
dc.contributor.author | Nguyen, Hai | |
dc.contributor.author | Qi, Xiaotian | |
dc.contributor.author | Fang, Cheng | |
dc.contributor.author | Saybolt, Kevin | |
dc.contributor.author | Li, Xiaohua | |
dc.contributor.author | Liu, Peng | |
dc.contributor.author | Zhu, Jianglong | |
dc.date.accessioned | 2020-05-05T19:34:20Z | |
dc.date.available | WITHHELD_12_MONTHS | |
dc.date.available | 2020-05-05T19:34:20Z | |
dc.date.issued | 2020-04-23 | |
dc.identifier.citation | Meng, Shuai; Bhetuwal, Bishwa Raj; Nguyen, Hai; Qi, Xiaotian; Fang, Cheng; Saybolt, Kevin; Li, Xiaohua; Liu, Peng; Zhu, Jianglong (2020). "β‐Mannosylation through O‐Alkylation of Anomeric Cesium Alkoxides: Mechanistic Studies and Synthesis of the Hexasaccharide Core of Complex Fucosylated N‐Linked Glycans." European Journal of Organic Chemistry 2020(15): 2291-2301. | |
dc.identifier.issn | 1434-193X | |
dc.identifier.issn | 1099-0690 | |
dc.identifier.uri | https://hdl.handle.net/2027.42/154903 | |
dc.publisher | Wiley Periodicals, Inc. | |
dc.publisher | CRC Press | |
dc.subject.other | Synthetic methods | |
dc.subject.other | Glycosylation | |
dc.subject.other | Carbohydrates | |
dc.subject.other | Glycans | |
dc.subject.other | Mannosylation | |
dc.title | β‐Mannosylation through O‐Alkylation of Anomeric Cesium Alkoxides: Mechanistic Studies and Synthesis of the Hexasaccharide Core of Complex Fucosylated N‐Linked Glycans | |
dc.type | Article | |
dc.rights.robots | IndexNoFollow | |
dc.subject.hlbsecondlevel | Materials Science and Engineering | |
dc.subject.hlbsecondlevel | Biological Chemistry | |
dc.subject.hlbsecondlevel | Chemical Engineering | |
dc.subject.hlbsecondlevel | Chemistry | |
dc.subject.hlbtoplevel | Health Sciences | |
dc.subject.hlbtoplevel | Science | |
dc.subject.hlbtoplevel | Engineering | |
dc.description.peerreviewed | Peer Reviewed | |
dc.description.bitstreamurl | https://deepblue.lib.umich.edu/bitstream/2027.42/154903/1/ejoc202000313.pdf | |
dc.description.bitstreamurl | https://deepblue.lib.umich.edu/bitstream/2027.42/154903/2/ejoc202000313-sup-0001-SupMat.pdf | |
dc.description.bitstreamurl | https://deepblue.lib.umich.edu/bitstream/2027.42/154903/3/ejoc202000313_am.pdf | |
dc.identifier.doi | 10.1002/ejoc.202000313 | |
dc.identifier.source | European Journal of Organic Chemistry | |
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dc.identifier.citedreference | Extensive NMR studies of anomeric cesium alkoxide ( 45 ) at room temperature or 40 °C did not show much difference. | |
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dc.identifier.citedreference | This cesium carbonate‐mediated β ‐mannosylation via anomeric O ‐alkylation gives comparable results in 1,2‐dichloroethane (DCE) and chloroform (CHCl 3 ). | |
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dc.identifier.citedreference | Deprotonation of C2‐OH is not required for this anomeric O ‐alkylation to occur, as anomeric O‐alkylation of 2,3,4,6‐tetra‐ O ‐benzyl‐D‐mannopyranose also afford the desired β‐mannoside in good yield and anomeric selectivity. However, we can not rule out the possibility that the C2‐OH of mannose is deprotonated in a thermodynamically unfavorable, rate‐limiting step to generate a bis‐alkoxide which is rapidly alkylated at the anomeric position. We sincerely thank one of the reviewers for pointing this out. | |
dc.identifier.citedreference | Whether the C2‐OH of intermediates 52 and 54 is deprotonated or not can not be concluded from the 1 H NMR data; however, it is believed that it remains mainly as undeprotonated form in consideration of its p K a value. In addition, our experimental analysis of the weight of cesium alkoxide 42 is consistent with the presence of one cesium ion in the majority component. | |
dc.identifier.citedreference | The chelating Cs–O distances in the optimized structures are typically shorter than 3 Å, which indicates relatively strong interactions, see: O. C. Gagné and F. C. Hawthorne, Acta Crystallogr., Sect. B Struct. Sci, 2018, 74, 63 – 78. | |
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dc.identifier.citedreference | Although the data prove that monomeric cesium alkoxide 42 β should be the real reactive species for this anomeric O ‐alkylation at 0.1–0.2 M of initial concentration of mannose 7, other forms of cesium alkoxide 42 β, e.g., dimeric form, can not be ruled out at higher concentration. | |
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dc.identifier.citedreference | Previous studies also indicated that due to electron‐electron repulsion anomeric C1‐alkoxide is more nucleophilic than non‐anomeric alkoxide, see: ref.[ 9c ],,. | |
dc.owningcollname | Interdisciplinary and Peer-Reviewed |
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