ortho-Methoxycarbonylethynylphenyl Thioglycosides (MCEPTs): Versatile Glycosyl Donors Enabled by Electron-Withdrawing Substituents and Catalyzed by Gold(I) or Cu(II) Complexes
With easily accessible and operator-friendly reagents, shelf-stable ortho-methoxycarbonylethynylphenyl thioglycosides were efficiently prepared. Based on these MCEPT glycoside donors, a novel glycosylation protocol featuring mild and catalytic promotion conditions with Au(I) or Cu(II) complexes, e...
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Veröffentlicht in: | Journal of the American Chemical Society 2023-02, Vol.145 (6), p.3682-3695 |
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description | With easily accessible and operator-friendly reagents, shelf-stable ortho-methoxycarbonylethynylphenyl thioglycosides were efficiently prepared. Based on these MCEPT glycoside donors, a novel glycosylation protocol featuring mild and catalytic promotion conditions with Au(I) or Cu(II) complexes, expanded substrate scope encompassing challenging donors and acceptors and clinically used pharmaceuticals, and versatility in various strategies for highly efficient synthesis of glycosides has been established. The practicality of the MCEPT glycosylation protocol was fully exhibited by highly efficient and scalable synthesis of surface polysaccharide subunits of Acinetobacter baumannii via latent–active, reagent-controlled divergent orthogonal one-pot and orthogonal one-pot strategies. The underlying reaction mechanism was investigated systematically through control reactions, leading to the isolation and characterization of the vital catalyst species in MCEPT glycosylation, the benzothiophen-3-yl-gold(I) complex. Based on the results obtained both from control reactions and from studies leading to the glycosylation protocol establishment, an operative mechanism was proposed and the effect of the vital catalyst species reactivity on the results of metal-catalyzed alkyne-containing donor-involved glycosylation was disclosed. Moreover, the mechanism for C-glycosylation side product formation from ortho-(substituted)ethynylphenyl thioglycoside donors with electron-donating substituents was also illuminated. |
doi_str_mv | 10.1021/jacs.2c13018 |
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Based on these MCEPT glycoside donors, a novel glycosylation protocol featuring mild and catalytic promotion conditions with Au(I) or Cu(II) complexes, expanded substrate scope encompassing challenging donors and acceptors and clinically used pharmaceuticals, and versatility in various strategies for highly efficient synthesis of glycosides has been established. The practicality of the MCEPT glycosylation protocol was fully exhibited by highly efficient and scalable synthesis of surface polysaccharide subunits of Acinetobacter baumannii via latent–active, reagent-controlled divergent orthogonal one-pot and orthogonal one-pot strategies. The underlying reaction mechanism was investigated systematically through control reactions, leading to the isolation and characterization of the vital catalyst species in MCEPT glycosylation, the benzothiophen-3-yl-gold(I) complex. Based on the results obtained both from control reactions and from studies leading to the glycosylation protocol establishment, an operative mechanism was proposed and the effect of the vital catalyst species reactivity on the results of metal-catalyzed alkyne-containing donor-involved glycosylation was disclosed. Moreover, the mechanism for C-glycosylation side product formation from ortho-(substituted)ethynylphenyl thioglycoside donors with electron-donating substituents was also illuminated.</description><identifier>ISSN: 0002-7863</identifier><identifier>EISSN: 1520-5126</identifier><identifier>DOI: 10.1021/jacs.2c13018</identifier><identifier>PMID: 36727591</identifier><language>eng</language><publisher>United States: American Chemical Society</publisher><ispartof>Journal of the American Chemical Society, 2023-02, Vol.145 (6), p.3682-3695</ispartof><rights>2023 American Chemical Society</rights><lds50>peer_reviewed</lds50><woscitedreferencessubscribed>false</woscitedreferencessubscribed><citedby>FETCH-LOGICAL-a324t-f5e4cf011532143067969a3325e308e574fadbfeb0f79a20578c4059fded6d923</citedby><cites>FETCH-LOGICAL-a324t-f5e4cf011532143067969a3325e308e574fadbfeb0f79a20578c4059fded6d923</cites><orcidid>0000-0001-6413-943X</orcidid></display><links><openurl>$$Topenurl_article</openurl><openurlfulltext>$$Topenurlfull_article</openurlfulltext><thumbnail>$$Tsyndetics_thumb_exl</thumbnail><linktopdf>$$Uhttps://pubs.acs.org/doi/pdf/10.1021/jacs.2c13018$$EPDF$$P50$$Gacs$$H</linktopdf><linktohtml>$$Uhttps://pubs.acs.org/doi/10.1021/jacs.2c13018$$EHTML$$P50$$Gacs$$H</linktohtml><link.rule.ids>314,780,784,2765,27076,27924,27925,56738,56788</link.rule.ids><backlink>$$Uhttps://www.ncbi.nlm.nih.gov/pubmed/36727591$$D View this record in MEDLINE/PubMed$$Hfree_for_read</backlink></links><search><creatorcontrib>Liu, Hui</creatorcontrib><creatorcontrib>Liang, Zhi-Fen</creatorcontrib><creatorcontrib>Liu, Han-Jian</creatorcontrib><creatorcontrib>Liao, Jin-Xi</creatorcontrib><creatorcontrib>Zhong, Li-Jun</creatorcontrib><creatorcontrib>Tu, Yuan-Hong</creatorcontrib><creatorcontrib>Zhang, Qing-Ju</creatorcontrib><creatorcontrib>Xiong, Bin</creatorcontrib><creatorcontrib>Sun, Jian-Song</creatorcontrib><title>ortho-Methoxycarbonylethynylphenyl Thioglycosides (MCEPTs): Versatile Glycosyl Donors Enabled by Electron-Withdrawing Substituents and Catalyzed by Gold(I) or Cu(II) Complexes</title><title>Journal of the American Chemical Society</title><addtitle>J. Am. Chem. Soc</addtitle><description>With easily accessible and operator-friendly reagents, shelf-stable ortho-methoxycarbonylethynylphenyl thioglycosides were efficiently prepared. Based on these MCEPT glycoside donors, a novel glycosylation protocol featuring mild and catalytic promotion conditions with Au(I) or Cu(II) complexes, expanded substrate scope encompassing challenging donors and acceptors and clinically used pharmaceuticals, and versatility in various strategies for highly efficient synthesis of glycosides has been established. The practicality of the MCEPT glycosylation protocol was fully exhibited by highly efficient and scalable synthesis of surface polysaccharide subunits of Acinetobacter baumannii via latent–active, reagent-controlled divergent orthogonal one-pot and orthogonal one-pot strategies. The underlying reaction mechanism was investigated systematically through control reactions, leading to the isolation and characterization of the vital catalyst species in MCEPT glycosylation, the benzothiophen-3-yl-gold(I) complex. Based on the results obtained both from control reactions and from studies leading to the glycosylation protocol establishment, an operative mechanism was proposed and the effect of the vital catalyst species reactivity on the results of metal-catalyzed alkyne-containing donor-involved glycosylation was disclosed. Moreover, the mechanism for C-glycosylation side product formation from ortho-(substituted)ethynylphenyl thioglycoside donors with electron-donating substituents was also illuminated.</description><issn>0002-7863</issn><issn>1520-5126</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2023</creationdate><recordtype>article</recordtype><recordid>eNptkU2P0zAQhi0EYsvCjTPysSuRXX_EccINhdKttCuQKHCMnHiyTeXaxXbEhj_FX8TdFvbCZT40z7yj0YvQa0ouKWH0aqu6cMk6ygktn6AZFYxkgrLiKZoRQlgmy4KfoRchbFObs5I-R2e8kEyKis7Qb-fjxmW3kOL91CnfOjuZ1E0p7TeQIl5vBndnps6FQUPA89t68XkdLt7hb-CDioMBvHwYJ_aDs84HvLCqNaBxO-GFgS56Z7PvQ9xor34O9g5_GdsQhziCjQErq3GtojLTr-PK0hk9X11g53E9zlepqt1ub-Aewkv0rFcmwKtTPkdfPy7W9XV282m5qt_fZIqzPGa9gLzrCaWCM5pzUsiqqBTnTAAnJQiZ90q3PbSkl5ViRMiyy4moeg260BXj52h-1N1792OEEJvdEDowRllwY2iYlLTiFadlQt8e0c67EDz0zd4PO-WnhpLmYFFzsKg5WZTwNyflsd2B_gf_9eTx9GFr60Zv06P_1_oDCm-ctw</recordid><startdate>20230215</startdate><enddate>20230215</enddate><creator>Liu, Hui</creator><creator>Liang, Zhi-Fen</creator><creator>Liu, Han-Jian</creator><creator>Liao, Jin-Xi</creator><creator>Zhong, Li-Jun</creator><creator>Tu, Yuan-Hong</creator><creator>Zhang, Qing-Ju</creator><creator>Xiong, Bin</creator><creator>Sun, Jian-Song</creator><general>American Chemical Society</general><scope>NPM</scope><scope>AAYXX</scope><scope>CITATION</scope><scope>7X8</scope><orcidid>https://orcid.org/0000-0001-6413-943X</orcidid></search><sort><creationdate>20230215</creationdate><title>ortho-Methoxycarbonylethynylphenyl Thioglycosides (MCEPTs): Versatile Glycosyl Donors Enabled by Electron-Withdrawing Substituents and Catalyzed by Gold(I) or Cu(II) Complexes</title><author>Liu, Hui ; Liang, Zhi-Fen ; Liu, Han-Jian ; Liao, Jin-Xi ; Zhong, Li-Jun ; Tu, Yuan-Hong ; Zhang, Qing-Ju ; Xiong, Bin ; Sun, Jian-Song</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-a324t-f5e4cf011532143067969a3325e308e574fadbfeb0f79a20578c4059fded6d923</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2023</creationdate><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Liu, Hui</creatorcontrib><creatorcontrib>Liang, Zhi-Fen</creatorcontrib><creatorcontrib>Liu, Han-Jian</creatorcontrib><creatorcontrib>Liao, Jin-Xi</creatorcontrib><creatorcontrib>Zhong, Li-Jun</creatorcontrib><creatorcontrib>Tu, Yuan-Hong</creatorcontrib><creatorcontrib>Zhang, Qing-Ju</creatorcontrib><creatorcontrib>Xiong, Bin</creatorcontrib><creatorcontrib>Sun, Jian-Song</creatorcontrib><collection>PubMed</collection><collection>CrossRef</collection><collection>MEDLINE - Academic</collection><jtitle>Journal of the American Chemical Society</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Liu, Hui</au><au>Liang, Zhi-Fen</au><au>Liu, Han-Jian</au><au>Liao, Jin-Xi</au><au>Zhong, Li-Jun</au><au>Tu, Yuan-Hong</au><au>Zhang, Qing-Ju</au><au>Xiong, Bin</au><au>Sun, Jian-Song</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>ortho-Methoxycarbonylethynylphenyl Thioglycosides (MCEPTs): Versatile Glycosyl Donors Enabled by Electron-Withdrawing Substituents and Catalyzed by Gold(I) or Cu(II) Complexes</atitle><jtitle>Journal of the American Chemical Society</jtitle><addtitle>J. Am. Chem. Soc</addtitle><date>2023-02-15</date><risdate>2023</risdate><volume>145</volume><issue>6</issue><spage>3682</spage><epage>3695</epage><pages>3682-3695</pages><issn>0002-7863</issn><eissn>1520-5126</eissn><abstract>With easily accessible and operator-friendly reagents, shelf-stable ortho-methoxycarbonylethynylphenyl thioglycosides were efficiently prepared. Based on these MCEPT glycoside donors, a novel glycosylation protocol featuring mild and catalytic promotion conditions with Au(I) or Cu(II) complexes, expanded substrate scope encompassing challenging donors and acceptors and clinically used pharmaceuticals, and versatility in various strategies for highly efficient synthesis of glycosides has been established. The practicality of the MCEPT glycosylation protocol was fully exhibited by highly efficient and scalable synthesis of surface polysaccharide subunits of Acinetobacter baumannii via latent–active, reagent-controlled divergent orthogonal one-pot and orthogonal one-pot strategies. The underlying reaction mechanism was investigated systematically through control reactions, leading to the isolation and characterization of the vital catalyst species in MCEPT glycosylation, the benzothiophen-3-yl-gold(I) complex. Based on the results obtained both from control reactions and from studies leading to the glycosylation protocol establishment, an operative mechanism was proposed and the effect of the vital catalyst species reactivity on the results of metal-catalyzed alkyne-containing donor-involved glycosylation was disclosed. Moreover, the mechanism for C-glycosylation side product formation from ortho-(substituted)ethynylphenyl thioglycoside donors with electron-donating substituents was also illuminated.</abstract><cop>United States</cop><pub>American Chemical Society</pub><pmid>36727591</pmid><doi>10.1021/jacs.2c13018</doi><tpages>14</tpages><orcidid>https://orcid.org/0000-0001-6413-943X</orcidid></addata></record> |
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title | ortho-Methoxycarbonylethynylphenyl Thioglycosides (MCEPTs): Versatile Glycosyl Donors Enabled by Electron-Withdrawing Substituents and Catalyzed by Gold(I) or Cu(II) Complexes |
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