Reaction contest: hydrolysis versus intramolecular cyclisation reaction in alkyl squaramate esters
The stability and hydrolytic behavior of squaramate esters in aqueous solutions have been investigated. The structure of squaramates and the nature of adjacent groups significantly influence their aqueous stability and reactivity towards nucleophiles. Squaramate esters, lacking or containing weakly...
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| creator | Ximenis, Marta Cañellas, Santiago Gomila, Rosa M Galmés, Bartomeu Frontera, Antonio Costa, Antonio Rotger, Carmen |
| description | The stability and hydrolytic behavior of squaramate esters in aqueous solutions have been investigated. The structure of squaramates and the nature of adjacent groups significantly influence their aqueous stability and reactivity towards nucleophiles. Squaramate esters, lacking or containing weakly basic neighboring group participation (NGP) substitutions, remain stable up to pH 9. Their hydrolysis rate (
≈ 10
M
s
) is 1000 times faster than that of squaramides, following a second-order rate law. Squaramate esters functionalized with basic NGP groups, such as amines, display a pH-dependent hydrolysis rate due to anchimeric assistance of the terminal amino group, reducing stability to pH 5. However, when the squaramate ester has a terminal nucleophilic group in the γ position of the alkyl chain, it undergoes rapid intramolecular cyclization, forming cyclic squaramides. |
| doi_str_mv | 10.1039/d4ra04362f |
| format | Article |
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≈ 10
M
s
) is 1000 times faster than that of squaramides, following a second-order rate law. Squaramate esters functionalized with basic NGP groups, such as amines, display a pH-dependent hydrolysis rate due to anchimeric assistance of the terminal amino group, reducing stability to pH 5. However, when the squaramate ester has a terminal nucleophilic group in the γ position of the alkyl chain, it undergoes rapid intramolecular cyclization, forming cyclic squaramides.</description><identifier>ISSN: 2046-2069</identifier><identifier>EISSN: 2046-2069</identifier><identifier>DOI: 10.1039/d4ra04362f</identifier><identifier>PMID: 39399256</identifier><language>eng</language><publisher>England: Royal Society of Chemistry</publisher><subject>Amines ; Aqueous solutions ; Esters ; Hydrolysis ; Nucleophiles ; Stability</subject><ispartof>RSC advances, 2024-10, Vol.14 (44), p.32126-32132</ispartof><rights>This journal is © The Royal Society of Chemistry.</rights><rights>Copyright Royal Society of Chemistry 2024</rights><lds50>peer_reviewed</lds50><oa>free_for_read</oa><woscitedreferencessubscribed>false</woscitedreferencessubscribed><cites>FETCH-LOGICAL-c240t-26a5c7c89c3b79d5f774db397861ec329b18f78027e5f52fb4e89010c10e0df53</cites><orcidid>0000-0003-2478-3807 ; 0000-0002-0827-8504 ; 0000-0001-7840-2139 ; 0000-0002-6550-6307 ; 0000-0002-8700-4615 ; 0000-0002-9418-7798</orcidid></display><links><openurl>$$Topenurl_article</openurl><openurlfulltext>$$Topenurlfull_article</openurlfulltext><thumbnail>$$Tsyndetics_thumb_exl</thumbnail><link.rule.ids>314,776,780,860,27901,27902</link.rule.ids><backlink>$$Uhttps://www.ncbi.nlm.nih.gov/pubmed/39399256$$D View this record in MEDLINE/PubMed$$Hfree_for_read</backlink></links><search><creatorcontrib>Ximenis, Marta</creatorcontrib><creatorcontrib>Cañellas, Santiago</creatorcontrib><creatorcontrib>Gomila, Rosa M</creatorcontrib><creatorcontrib>Galmés, Bartomeu</creatorcontrib><creatorcontrib>Frontera, Antonio</creatorcontrib><creatorcontrib>Costa, Antonio</creatorcontrib><creatorcontrib>Rotger, Carmen</creatorcontrib><title>Reaction contest: hydrolysis versus intramolecular cyclisation reaction in alkyl squaramate esters</title><title>RSC advances</title><addtitle>RSC Adv</addtitle><description>The stability and hydrolytic behavior of squaramate esters in aqueous solutions have been investigated. The structure of squaramates and the nature of adjacent groups significantly influence their aqueous stability and reactivity towards nucleophiles. Squaramate esters, lacking or containing weakly basic neighboring group participation (NGP) substitutions, remain stable up to pH 9. Their hydrolysis rate (
≈ 10
M
s
) is 1000 times faster than that of squaramides, following a second-order rate law. Squaramate esters functionalized with basic NGP groups, such as amines, display a pH-dependent hydrolysis rate due to anchimeric assistance of the terminal amino group, reducing stability to pH 5. However, when the squaramate ester has a terminal nucleophilic group in the γ position of the alkyl chain, it undergoes rapid intramolecular cyclization, forming cyclic squaramides.</description><subject>Amines</subject><subject>Aqueous solutions</subject><subject>Esters</subject><subject>Hydrolysis</subject><subject>Nucleophiles</subject><subject>Stability</subject><issn>2046-2069</issn><issn>2046-2069</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2024</creationdate><recordtype>article</recordtype><recordid>eNpdkE1LAzEQhoMottRe_AES8CLCar6z8VaqVaEgFD0v2WwWt6a7bbIr7L83_RJxLjOHZ54ZXgAuMbrDiKr7gnmNGBWkPAFDgphICBLq9M88AOMQliiW4JgIfA4GVFGlCBdDkC-sNm3V1NA0dWtD-wA_-8I3rg9VgN_Why7Aqm69XjXOms5pD01vXBX0bssf16saavfVOxg2nY60bi2Muii4AGeldsGOD30EPmZP79OXZP72_DqdzBNDGGoTIjQ30qTK0FyqgpdSsiKnSqYCW0OJynFayhQRaXnJSZkzmyqEkcHIoqLkdARu9t61bzZdvJ2tqmCsc7q2TRcyirGgVKacRfT6H7psOl_H77aUpJRItqVu95TxTQjeltnaVyvt-wyjbBt-9sgWk134swhfHZRdvrLFL3qMmv4A_85_8A</recordid><startdate>20241009</startdate><enddate>20241009</enddate><creator>Ximenis, Marta</creator><creator>Cañellas, Santiago</creator><creator>Gomila, Rosa M</creator><creator>Galmés, Bartomeu</creator><creator>Frontera, Antonio</creator><creator>Costa, Antonio</creator><creator>Rotger, Carmen</creator><general>Royal Society of Chemistry</general><scope>NPM</scope><scope>AAYXX</scope><scope>CITATION</scope><scope>7SR</scope><scope>8BQ</scope><scope>8FD</scope><scope>JG9</scope><scope>7X8</scope><orcidid>https://orcid.org/0000-0003-2478-3807</orcidid><orcidid>https://orcid.org/0000-0002-0827-8504</orcidid><orcidid>https://orcid.org/0000-0001-7840-2139</orcidid><orcidid>https://orcid.org/0000-0002-6550-6307</orcidid><orcidid>https://orcid.org/0000-0002-8700-4615</orcidid><orcidid>https://orcid.org/0000-0002-9418-7798</orcidid></search><sort><creationdate>20241009</creationdate><title>Reaction contest: hydrolysis versus intramolecular cyclisation reaction in alkyl squaramate esters</title><author>Ximenis, Marta ; Cañellas, Santiago ; Gomila, Rosa M ; Galmés, Bartomeu ; Frontera, Antonio ; Costa, Antonio ; Rotger, Carmen</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-c240t-26a5c7c89c3b79d5f774db397861ec329b18f78027e5f52fb4e89010c10e0df53</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2024</creationdate><topic>Amines</topic><topic>Aqueous solutions</topic><topic>Esters</topic><topic>Hydrolysis</topic><topic>Nucleophiles</topic><topic>Stability</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Ximenis, Marta</creatorcontrib><creatorcontrib>Cañellas, Santiago</creatorcontrib><creatorcontrib>Gomila, Rosa M</creatorcontrib><creatorcontrib>Galmés, Bartomeu</creatorcontrib><creatorcontrib>Frontera, Antonio</creatorcontrib><creatorcontrib>Costa, Antonio</creatorcontrib><creatorcontrib>Rotger, Carmen</creatorcontrib><collection>PubMed</collection><collection>CrossRef</collection><collection>Engineered Materials Abstracts</collection><collection>METADEX</collection><collection>Technology Research Database</collection><collection>Materials Research Database</collection><collection>MEDLINE - Academic</collection><jtitle>RSC advances</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Ximenis, Marta</au><au>Cañellas, Santiago</au><au>Gomila, Rosa M</au><au>Galmés, Bartomeu</au><au>Frontera, Antonio</au><au>Costa, Antonio</au><au>Rotger, Carmen</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Reaction contest: hydrolysis versus intramolecular cyclisation reaction in alkyl squaramate esters</atitle><jtitle>RSC advances</jtitle><addtitle>RSC Adv</addtitle><date>2024-10-09</date><risdate>2024</risdate><volume>14</volume><issue>44</issue><spage>32126</spage><epage>32132</epage><pages>32126-32132</pages><issn>2046-2069</issn><eissn>2046-2069</eissn><abstract>The stability and hydrolytic behavior of squaramate esters in aqueous solutions have been investigated. The structure of squaramates and the nature of adjacent groups significantly influence their aqueous stability and reactivity towards nucleophiles. Squaramate esters, lacking or containing weakly basic neighboring group participation (NGP) substitutions, remain stable up to pH 9. Their hydrolysis rate (
≈ 10
M
s
) is 1000 times faster than that of squaramides, following a second-order rate law. Squaramate esters functionalized with basic NGP groups, such as amines, display a pH-dependent hydrolysis rate due to anchimeric assistance of the terminal amino group, reducing stability to pH 5. However, when the squaramate ester has a terminal nucleophilic group in the γ position of the alkyl chain, it undergoes rapid intramolecular cyclization, forming cyclic squaramides.</abstract><cop>England</cop><pub>Royal Society of Chemistry</pub><pmid>39399256</pmid><doi>10.1039/d4ra04362f</doi><tpages>7</tpages><orcidid>https://orcid.org/0000-0003-2478-3807</orcidid><orcidid>https://orcid.org/0000-0002-0827-8504</orcidid><orcidid>https://orcid.org/0000-0001-7840-2139</orcidid><orcidid>https://orcid.org/0000-0002-6550-6307</orcidid><orcidid>https://orcid.org/0000-0002-8700-4615</orcidid><orcidid>https://orcid.org/0000-0002-9418-7798</orcidid><oa>free_for_read</oa></addata></record> |
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| language | eng |
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| source | Open Access: PubMed Central; DOAJ Directory of Open Access Journals; EZB Electronic Journals Library; PubMed Central Open Access |
| subjects | Amines Aqueous solutions Esters Hydrolysis Nucleophiles Stability |
| title | Reaction contest: hydrolysis versus intramolecular cyclisation reaction in alkyl squaramate esters |
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