Nucleophilic catalysis of p-substituted aniline derivatives in acylhydrazone formation and exchange
Hydrazone bond formation is a versatile reaction employed in several research fields. It is one of the most popular reversible reactions in dynamic combinatorial chemistry. Under physiological conditions, hydrazone exchange benefits from the addition of a nucleophilic catalyst. We report a mechanist...
Gespeichert in:
| Veröffentlicht in: | Organic & biomolecular chemistry 2021-09, Vol.19 (33), p.7202-7210 |
|---|---|
| Hauptverfasser: | , , , , , |
| Format: | Artikel |
| Sprache: | eng |
| Schlagworte: | |
| Online-Zugang: | Volltext |
| Tags: |
Tag hinzufügen
Keine Tags, Fügen Sie den ersten Tag hinzu!
|
| container_end_page | 7210 |
|---|---|
| container_issue | 33 |
| container_start_page | 7202 |
| container_title | Organic & biomolecular chemistry |
| container_volume | 19 |
| creator | Canal-Martín, Andrea Navo, Claudio D Sáez, Elena Molero, Dolores Jiménez-Osés, Gonzalo Pérez-Fernández, Ruth |
| description | Hydrazone bond formation is a versatile reaction employed in several research fields. It is one of the most popular reversible reactions in dynamic combinatorial chemistry. Under physiological conditions, hydrazone exchange benefits from the addition of a nucleophilic catalyst. We report a mechanistic study and superior performance of electron-rich p-substituted aniline derivatives as catalysts for efficient hydrazone formation and exchange in both protic and aprotic solvents. Rigorous kinetic analyses demonstrate that imine formation with 3-hydroxy-4-nitrobenzaldehyde and aniline derivatives proceeds with unprecedented third-order kinetics in which the aldehyde consistently shows a partial order of two. Computational investigations provide insights into the mechanisms of these transformations. |
| doi_str_mv | 10.1039/d1ob00871d |
| format | Article |
| fullrecord | <record><control><sourceid>proquest_cross</sourceid><recordid>TN_cdi_proquest_miscellaneous_2579634575</recordid><sourceformat>XML</sourceformat><sourcesystem>PC</sourcesystem><sourcerecordid>2579634575</sourcerecordid><originalsourceid>FETCH-LOGICAL-c315t-d4e60240405f14b73b0b1c7756fdc73b2a86b944cc632dedd3be6c8334e6f8923</originalsourceid><addsrcrecordid>eNpdkMlOwzAURS0EomXY8AHIEhuEFPAUO1lCyyRVdAPryLEd6iqJi51UhK_H0NIFqzfc866eLgBnGF1jRPMbjV2JUCaw3gNjzIRIUErz_V1P0AgchbBECOeCs0MwooxjQhkZA_XSq9q41cLWVkElO1kPwQboKrhKQl-GznZ9ZzSUbSRaA7Xxdi07uzYB2hZKNdSLQXv55aJYOd9EzcV9q6H5VAvZvpsTcFDJOpjTbT0Gbw_3r5OnZDZ_fJ7czhJFcdolmhmOCEMMpRVmpaAlKrESIuWVVnEiMuNlzphSnBJttKal4SqjNN5VWU7oMbjc-K68--hN6IrGBmXqWrbG9aEgqcg5ZalII3rxD1263rfxu0hxhqhgWRapqw2lvAvBm6pYedtIPxQYFT_RF1M8v_uNfhrh861lXzZG79C_rOk3NTF_hg</addsrcrecordid><sourcetype>Aggregation Database</sourcetype><iscdi>true</iscdi><recordtype>article</recordtype><pqid>2564037488</pqid></control><display><type>article</type><title>Nucleophilic catalysis of p-substituted aniline derivatives in acylhydrazone formation and exchange</title><source>Royal Society Of Chemistry Journals 2008-</source><source>Alma/SFX Local Collection</source><creator>Canal-Martín, Andrea ; Navo, Claudio D ; Sáez, Elena ; Molero, Dolores ; Jiménez-Osés, Gonzalo ; Pérez-Fernández, Ruth</creator><creatorcontrib>Canal-Martín, Andrea ; Navo, Claudio D ; Sáez, Elena ; Molero, Dolores ; Jiménez-Osés, Gonzalo ; Pérez-Fernández, Ruth</creatorcontrib><description>Hydrazone bond formation is a versatile reaction employed in several research fields. It is one of the most popular reversible reactions in dynamic combinatorial chemistry. Under physiological conditions, hydrazone exchange benefits from the addition of a nucleophilic catalyst. We report a mechanistic study and superior performance of electron-rich p-substituted aniline derivatives as catalysts for efficient hydrazone formation and exchange in both protic and aprotic solvents. Rigorous kinetic analyses demonstrate that imine formation with 3-hydroxy-4-nitrobenzaldehyde and aniline derivatives proceeds with unprecedented third-order kinetics in which the aldehyde consistently shows a partial order of two. Computational investigations provide insights into the mechanisms of these transformations.</description><identifier>ISSN: 1477-0520</identifier><identifier>EISSN: 1477-0539</identifier><identifier>DOI: 10.1039/d1ob00871d</identifier><identifier>PMID: 34612342</identifier><language>eng</language><publisher>England: Royal Society of Chemistry</publisher><subject>Aldehydes ; Aniline ; Catalysis ; Catalysts ; Combinatorial analysis ; Combinatorial chemistry ; Computer applications ; Exchanging ; Hydrazones ; NMR ; Nuclear magnetic resonance ; Substitutes</subject><ispartof>Organic & biomolecular chemistry, 2021-09, Vol.19 (33), p.7202-7210</ispartof><rights>Copyright Royal Society of Chemistry 2021</rights><lds50>peer_reviewed</lds50><oa>free_for_read</oa><woscitedreferencessubscribed>false</woscitedreferencessubscribed><citedby>FETCH-LOGICAL-c315t-d4e60240405f14b73b0b1c7756fdc73b2a86b944cc632dedd3be6c8334e6f8923</citedby><cites>FETCH-LOGICAL-c315t-d4e60240405f14b73b0b1c7756fdc73b2a86b944cc632dedd3be6c8334e6f8923</cites><orcidid>0000-0003-0105-4337 ; 0000-0003-0148-6455 ; 0000-0003-0161-412X</orcidid></display><links><openurl>$$Topenurl_article</openurl><openurlfulltext>$$Topenurlfull_article</openurlfulltext><thumbnail>$$Tsyndetics_thumb_exl</thumbnail><link.rule.ids>314,780,784,27924,27925</link.rule.ids><backlink>$$Uhttps://www.ncbi.nlm.nih.gov/pubmed/34612342$$D View this record in MEDLINE/PubMed$$Hfree_for_read</backlink></links><search><creatorcontrib>Canal-Martín, Andrea</creatorcontrib><creatorcontrib>Navo, Claudio D</creatorcontrib><creatorcontrib>Sáez, Elena</creatorcontrib><creatorcontrib>Molero, Dolores</creatorcontrib><creatorcontrib>Jiménez-Osés, Gonzalo</creatorcontrib><creatorcontrib>Pérez-Fernández, Ruth</creatorcontrib><title>Nucleophilic catalysis of p-substituted aniline derivatives in acylhydrazone formation and exchange</title><title>Organic & biomolecular chemistry</title><addtitle>Org Biomol Chem</addtitle><description>Hydrazone bond formation is a versatile reaction employed in several research fields. It is one of the most popular reversible reactions in dynamic combinatorial chemistry. Under physiological conditions, hydrazone exchange benefits from the addition of a nucleophilic catalyst. We report a mechanistic study and superior performance of electron-rich p-substituted aniline derivatives as catalysts for efficient hydrazone formation and exchange in both protic and aprotic solvents. Rigorous kinetic analyses demonstrate that imine formation with 3-hydroxy-4-nitrobenzaldehyde and aniline derivatives proceeds with unprecedented third-order kinetics in which the aldehyde consistently shows a partial order of two. Computational investigations provide insights into the mechanisms of these transformations.</description><subject>Aldehydes</subject><subject>Aniline</subject><subject>Catalysis</subject><subject>Catalysts</subject><subject>Combinatorial analysis</subject><subject>Combinatorial chemistry</subject><subject>Computer applications</subject><subject>Exchanging</subject><subject>Hydrazones</subject><subject>NMR</subject><subject>Nuclear magnetic resonance</subject><subject>Substitutes</subject><issn>1477-0520</issn><issn>1477-0539</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2021</creationdate><recordtype>article</recordtype><recordid>eNpdkMlOwzAURS0EomXY8AHIEhuEFPAUO1lCyyRVdAPryLEd6iqJi51UhK_H0NIFqzfc866eLgBnGF1jRPMbjV2JUCaw3gNjzIRIUErz_V1P0AgchbBECOeCs0MwooxjQhkZA_XSq9q41cLWVkElO1kPwQboKrhKQl-GznZ9ZzSUbSRaA7Xxdi07uzYB2hZKNdSLQXv55aJYOd9EzcV9q6H5VAvZvpsTcFDJOpjTbT0Gbw_3r5OnZDZ_fJ7czhJFcdolmhmOCEMMpRVmpaAlKrESIuWVVnEiMuNlzphSnBJttKal4SqjNN5VWU7oMbjc-K68--hN6IrGBmXqWrbG9aEgqcg5ZalII3rxD1263rfxu0hxhqhgWRapqw2lvAvBm6pYedtIPxQYFT_RF1M8v_uNfhrh861lXzZG79C_rOk3NTF_hg</recordid><startdate>20210907</startdate><enddate>20210907</enddate><creator>Canal-Martín, Andrea</creator><creator>Navo, Claudio D</creator><creator>Sáez, Elena</creator><creator>Molero, Dolores</creator><creator>Jiménez-Osés, Gonzalo</creator><creator>Pérez-Fernández, Ruth</creator><general>Royal Society of Chemistry</general><scope>NPM</scope><scope>AAYXX</scope><scope>CITATION</scope><scope>7QO</scope><scope>7T7</scope><scope>7TM</scope><scope>8FD</scope><scope>C1K</scope><scope>FR3</scope><scope>P64</scope><scope>7X8</scope><orcidid>https://orcid.org/0000-0003-0105-4337</orcidid><orcidid>https://orcid.org/0000-0003-0148-6455</orcidid><orcidid>https://orcid.org/0000-0003-0161-412X</orcidid></search><sort><creationdate>20210907</creationdate><title>Nucleophilic catalysis of p-substituted aniline derivatives in acylhydrazone formation and exchange</title><author>Canal-Martín, Andrea ; Navo, Claudio D ; Sáez, Elena ; Molero, Dolores ; Jiménez-Osés, Gonzalo ; Pérez-Fernández, Ruth</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-c315t-d4e60240405f14b73b0b1c7756fdc73b2a86b944cc632dedd3be6c8334e6f8923</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2021</creationdate><topic>Aldehydes</topic><topic>Aniline</topic><topic>Catalysis</topic><topic>Catalysts</topic><topic>Combinatorial analysis</topic><topic>Combinatorial chemistry</topic><topic>Computer applications</topic><topic>Exchanging</topic><topic>Hydrazones</topic><topic>NMR</topic><topic>Nuclear magnetic resonance</topic><topic>Substitutes</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Canal-Martín, Andrea</creatorcontrib><creatorcontrib>Navo, Claudio D</creatorcontrib><creatorcontrib>Sáez, Elena</creatorcontrib><creatorcontrib>Molero, Dolores</creatorcontrib><creatorcontrib>Jiménez-Osés, Gonzalo</creatorcontrib><creatorcontrib>Pérez-Fernández, Ruth</creatorcontrib><collection>PubMed</collection><collection>CrossRef</collection><collection>Biotechnology Research Abstracts</collection><collection>Industrial and Applied Microbiology Abstracts (Microbiology A)</collection><collection>Nucleic Acids Abstracts</collection><collection>Technology Research Database</collection><collection>Environmental Sciences and Pollution Management</collection><collection>Engineering Research Database</collection><collection>Biotechnology and BioEngineering Abstracts</collection><collection>MEDLINE - Academic</collection><jtitle>Organic & biomolecular chemistry</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Canal-Martín, Andrea</au><au>Navo, Claudio D</au><au>Sáez, Elena</au><au>Molero, Dolores</au><au>Jiménez-Osés, Gonzalo</au><au>Pérez-Fernández, Ruth</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Nucleophilic catalysis of p-substituted aniline derivatives in acylhydrazone formation and exchange</atitle><jtitle>Organic & biomolecular chemistry</jtitle><addtitle>Org Biomol Chem</addtitle><date>2021-09-07</date><risdate>2021</risdate><volume>19</volume><issue>33</issue><spage>7202</spage><epage>7210</epage><pages>7202-7210</pages><issn>1477-0520</issn><eissn>1477-0539</eissn><abstract>Hydrazone bond formation is a versatile reaction employed in several research fields. It is one of the most popular reversible reactions in dynamic combinatorial chemistry. Under physiological conditions, hydrazone exchange benefits from the addition of a nucleophilic catalyst. We report a mechanistic study and superior performance of electron-rich p-substituted aniline derivatives as catalysts for efficient hydrazone formation and exchange in both protic and aprotic solvents. Rigorous kinetic analyses demonstrate that imine formation with 3-hydroxy-4-nitrobenzaldehyde and aniline derivatives proceeds with unprecedented third-order kinetics in which the aldehyde consistently shows a partial order of two. Computational investigations provide insights into the mechanisms of these transformations.</abstract><cop>England</cop><pub>Royal Society of Chemistry</pub><pmid>34612342</pmid><doi>10.1039/d1ob00871d</doi><tpages>9</tpages><orcidid>https://orcid.org/0000-0003-0105-4337</orcidid><orcidid>https://orcid.org/0000-0003-0148-6455</orcidid><orcidid>https://orcid.org/0000-0003-0161-412X</orcidid><oa>free_for_read</oa></addata></record> |
| fulltext | fulltext |
| identifier | ISSN: 1477-0520 |
| ispartof | Organic & biomolecular chemistry, 2021-09, Vol.19 (33), p.7202-7210 |
| issn | 1477-0520 1477-0539 |
| language | eng |
| recordid | cdi_proquest_miscellaneous_2579634575 |
| source | Royal Society Of Chemistry Journals 2008-; Alma/SFX Local Collection |
| subjects | Aldehydes Aniline Catalysis Catalysts Combinatorial analysis Combinatorial chemistry Computer applications Exchanging Hydrazones NMR Nuclear magnetic resonance Substitutes |
| title | Nucleophilic catalysis of p-substituted aniline derivatives in acylhydrazone formation and exchange |
| url | https://sfx.bib-bvb.de/sfx_tum?ctx_ver=Z39.88-2004&ctx_enc=info:ofi/enc:UTF-8&ctx_tim=2024-12-20T16%3A55%3A22IST&url_ver=Z39.88-2004&url_ctx_fmt=infofi/fmt:kev:mtx:ctx&rfr_id=info:sid/primo.exlibrisgroup.com:primo3-Article-proquest_cross&rft_val_fmt=info:ofi/fmt:kev:mtx:journal&rft.genre=article&rft.atitle=Nucleophilic%20catalysis%20of%20p-substituted%20aniline%20derivatives%20in%20acylhydrazone%20formation%20and%20exchange&rft.jtitle=Organic%20&%20biomolecular%20chemistry&rft.au=Canal-Mart%C3%ADn,%20Andrea&rft.date=2021-09-07&rft.volume=19&rft.issue=33&rft.spage=7202&rft.epage=7210&rft.pages=7202-7210&rft.issn=1477-0520&rft.eissn=1477-0539&rft_id=info:doi/10.1039/d1ob00871d&rft_dat=%3Cproquest_cross%3E2579634575%3C/proquest_cross%3E%3Curl%3E%3C/url%3E&disable_directlink=true&sfx.directlink=off&sfx.report_link=0&rft_id=info:oai/&rft_pqid=2564037488&rft_id=info:pmid/34612342&rfr_iscdi=true |