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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.authorMeng, Shuai
dc.contributor.authorBhetuwal, Bishwa Raj
dc.contributor.authorNguyen, Hai
dc.contributor.authorQi, Xiaotian
dc.contributor.authorFang, Cheng
dc.contributor.authorSaybolt, Kevin
dc.contributor.authorLi, Xiaohua
dc.contributor.authorLiu, Peng
dc.contributor.authorZhu, Jianglong
dc.date.accessioned2020-05-05T19:34:20Z
dc.date.availableWITHHELD_12_MONTHS
dc.date.available2020-05-05T19:34:20Z
dc.date.issued2020-04-23
dc.identifier.citationMeng, 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.issn1434-193X
dc.identifier.issn1099-0690
dc.identifier.urihttps://hdl.handle.net/2027.42/154903
dc.publisherWiley Periodicals, Inc.
dc.publisherCRC Press
dc.subject.otherSynthetic methods
dc.subject.otherGlycosylation
dc.subject.otherCarbohydrates
dc.subject.otherGlycans
dc.subject.otherMannosylation
dc.titleβ‐Mannosylation through O‐Alkylation of Anomeric Cesium Alkoxides: Mechanistic Studies and Synthesis of the Hexasaccharide Core of Complex Fucosylated N‐Linked Glycans
dc.typeArticle
dc.rights.robotsIndexNoFollow
dc.subject.hlbsecondlevelMaterials Science and Engineering
dc.subject.hlbsecondlevelBiological Chemistry
dc.subject.hlbsecondlevelChemical Engineering
dc.subject.hlbsecondlevelChemistry
dc.subject.hlbtoplevelHealth Sciences
dc.subject.hlbtoplevelScience
dc.subject.hlbtoplevelEngineering
dc.description.peerreviewedPeer Reviewed
dc.description.bitstreamurlhttps://deepblue.lib.umich.edu/bitstream/2027.42/154903/1/ejoc202000313.pdf
dc.description.bitstreamurlhttps://deepblue.lib.umich.edu/bitstream/2027.42/154903/2/ejoc202000313-sup-0001-SupMat.pdf
dc.description.bitstreamurlhttps://deepblue.lib.umich.edu/bitstream/2027.42/154903/3/ejoc202000313_am.pdf
dc.identifier.doi10.1002/ejoc.202000313
dc.identifier.sourceEuropean Journal of Organic Chemistry
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dc.identifier.citedreferenceExtensive NMR studies of anomeric cesium alkoxide ( 45 ) at room temperature or 40 °C did not show much difference.
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dc.identifier.citedreferenceSee Supporting Information for details.
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dc.identifier.citedreferenceWhether 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.
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dc.identifier.citedreferenceComputationally it is not feasible to accurately model the deprotonation using the experimentally used base Cs 2 CO 3, which does not completely dissolve under the experimental conditions. Here, using 7‐Cs as the model base will not affect the relative acidity trend.
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dc.identifier.citedreferencePrevious studies also indicated that due to electron‐electron repulsion anomeric C1‐alkoxide is more nucleophilic than non‐anomeric alkoxide, see: ref.[ 9c ],,.
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