Directing-Group-Free Arene C(sp2)–H Amination Using Bulky Aminium Radicals and DFT Analysis of Regioselectivity

A hydroxylamine-derived electrophilic aminating reagent produces a transient and bulky aminium radical intermediate upon in situ activation by either TMSOTf or TFA and a subsequent electron transfer from an iron(II) catalyst. Density functional theory calculations were used to examine the regiosele...

Ausführliche Beschreibung

Gespeichert in:

Bibliographische Detailangaben
Veröffentlicht in:	Journal of organic chemistry 2023-08, Vol.88 (16), p.11847-11854
Hauptverfasser:	Behnke, Nicole Erin, Kwon, Young-Do, Davenport, Michael T., Ess, Daniel H., Kürti, László
Format:	Artikel
Sprache:	eng
Schlagworte:	amination aromatic hydrocarbons catalysts density functional theory electron transfer iron Lewis acids organic chemistry prediction regioselectivity
Online-Zugang:	Volltext
Tags:	Tag hinzufügen Keine Tags, Fügen Sie den ersten Tag hinzu!

container_end_page	11854
container_issue	16
container_start_page	11847
container_title	Journal of organic chemistry
container_volume	88
creator	Behnke, Nicole Erin Kwon, Young-Do Davenport, Michael T. Ess, Daniel H. Kürti, László
description	A hydroxylamine-derived electrophilic aminating reagent produces a transient and bulky aminium radical intermediate upon in situ activation by either TMSOTf or TFA and a subsequent electron transfer from an iron(II) catalyst. Density functional theory calculations were used to examine the regioselectivity of arene C–H amination reactions on diversely substituted arenes. The calculations suggest a simple charge-controlled regioselectivity model that enables prediction of the major C(sp2)–H amination product.
doi_str_mv	10.1021/acs.joc.3c01127
format	Article
fullrecord	<record><control><sourceid>proquest_cross</sourceid><recordid>TN_cdi_proquest_miscellaneous_3153646764</recordid><sourceformat>XML</sourceformat><sourcesystem>PC</sourcesystem><sourcerecordid>2853941704</sourcerecordid><originalsourceid>FETCH-LOGICAL-a407t-41da8d956aab63150c66df50ff7463cc6fc5a3d3e6b32c76d50211af323ab4813</originalsourceid><addsrcrecordid>eNqFkU1LAzEQhoMotlbP3iTHimybj022PdbWtkJBKO15yWazJXW_muwKe_M_-A_9JaZu9SbOZWB45h2YB4BbjAYYETwU0g72hRxQiTAmwRnoYkaQx8fIPwddhAjxKOG0A66s3SNXjLFL0KEBQ5wy0gWHmTZKVjrfeQtT1KU3N0rBiVG5gtO-Lcn95_vHEk4ynYtKFzncWsfCxzp9bb6nus7gWsRaitRCkcdwNt_ASS7SxmoLiwSu1U4XVqXHK2-6aq7BReJYdXPqPbCdP22mS2_1snieTlae8FFQeT6OxSgeMy5ExClmSHIeJwwlSeBzKiVPJBM0popHlMiAx8z9A4uEEioif4RpD_Tb3NIUh1rZKsy0lSpNRa6K2oYuk3KfB9z_FyUjRsc-DtARHbaoNIW1RiVhaXQmTBNiFB6VhE5J6JSEJyVu4-4UXkeZin_5HwcOeGiBdrM27nn2z7gv-siWtw</addsrcrecordid><sourcetype>Aggregation Database</sourcetype><iscdi>true</iscdi><recordtype>article</recordtype><pqid>2853941704</pqid></control><display><type>article</type><title>Directing-Group-Free Arene C(sp2)–H Amination Using Bulky Aminium Radicals and DFT Analysis of Regioselectivity</title><source>American Chemical Society Journals</source><creator>Behnke, Nicole Erin ; Kwon, Young-Do ; Davenport, Michael T. ; Ess, Daniel H. ; Kürti, László</creator><creatorcontrib>Behnke, Nicole Erin ; Kwon, Young-Do ; Davenport, Michael T. ; Ess, Daniel H. ; Kürti, László</creatorcontrib><description>A hydroxylamine-derived electrophilic aminating reagent produces a transient and bulky aminium radical intermediate upon in situ activation by either TMSOTf or TFA and a subsequent electron transfer from an iron(II) catalyst. Density functional theory calculations were used to examine the regioselectivity of arene C–H amination reactions on diversely substituted arenes. The calculations suggest a simple charge-controlled regioselectivity model that enables prediction of the major C(sp2)–H amination product.</description><identifier>ISSN: 0022-3263</identifier><identifier>ISSN: 1520-6904</identifier><identifier>EISSN: 1520-6904</identifier><identifier>DOI: 10.1021/acs.joc.3c01127</identifier><identifier>PMID: 37506352</identifier><language>eng</language><publisher>United States: American Chemical Society</publisher><subject>amination ; aromatic hydrocarbons ; catalysts ; density functional theory ; electron transfer ; iron ; Lewis acids ; organic chemistry ; prediction ; regioselectivity</subject><ispartof>Journal of organic chemistry, 2023-08, Vol.88 (16), p.11847-11854</ispartof><rights>2023 American Chemical Society</rights><lds50>peer_reviewed</lds50><oa>free_for_read</oa><woscitedreferencessubscribed>false</woscitedreferencessubscribed><citedby>FETCH-LOGICAL-a407t-41da8d956aab63150c66df50ff7463cc6fc5a3d3e6b32c76d50211af323ab4813</citedby><cites>FETCH-LOGICAL-a407t-41da8d956aab63150c66df50ff7463cc6fc5a3d3e6b32c76d50211af323ab4813</cites><orcidid>0000-0002-7515-6021 ; 0000-0001-7483-5260 ; 0000-0001-5689-9762 ; 0000-0002-3412-5894</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/acs.joc.3c01127$$EPDF$$P50$$Gacs$$H</linktopdf><linktohtml>$$Uhttps://pubs.acs.org/doi/10.1021/acs.joc.3c01127$$EHTML$$P50$$Gacs$$H</linktohtml><link.rule.ids>314,778,782,2754,27063,27911,27912,56725,56775</link.rule.ids><backlink>$$Uhttps://www.ncbi.nlm.nih.gov/pubmed/37506352$$D View this record in MEDLINE/PubMed$$Hfree_for_read</backlink></links><search><creatorcontrib>Behnke, Nicole Erin</creatorcontrib><creatorcontrib>Kwon, Young-Do</creatorcontrib><creatorcontrib>Davenport, Michael T.</creatorcontrib><creatorcontrib>Ess, Daniel H.</creatorcontrib><creatorcontrib>Kürti, László</creatorcontrib><title>Directing-Group-Free Arene C(sp2)–H Amination Using Bulky Aminium Radicals and DFT Analysis of Regioselectivity</title><title>Journal of organic chemistry</title><addtitle>J. Org. Chem</addtitle><description>A hydroxylamine-derived electrophilic aminating reagent produces a transient and bulky aminium radical intermediate upon in situ activation by either TMSOTf or TFA and a subsequent electron transfer from an iron(II) catalyst. Density functional theory calculations were used to examine the regioselectivity of arene C–H amination reactions on diversely substituted arenes. The calculations suggest a simple charge-controlled regioselectivity model that enables prediction of the major C(sp2)–H amination product.</description><subject>amination</subject><subject>aromatic hydrocarbons</subject><subject>catalysts</subject><subject>density functional theory</subject><subject>electron transfer</subject><subject>iron</subject><subject>Lewis acids</subject><subject>organic chemistry</subject><subject>prediction</subject><subject>regioselectivity</subject><issn>0022-3263</issn><issn>1520-6904</issn><issn>1520-6904</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2023</creationdate><recordtype>article</recordtype><recordid>eNqFkU1LAzEQhoMotlbP3iTHimybj022PdbWtkJBKO15yWazJXW_muwKe_M_-A_9JaZu9SbOZWB45h2YB4BbjAYYETwU0g72hRxQiTAmwRnoYkaQx8fIPwddhAjxKOG0A66s3SNXjLFL0KEBQ5wy0gWHmTZKVjrfeQtT1KU3N0rBiVG5gtO-Lcn95_vHEk4ynYtKFzncWsfCxzp9bb6nus7gWsRaitRCkcdwNt_ASS7SxmoLiwSu1U4XVqXHK2-6aq7BReJYdXPqPbCdP22mS2_1snieTlae8FFQeT6OxSgeMy5ExClmSHIeJwwlSeBzKiVPJBM0popHlMiAx8z9A4uEEioif4RpD_Tb3NIUh1rZKsy0lSpNRa6K2oYuk3KfB9z_FyUjRsc-DtARHbaoNIW1RiVhaXQmTBNiFB6VhE5J6JSEJyVu4-4UXkeZin_5HwcOeGiBdrM27nn2z7gv-siWtw</recordid><startdate>20230818</startdate><enddate>20230818</enddate><creator>Behnke, Nicole Erin</creator><creator>Kwon, Young-Do</creator><creator>Davenport, Michael T.</creator><creator>Ess, Daniel H.</creator><creator>Kürti, László</creator><general>American Chemical Society</general><scope>NPM</scope><scope>AAYXX</scope><scope>CITATION</scope><scope>7X8</scope><scope>7S9</scope><scope>L.6</scope><orcidid>https://orcid.org/0000-0002-7515-6021</orcidid><orcidid>https://orcid.org/0000-0001-7483-5260</orcidid><orcidid>https://orcid.org/0000-0001-5689-9762</orcidid><orcidid>https://orcid.org/0000-0002-3412-5894</orcidid></search><sort><creationdate>20230818</creationdate><title>Directing-Group-Free Arene C(sp2)–H Amination Using Bulky Aminium Radicals and DFT Analysis of Regioselectivity</title><author>Behnke, Nicole Erin ; Kwon, Young-Do ; Davenport, Michael T. ; Ess, Daniel H. ; Kürti, László</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-a407t-41da8d956aab63150c66df50ff7463cc6fc5a3d3e6b32c76d50211af323ab4813</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2023</creationdate><topic>amination</topic><topic>aromatic hydrocarbons</topic><topic>catalysts</topic><topic>density functional theory</topic><topic>electron transfer</topic><topic>iron</topic><topic>Lewis acids</topic><topic>organic chemistry</topic><topic>prediction</topic><topic>regioselectivity</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Behnke, Nicole Erin</creatorcontrib><creatorcontrib>Kwon, Young-Do</creatorcontrib><creatorcontrib>Davenport, Michael T.</creatorcontrib><creatorcontrib>Ess, Daniel H.</creatorcontrib><creatorcontrib>Kürti, László</creatorcontrib><collection>PubMed</collection><collection>CrossRef</collection><collection>MEDLINE - Academic</collection><collection>AGRICOLA</collection><collection>AGRICOLA - Academic</collection><jtitle>Journal of organic chemistry</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Behnke, Nicole Erin</au><au>Kwon, Young-Do</au><au>Davenport, Michael T.</au><au>Ess, Daniel H.</au><au>Kürti, László</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Directing-Group-Free Arene C(sp2)–H Amination Using Bulky Aminium Radicals and DFT Analysis of Regioselectivity</atitle><jtitle>Journal of organic chemistry</jtitle><addtitle>J. Org. Chem</addtitle><date>2023-08-18</date><risdate>2023</risdate><volume>88</volume><issue>16</issue><spage>11847</spage><epage>11854</epage><pages>11847-11854</pages><issn>0022-3263</issn><issn>1520-6904</issn><eissn>1520-6904</eissn><abstract>A hydroxylamine-derived electrophilic aminating reagent produces a transient and bulky aminium radical intermediate upon in situ activation by either TMSOTf or TFA and a subsequent electron transfer from an iron(II) catalyst. Density functional theory calculations were used to examine the regioselectivity of arene C–H amination reactions on diversely substituted arenes. The calculations suggest a simple charge-controlled regioselectivity model that enables prediction of the major C(sp2)–H amination product.</abstract><cop>United States</cop><pub>American Chemical Society</pub><pmid>37506352</pmid><doi>10.1021/acs.joc.3c01127</doi><tpages>8</tpages><orcidid>https://orcid.org/0000-0002-7515-6021</orcidid><orcidid>https://orcid.org/0000-0001-7483-5260</orcidid><orcidid>https://orcid.org/0000-0001-5689-9762</orcidid><orcidid>https://orcid.org/0000-0002-3412-5894</orcidid><oa>free_for_read</oa></addata></record>
fulltext	fulltext
identifier	ISSN: 0022-3263
ispartof	Journal of organic chemistry, 2023-08, Vol.88 (16), p.11847-11854
issn	0022-3263 1520-6904 1520-6904
language	eng
recordid	cdi_proquest_miscellaneous_3153646764
source	American Chemical Society Journals
subjects	amination aromatic hydrocarbons catalysts density functional theory electron transfer iron Lewis acids organic chemistry prediction regioselectivity
title	Directing-Group-Free Arene C(sp2)–H Amination Using Bulky Aminium Radicals and DFT Analysis of Regioselectivity
url	https://sfx.bib-bvb.de/sfx_tum?ctx_ver=Z39.88-2004&ctx_enc=info:ofi/enc:UTF-8&ctx_tim=2025-01-15T12%3A21%3A41IST&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=Directing-Group-Free%20Arene%20C(sp2)%E2%80%93H%20Amination%20Using%20Bulky%20Aminium%20Radicals%20and%20DFT%20Analysis%20of%20Regioselectivity&rft.jtitle=Journal%20of%20organic%20chemistry&rft.au=Behnke,%20Nicole%20Erin&rft.date=2023-08-18&rft.volume=88&rft.issue=16&rft.spage=11847&rft.epage=11854&rft.pages=11847-11854&rft.issn=0022-3263&rft.eissn=1520-6904&rft_id=info:doi/10.1021/acs.joc.3c01127&rft_dat=%3Cproquest_cross%3E2853941704%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=2853941704&rft_id=info:pmid/37506352&rfr_iscdi=true