Remarkably regioselective deacylation of cellulose esters using tetraalkylammonium salts of the strongly basic hydroxide ion
•Discovered regioselective cellulose ester deacylation by tetralkylammonium hydroxides.•One step process requiring no protective groups.•Route to cellulose 6-esters and 2,3-A-6-B-triesters.•Regioselective deacylation even with limited equiv of NaOH. Tetraalkylammonium hydroxides have been found to m...
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| Veröffentlicht in: | Carbohydrate polymers 2014-10, Vol.111, p.25-32 |
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| creator | Zheng, Xueyan Gandour, Richard D. Edgar, Kevin J. |
| description | •Discovered regioselective cellulose ester deacylation by tetralkylammonium hydroxides.•One step process requiring no protective groups.•Route to cellulose 6-esters and 2,3-A-6-B-triesters.•Regioselective deacylation even with limited equiv of NaOH.
Tetraalkylammonium hydroxides have been found to mediate regioselective deacylation of cellulose esters. This deacylation surprisingly shows substantial selectivity for the removal of the acyl groups at O-2/3, affording cellulose-6-O-esters by a simple, efficient one-step process. The mechanism for this deacylation was investigated by studying the effect of tetraalkylammonium cation size upon ester deacylation selectivity. We hypothesize that coordination of the tetraalkylammonium cation by the ester oxygen atoms of the vicinal 2,3-acetate groups may drive the unexpected regioselectivity at the secondary alcohol esters. Broad scope with respect to ester type was demonstrated; regioselective O-2,3 deacylation was observed with cellulose acetate, propionate, butyrate, hexanoate and benzoate triesters. The scope of this deacylation of cellulose acetates has been investigated to understand how to carry it out most efficiently. Reaction with TBAOH in pyridine was the most effective process, providing the highest selectivity. |
| doi_str_mv | 10.1016/j.carbpol.2014.04.014 |
| format | Article |
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Tetraalkylammonium hydroxides have been found to mediate regioselective deacylation of cellulose esters. This deacylation surprisingly shows substantial selectivity for the removal of the acyl groups at O-2/3, affording cellulose-6-O-esters by a simple, efficient one-step process. The mechanism for this deacylation was investigated by studying the effect of tetraalkylammonium cation size upon ester deacylation selectivity. We hypothesize that coordination of the tetraalkylammonium cation by the ester oxygen atoms of the vicinal 2,3-acetate groups may drive the unexpected regioselectivity at the secondary alcohol esters. Broad scope with respect to ester type was demonstrated; regioselective O-2,3 deacylation was observed with cellulose acetate, propionate, butyrate, hexanoate and benzoate triesters. The scope of this deacylation of cellulose acetates has been investigated to understand how to carry it out most efficiently. Reaction with TBAOH in pyridine was the most effective process, providing the highest selectivity.</description><identifier>ISSN: 0144-8617</identifier><identifier>EISSN: 1879-1344</identifier><identifier>DOI: 10.1016/j.carbpol.2014.04.014</identifier><identifier>PMID: 25037325</identifier><identifier>CODEN: CAPOD8</identifier><language>eng</language><publisher>Kidlington: Elsevier Ltd</publisher><subject>Acylation ; Alkylation ; Ammonium Compounds - chemistry ; Applied sciences ; Catalysis ; Cellulose - analogs & derivatives ; Cellulose - chemistry ; Cellulose and derivatives ; Cellulose ester ; Deacylation ; Esters - chemistry ; Exact sciences and technology ; Hydrolysis ; Hydroxides - chemistry ; Mechanism ; Natural polymers ; Physicochemistry of polymers ; Regioselectivity ; Salts - chemistry ; Stereoisomerism</subject><ispartof>Carbohydrate polymers, 2014-10, Vol.111, p.25-32</ispartof><rights>2014 Elsevier Ltd</rights><rights>2015 INIST-CNRS</rights><rights>Copyright © 2014 Elsevier Ltd. All rights reserved.</rights><lds50>peer_reviewed</lds50><woscitedreferencessubscribed>false</woscitedreferencessubscribed><citedby>FETCH-LOGICAL-c461t-97fd0b5406c98e0da69c841444cb21c199c80a7f595397b4927f6494cce104f93</citedby><cites>FETCH-LOGICAL-c461t-97fd0b5406c98e0da69c841444cb21c199c80a7f595397b4927f6494cce104f93</cites><orcidid>0000-0001-5941-9517</orcidid></display><links><openurl>$$Topenurl_article</openurl><openurlfulltext>$$Topenurlfull_article</openurlfulltext><thumbnail>$$Tsyndetics_thumb_exl</thumbnail><linktohtml>$$Uhttps://www.sciencedirect.com/science/article/pii/S0144861714003713$$EHTML$$P50$$Gelsevier$$H</linktohtml><link.rule.ids>314,776,780,3537,27901,27902,65534</link.rule.ids><backlink>$$Uhttp://pascal-francis.inist.fr/vibad/index.php?action=getRecordDetail&idt=28614190$$DView record in Pascal Francis$$Hfree_for_read</backlink><backlink>$$Uhttps://www.ncbi.nlm.nih.gov/pubmed/25037325$$D View this record in MEDLINE/PubMed$$Hfree_for_read</backlink></links><search><creatorcontrib>Zheng, Xueyan</creatorcontrib><creatorcontrib>Gandour, Richard D.</creatorcontrib><creatorcontrib>Edgar, Kevin J.</creatorcontrib><title>Remarkably regioselective deacylation of cellulose esters using tetraalkylammonium salts of the strongly basic hydroxide ion</title><title>Carbohydrate polymers</title><addtitle>Carbohydr Polym</addtitle><description>•Discovered regioselective cellulose ester deacylation by tetralkylammonium hydroxides.•One step process requiring no protective groups.•Route to cellulose 6-esters and 2,3-A-6-B-triesters.•Regioselective deacylation even with limited equiv of NaOH.
Tetraalkylammonium hydroxides have been found to mediate regioselective deacylation of cellulose esters. This deacylation surprisingly shows substantial selectivity for the removal of the acyl groups at O-2/3, affording cellulose-6-O-esters by a simple, efficient one-step process. The mechanism for this deacylation was investigated by studying the effect of tetraalkylammonium cation size upon ester deacylation selectivity. We hypothesize that coordination of the tetraalkylammonium cation by the ester oxygen atoms of the vicinal 2,3-acetate groups may drive the unexpected regioselectivity at the secondary alcohol esters. Broad scope with respect to ester type was demonstrated; regioselective O-2,3 deacylation was observed with cellulose acetate, propionate, butyrate, hexanoate and benzoate triesters. The scope of this deacylation of cellulose acetates has been investigated to understand how to carry it out most efficiently. Reaction with TBAOH in pyridine was the most effective process, providing the highest selectivity.</description><subject>Acylation</subject><subject>Alkylation</subject><subject>Ammonium Compounds - chemistry</subject><subject>Applied sciences</subject><subject>Catalysis</subject><subject>Cellulose - analogs & derivatives</subject><subject>Cellulose - chemistry</subject><subject>Cellulose and derivatives</subject><subject>Cellulose ester</subject><subject>Deacylation</subject><subject>Esters - chemistry</subject><subject>Exact sciences and technology</subject><subject>Hydrolysis</subject><subject>Hydroxides - chemistry</subject><subject>Mechanism</subject><subject>Natural polymers</subject><subject>Physicochemistry of polymers</subject><subject>Regioselectivity</subject><subject>Salts - chemistry</subject><subject>Stereoisomerism</subject><issn>0144-8617</issn><issn>1879-1344</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2014</creationdate><recordtype>article</recordtype><sourceid>EIF</sourceid><recordid>eNqFkVFrFDEQx4NY7Fn9CEpeBF_2THazu5cnkVKtUBBKfQ7Z7Ow11-zmzGSLB374znJnfTQMhCS__2TmP4y9k2IthWw-7dbOpm4fw7oUUq0FhVQv2EpuWl3ISqmXbEU3qtg0sj1nrxF3glYjxSt2XtaiaquyXrE_tzDa9GC7cOAJtj4iBHDZPwLvwbpDsNnHiceBOwhhDvTOATMk5DP6acsz5GRteCByHOPk55GjDRkXSb4HjjnFaUvZO4ve8ftDn-Jv3wOntG_Y2WADwtvTfsF-fr26u7wubn58-3755aZwqpG50O3Qi65WonF6A6K3jXYbRb0p15XSSU1HYduh1nWl207psh0apZVzIIUadHXBPh7z7lP8NVP5ZvS49GMniDMaWau2rtpSLGh9RF2KiAkGs0-eHDoYKcxivNmZk_FmMd4ICqlI9_70xdyN0D-r_jpNwIcTYNHZMCQ7OY__OBqTkloQ9_nIARny6CEZdB4mB71PNBjTR_-fUp4ApIumig</recordid><startdate>20141013</startdate><enddate>20141013</enddate><creator>Zheng, Xueyan</creator><creator>Gandour, Richard D.</creator><creator>Edgar, Kevin J.</creator><general>Elsevier Ltd</general><general>Elsevier</general><scope>IQODW</scope><scope>CGR</scope><scope>CUY</scope><scope>CVF</scope><scope>ECM</scope><scope>EIF</scope><scope>NPM</scope><scope>AAYXX</scope><scope>CITATION</scope><scope>7X8</scope><orcidid>https://orcid.org/0000-0001-5941-9517</orcidid></search><sort><creationdate>20141013</creationdate><title>Remarkably regioselective deacylation of cellulose esters using tetraalkylammonium salts of the strongly basic hydroxide ion</title><author>Zheng, Xueyan ; Gandour, Richard D. ; Edgar, Kevin J.</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-c461t-97fd0b5406c98e0da69c841444cb21c199c80a7f595397b4927f6494cce104f93</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2014</creationdate><topic>Acylation</topic><topic>Alkylation</topic><topic>Ammonium Compounds - chemistry</topic><topic>Applied sciences</topic><topic>Catalysis</topic><topic>Cellulose - analogs & derivatives</topic><topic>Cellulose - chemistry</topic><topic>Cellulose and derivatives</topic><topic>Cellulose ester</topic><topic>Deacylation</topic><topic>Esters - chemistry</topic><topic>Exact sciences and technology</topic><topic>Hydrolysis</topic><topic>Hydroxides - chemistry</topic><topic>Mechanism</topic><topic>Natural polymers</topic><topic>Physicochemistry of polymers</topic><topic>Regioselectivity</topic><topic>Salts - chemistry</topic><topic>Stereoisomerism</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Zheng, Xueyan</creatorcontrib><creatorcontrib>Gandour, Richard D.</creatorcontrib><creatorcontrib>Edgar, Kevin J.</creatorcontrib><collection>Pascal-Francis</collection><collection>Medline</collection><collection>MEDLINE</collection><collection>MEDLINE (Ovid)</collection><collection>MEDLINE</collection><collection>MEDLINE</collection><collection>PubMed</collection><collection>CrossRef</collection><collection>MEDLINE - Academic</collection><jtitle>Carbohydrate polymers</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Zheng, Xueyan</au><au>Gandour, Richard D.</au><au>Edgar, Kevin J.</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Remarkably regioselective deacylation of cellulose esters using tetraalkylammonium salts of the strongly basic hydroxide ion</atitle><jtitle>Carbohydrate polymers</jtitle><addtitle>Carbohydr Polym</addtitle><date>2014-10-13</date><risdate>2014</risdate><volume>111</volume><spage>25</spage><epage>32</epage><pages>25-32</pages><issn>0144-8617</issn><eissn>1879-1344</eissn><coden>CAPOD8</coden><abstract>•Discovered regioselective cellulose ester deacylation by tetralkylammonium hydroxides.•One step process requiring no protective groups.•Route to cellulose 6-esters and 2,3-A-6-B-triesters.•Regioselective deacylation even with limited equiv of NaOH.
Tetraalkylammonium hydroxides have been found to mediate regioselective deacylation of cellulose esters. This deacylation surprisingly shows substantial selectivity for the removal of the acyl groups at O-2/3, affording cellulose-6-O-esters by a simple, efficient one-step process. The mechanism for this deacylation was investigated by studying the effect of tetraalkylammonium cation size upon ester deacylation selectivity. We hypothesize that coordination of the tetraalkylammonium cation by the ester oxygen atoms of the vicinal 2,3-acetate groups may drive the unexpected regioselectivity at the secondary alcohol esters. Broad scope with respect to ester type was demonstrated; regioselective O-2,3 deacylation was observed with cellulose acetate, propionate, butyrate, hexanoate and benzoate triesters. The scope of this deacylation of cellulose acetates has been investigated to understand how to carry it out most efficiently. Reaction with TBAOH in pyridine was the most effective process, providing the highest selectivity.</abstract><cop>Kidlington</cop><pub>Elsevier Ltd</pub><pmid>25037325</pmid><doi>10.1016/j.carbpol.2014.04.014</doi><tpages>8</tpages><orcidid>https://orcid.org/0000-0001-5941-9517</orcidid></addata></record> |
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| subjects | Acylation Alkylation Ammonium Compounds - chemistry Applied sciences Catalysis Cellulose - analogs & derivatives Cellulose - chemistry Cellulose and derivatives Cellulose ester Deacylation Esters - chemistry Exact sciences and technology Hydrolysis Hydroxides - chemistry Mechanism Natural polymers Physicochemistry of polymers Regioselectivity Salts - chemistry Stereoisomerism |
| title | Remarkably regioselective deacylation of cellulose esters using tetraalkylammonium salts of the strongly basic hydroxide ion |
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