Organocatalytic Glycosylation by Using Electron-Deficient Pyridinium Salts
A new organocatalytic glycosylation method based on electron‐deficient pyridinium salts is reported. At ambient temperature and catalyst loadings as low as 1 mol %, 2‐deoxyglycosides were formed from benzyl‐ and silyl‐protected glycals and primary or secondary glycosyl acceptors, with excellent yiel...
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| Veröffentlicht in: | Angewandte Chemie International Edition 2015-10, Vol.54 (42), p.12479-12483 |
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| creator | Das, Somnath Pekel, Daniel Neudörfl, Jörg-M. Berkessel, Albrecht |
| description | A new organocatalytic glycosylation method based on electron‐deficient pyridinium salts is reported. At ambient temperature and catalyst loadings as low as 1 mol %, 2‐deoxyglycosides were formed from benzyl‐ and silyl‐protected glycals and primary or secondary glycosyl acceptors, with excellent yields and anomeric selectivity. Mechanistic investigations point to alcohol–pyridinium conjugates (1,2‐addition products) as key intermediates in the catalytic cycle.
Less is more! Electron‐deficient pyridinium cations efficiently catalyze the glycosylation of benzyl‐ and silyl‐protected glycals. Both primary and secondary alcohols can act as glycosyl acceptors. The glycosylation shown proceeds at RT and affords exclusively the α‐galactoside. The 1,2‐addition product of the alcohol component to the pyridinium cation most likely acts as crucial catalysis intermediate. |
| doi_str_mv | 10.1002/anie.201503156 |
| format | Article |
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Less is more! Electron‐deficient pyridinium cations efficiently catalyze the glycosylation of benzyl‐ and silyl‐protected glycals. Both primary and secondary alcohols can act as glycosyl acceptors. The glycosylation shown proceeds at RT and affords exclusively the α‐galactoside. The 1,2‐addition product of the alcohol component to the pyridinium cation most likely acts as crucial catalysis intermediate.</description><edition>International ed. in English</edition><identifier>ISSN: 1433-7851</identifier><identifier>EISSN: 1521-3773</identifier><identifier>DOI: 10.1002/anie.201503156</identifier><identifier>PMID: 26220811</identifier><identifier>CODEN: ACIEAY</identifier><language>eng</language><publisher>Weinheim: WILEY-VCH Verlag</publisher><subject>acetals ; Alcohols ; Ambient temperature ; anion binding ; Catalysis ; Catalysts ; Cations ; Conjugates ; glycosylation ; organocatalysis ; pyridinium cations ; Selectivity</subject><ispartof>Angewandte Chemie International Edition, 2015-10, Vol.54 (42), p.12479-12483</ispartof><rights>2015 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim</rights><rights>2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.</rights><rights>2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim</rights><lds50>peer_reviewed</lds50><woscitedreferencessubscribed>false</woscitedreferencessubscribed><citedby>FETCH-LOGICAL-c5476-7076823b1c7f127a3c5577228072d56986ddcc1c1f833240836c384ae8e534503</citedby><cites>FETCH-LOGICAL-c5476-7076823b1c7f127a3c5577228072d56986ddcc1c1f833240836c384ae8e534503</cites></display><links><openurl>$$Topenurl_article</openurl><openurlfulltext>$$Topenurlfull_article</openurlfulltext><thumbnail>$$Tsyndetics_thumb_exl</thumbnail><linktopdf>$$Uhttps://onlinelibrary.wiley.com/doi/pdf/10.1002%2Fanie.201503156$$EPDF$$P50$$Gwiley$$H</linktopdf><linktohtml>$$Uhttps://onlinelibrary.wiley.com/doi/full/10.1002%2Fanie.201503156$$EHTML$$P50$$Gwiley$$H</linktohtml><link.rule.ids>314,780,784,1416,27923,27924,45573,45574</link.rule.ids><backlink>$$Uhttps://www.ncbi.nlm.nih.gov/pubmed/26220811$$D View this record in MEDLINE/PubMed$$Hfree_for_read</backlink></links><search><creatorcontrib>Das, Somnath</creatorcontrib><creatorcontrib>Pekel, Daniel</creatorcontrib><creatorcontrib>Neudörfl, Jörg-M.</creatorcontrib><creatorcontrib>Berkessel, Albrecht</creatorcontrib><title>Organocatalytic Glycosylation by Using Electron-Deficient Pyridinium Salts</title><title>Angewandte Chemie International Edition</title><addtitle>Angew. Chem. Int. Ed</addtitle><description>A new organocatalytic glycosylation method based on electron‐deficient pyridinium salts is reported. At ambient temperature and catalyst loadings as low as 1 mol %, 2‐deoxyglycosides were formed from benzyl‐ and silyl‐protected glycals and primary or secondary glycosyl acceptors, with excellent yields and anomeric selectivity. Mechanistic investigations point to alcohol–pyridinium conjugates (1,2‐addition products) as key intermediates in the catalytic cycle.
Less is more! Electron‐deficient pyridinium cations efficiently catalyze the glycosylation of benzyl‐ and silyl‐protected glycals. Both primary and secondary alcohols can act as glycosyl acceptors. The glycosylation shown proceeds at RT and affords exclusively the α‐galactoside. The 1,2‐addition product of the alcohol component to the pyridinium cation most likely acts as crucial catalysis intermediate.</description><subject>acetals</subject><subject>Alcohols</subject><subject>Ambient temperature</subject><subject>anion binding</subject><subject>Catalysis</subject><subject>Catalysts</subject><subject>Cations</subject><subject>Conjugates</subject><subject>glycosylation</subject><subject>organocatalysis</subject><subject>pyridinium cations</subject><subject>Selectivity</subject><issn>1433-7851</issn><issn>1521-3773</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2015</creationdate><recordtype>article</recordtype><recordid>eNqNkUtP4zAUha0RaHjNdpajSGzYpPja8SPLCkoBoTLSgJid5ToOcsd1ip0I8u9JVajQbGB17-I7n3R0EPoJeAQYk1MdnB0RDAxTYPwb2gdGIKdC0J3hLyjNhWSwhw5SWgy8lJh_R3uEE4IlwD66vo2POjRGt9r3rTPZ1PemSb3XrWtCNu-z--TCYzbx1rSxCfm5rZ1xNrTZ7z66ygXXLbM_2rfpCO3W2if74-0eovuLyd3ZZX5zO706G9_khhWC5wILLgmdgxE1EKGpYUwIQiQWpGK8lLyqjAEDtaSUFFhSbqgstJWW0WLoeYhONt5VbJ46m1q1dMlY73WwTZcUCD6UKzgrvoBCWQpOKQzo8X_oouliGIqsKVliAmQtHG0oE5uUoq3VKrqljr0CrNaDqPUgajvIEPj1pu3mS1tt8fcFBqDcAM_O2_4TnRrPriYf5fkm61JrX7ZZHf8pLqhg6mE2VX_Zw3VZiEvF6Cvav6OI</recordid><startdate>20151012</startdate><enddate>20151012</enddate><creator>Das, Somnath</creator><creator>Pekel, Daniel</creator><creator>Neudörfl, Jörg-M.</creator><creator>Berkessel, Albrecht</creator><general>WILEY-VCH Verlag</general><general>WILEY‐VCH Verlag</general><general>Wiley Subscription Services, Inc</general><scope>BSCLL</scope><scope>NPM</scope><scope>AAYXX</scope><scope>CITATION</scope><scope>7TM</scope><scope>K9.</scope><scope>7X8</scope><scope>7SR</scope><scope>8BQ</scope><scope>8FD</scope><scope>JG9</scope></search><sort><creationdate>20151012</creationdate><title>Organocatalytic Glycosylation by Using Electron-Deficient Pyridinium Salts</title><author>Das, Somnath ; Pekel, Daniel ; Neudörfl, Jörg-M. ; Berkessel, Albrecht</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-c5476-7076823b1c7f127a3c5577228072d56986ddcc1c1f833240836c384ae8e534503</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2015</creationdate><topic>acetals</topic><topic>Alcohols</topic><topic>Ambient temperature</topic><topic>anion binding</topic><topic>Catalysis</topic><topic>Catalysts</topic><topic>Cations</topic><topic>Conjugates</topic><topic>glycosylation</topic><topic>organocatalysis</topic><topic>pyridinium cations</topic><topic>Selectivity</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Das, Somnath</creatorcontrib><creatorcontrib>Pekel, Daniel</creatorcontrib><creatorcontrib>Neudörfl, Jörg-M.</creatorcontrib><creatorcontrib>Berkessel, Albrecht</creatorcontrib><collection>Istex</collection><collection>PubMed</collection><collection>CrossRef</collection><collection>Nucleic Acids Abstracts</collection><collection>ProQuest Health & Medical Complete (Alumni)</collection><collection>MEDLINE - Academic</collection><collection>Engineered Materials Abstracts</collection><collection>METADEX</collection><collection>Technology Research Database</collection><collection>Materials Research Database</collection><jtitle>Angewandte Chemie International Edition</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Das, Somnath</au><au>Pekel, Daniel</au><au>Neudörfl, Jörg-M.</au><au>Berkessel, Albrecht</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Organocatalytic Glycosylation by Using Electron-Deficient Pyridinium Salts</atitle><jtitle>Angewandte Chemie International Edition</jtitle><addtitle>Angew. Chem. Int. Ed</addtitle><date>2015-10-12</date><risdate>2015</risdate><volume>54</volume><issue>42</issue><spage>12479</spage><epage>12483</epage><pages>12479-12483</pages><issn>1433-7851</issn><eissn>1521-3773</eissn><coden>ACIEAY</coden><abstract>A new organocatalytic glycosylation method based on electron‐deficient pyridinium salts is reported. At ambient temperature and catalyst loadings as low as 1 mol %, 2‐deoxyglycosides were formed from benzyl‐ and silyl‐protected glycals and primary or secondary glycosyl acceptors, with excellent yields and anomeric selectivity. Mechanistic investigations point to alcohol–pyridinium conjugates (1,2‐addition products) as key intermediates in the catalytic cycle.
Less is more! Electron‐deficient pyridinium cations efficiently catalyze the glycosylation of benzyl‐ and silyl‐protected glycals. Both primary and secondary alcohols can act as glycosyl acceptors. The glycosylation shown proceeds at RT and affords exclusively the α‐galactoside. The 1,2‐addition product of the alcohol component to the pyridinium cation most likely acts as crucial catalysis intermediate.</abstract><cop>Weinheim</cop><pub>WILEY-VCH Verlag</pub><pmid>26220811</pmid><doi>10.1002/anie.201503156</doi><tpages>5</tpages><edition>International ed. in English</edition></addata></record> |
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| subjects | acetals Alcohols Ambient temperature anion binding Catalysis Catalysts Cations Conjugates glycosylation organocatalysis pyridinium cations Selectivity |
| title | Organocatalytic Glycosylation by Using Electron-Deficient Pyridinium Salts |
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