[{"data":1,"prerenderedAt":-1},["ShallowReactive",2],{"detail-sidebar-cat-1-en-105":3,"doc-seo-171440-105":53,"doc-detail-171440-en":126},{"code":4,"msg":5,"data":6},0,"success",[7,14,19,24,29,34,39,44,49],{"id":8,"doc_module":9,"doc_module_name":10,"category_name":11,"show_sort_weight":12,"slug":13},11,1,"Template","Presentations",90,"presentations",{"id":15,"doc_module":9,"doc_module_name":10,"category_name":16,"show_sort_weight":17,"slug":18},12,"Resumes",80,"resumes",{"id":20,"doc_module":9,"doc_module_name":10,"category_name":21,"show_sort_weight":22,"slug":23},14,"Invoices",70,"invoices",{"id":25,"doc_module":9,"doc_module_name":10,"category_name":26,"show_sort_weight":27,"slug":28},15,"Posters",60,"posters",{"id":30,"doc_module":9,"doc_module_name":10,"category_name":31,"show_sort_weight":32,"slug":33},16,"Social Media",50,"social-media",{"id":35,"doc_module":9,"doc_module_name":10,"category_name":36,"show_sort_weight":37,"slug":38},17,"Forms",40,"forms",{"id":40,"doc_module":9,"doc_module_name":10,"category_name":41,"show_sort_weight":42,"slug":43},18,"Letters",30,"letters",{"id":45,"doc_module":9,"doc_module_name":10,"category_name":46,"show_sort_weight":47,"slug":48},21,"Paper Templates",5,"papers-templates",{"id":50,"doc_module":9,"doc_module_name":10,"category_name":51,"show_sort_weight":4,"slug":52},158,"General","general-158",{"code":4,"msg":54,"data":55},"ok",{"site_id":56,"language":57,"slug":58,"title":59,"keywords":60,"description":61,"schema_data":62,"social_meta":119,"head_meta":121,"extra_data":123,"updated_unix":125},105,"en","merging-halogen-atom-transfer-xat-and-cobalt-catalysis-to-override-e2-selectivity-in-the-elimination-of-alkyl-halides","Merging Halogen-Atom Transfer (XAT) and Cobalt Catalysis to Override E2-Selectivity in the Elimination of Alkyl Halides","","A mechanistically distinct strategy enables E2-type eliminations of alkyl halides under mild conditions by combining α-aminoalkyl radical-mediated halogen-atom transfer (XAT) with desaturative cobalt catalysis. The method provides high yields, broad functional-group tolerance, and access to industrially relevant materials. Unlike thermal E2 processes that generate regioisomeric mixtures from unsymmetrical substrates, catalyst electronic and steric tuning achieves high olefin positional selectivity. The approach unlocks contra-thermodynamic olefins that remain elusive to conventional E2 eliminations.",{"@graph":63,"@context":118},[64,80,101],{"@type":65,"itemListElement":66},"BreadcrumbList",[67,71,74,77],{"item":68,"name":69,"@type":70,"position":9},"https://docshare.wps.com","Home","ListItem",{"item":72,"name":10,"@type":70,"position":73},"https://docshare.wps.com/template/",2,{"item":75,"name":11,"@type":70,"position":76},"https://docshare.wps.com/template/presentations/",3,{"item":78,"name":59,"@type":70,"position":79},"https://docshare.wps.com/template/merging-halogen-atom-transfer-xat-and-cobalt-catalysis-to-override-e2-selectivity-in-the-elimination-of-alkyl-halides/171440/",4,{"url":78,"name":59,"@type":81,"image":82,"author":87,"headline":59,"publisher":90,"fileFormat":93,"inLanguage":57,"description":61,"dateModified":94,"datePublished":95,"encodingFormat":93,"isAccessibleForFree":96,"interactionStatistic":97},"DigitalDocument",{"url":83,"@type":84,"width":85,"height":86},"https://docshare.wps.com/thumbnails/merging-halogen-atom-transfer-xat-and-cobalt-catalysis-to-override-e2-selectivity-in-the-elimination-of-alkyl-halides/171440.png","ImageObject",442,249,{"name":88,"@type":89},"Berry Peter","Person",{"url":68,"name":91,"@type":92},"DocShare","Organization","application/vnd.openxmlformats-officedocument.wordprocessingml.document","2026-10-14","2026-09-01",true,{"@type":98,"interactionType":99,"userInteractionCount":47},"InteractionCounter",{"@type":100},"ViewAction",{"@type":102,"mainEntity":103},"FAQPage",[104,110,114],{"name":105,"@type":106,"acceptedAnswer":107},"What does the strategy combine to control E2-type elimination selectivity?","Question",{"text":108,"@type":109},"It merges α-aminoalkyl radical-mediated halogen-atom transfer (XAT) with desaturative cobalt catalysis to drive E2-type eliminations with improved selectivity.","Answer",{"name":111,"@type":106,"acceptedAnswer":112},"How does this method differ from thermal E2 eliminations for unsymmetrical substrates?",{"text":113,"@type":109},"Thermal E2 eliminations typically produce regioisomeric mixtures, whereas cobalt-catalyst tuning enables high olefin positional selectivity.",{"name":115,"@type":106,"acceptedAnswer":116},"Why is the cobalt catalyst important for enabling contra-thermodynamic olefins?",{"text":117,"@type":109},"Fine-tuning the catalyst’s electronic and steric properties governs olefin positioning, making access to contra-thermodynamic olefins possible despite their elusiveness to conventional E2 routes.","https://schema.org",{"og:url":78,"og:type":120,"og:title":59,"og:site_name":91,"og:description":61},"article",{"robots":122,"canonical":78},"index,follow",{"doc_id":124,"site_id":56},171440,1788283120,{"code":4,"msg":5,"data":127},{"doc_id":124,"user_id":128,"nickname":88,"user_avatar":129,"doc_module":9,"category_id":8,"category_name":11,"doc_title":59,"doc_description":61,"doc_content":130,"file_id":131,"file_url":132,"file_type":133,"file_size":134,"view_count":47,"is_deleted":4,"is_public":9,"is_downloadable":9,"audit_status":9,"page_count":135,"language":136,"language_code":57,"site_id":56,"html_lang":57,"table_of_contents":137,"faqs":138,"seo_title":139,"seo_description":61,"update_tm":125,"read_time":79},1374402524268,"https://ap-avatar.wpscdn.com/davatar_3d24733baf745e90a7e4bdd5f77d97b2","\u000fMerging Halogen-Atom Transfer (XAT) and Cobalt Catalysis to Override E2-Selectivity in the Elimination of Alkyl Halides: A Mild Route Towards contra-Thermodynamic Olefins\nHuaibo Zhao,† Alastair J. McMillan,† Timothée Constantin, Rory C. Mykura, Fabio Juliá and Daniele Leonori*\nDepartment of Chemistry, University of Manchester, Oxford Road, Manchester M13 9PL, UK.\nABSTRACT: We report here a mechanistically distinct tactic to carry E2-type eliminations on alkyl halides. This strategy exploits the interplay of -aminoalkyl radicals-mediated halogen-atom transfer (XAT) with desaturative cobalt catalysis. The methodology is high-yielding, tolerates many functionalities and was used to access industrially-relevant materials. In contrast to thermal E2 eliminations where unsymmetrical substrates give regioisomeric mixtures, this approach enables, by fine-tuning of the electronic and steric properties of the cobalt catalyst, to obtain high olefin positional selectivity. This unprecedented mechanistic feature has allowed access to contra-thermodynamic olefins, elusive by E2 eliminations.\nIntroduction\nThe base-promoted -elimination (E2, bimolecular elimination) is a classical reaction of alkyl halides used to access olefin products.\u0013 ADDIN EN.CITE \u003CEndNote>\u003CCite>\u003CAuthor>Knipe\u003C/Author>\u003CYear>1975\u003C/Year>\u003CRecNum>3378\u003C/RecNum>\u003CDisplayText>\u003Cstyle face=\"superscript\">1\u003C/style>\u003C/DisplayText>\u003Crecord>\u003Crec-number>3378\u003C/rec-number>\u003Cforeign-keys>\u003Ckey app=\"EN\" db-id=\"f9arva0tlwwezbewzd8prsrtvefxvzesw2w2\" timestamp=\"1623326465\">3378\u003C/key>\u003C/foreign-keys>\u003Cref-type name=\"Book Section\">5\u003C/ref-type>\u003Ccontributors>\u003Cauthors>\u003Cauthor>Knipe, A. C.\u003C/author>\u003C/authors>\u003C/contributors>\u003Ctitles>\u003Ctitle>Elimination Reactions\u003C/title>\u003Csecondary-title>Organic Reaction Mechanisms · 1973\u003C/secondary-title>\u003C/titles>\u003Cpages>361-380\u003C/pages>\u003Cdates>\u003Cyear>1975\u003C/year>\u003C/dates>\u003Curls>\u003Crelated-urls>\u003Curl>https://onlinelibrary.wiley.com/doi/abs/10.1002/9780470067086.ch11\u003C/url>\u003C/related-urls>\u003C/urls>\u003Celectronic-resource-num>https://doi.org/10.1002/9780470067086.ch11\u003C/electronic-resource-num>\u003C/record>\u003C/Cite>\u003C/EndNote>\u00141\u0015 This reactivity often requires forcing conditions (i.e. strong bases, high T) and, in the case of unsymmetrical substrates, delivers mixtures of regioisomers (Scheme 1A).\u0013 ADDIN EN.CITE \u0013 ADDIN EN.CITE.DATA \u0015\u00142\u0015 Furthermore, primary alkyl halides are notoriously challenging to engage as they undergo nucleophilic substitution (SN2) with the base. Despite these drawbacks, the versatility that olefins offer in terms of further functionalization makes E2 eliminations frequently encountered in the preparation of high-value materials (Scheme 1B).\u0013 ADDIN EN.CITE \u0013 ADDIN EN.CITE.DATA \u0015\u00143\u0015\nIn recent years, alternative approaches aimed at performing these reactions under milder conditions have been developed. Yorimitsu and Oshima\u0013 ADDIN EN.CITE \u003CEndNote>\u003CCite>\u003CAuthor>Kobayashi\u003C/Author>\u003CYear>2008\u003C/Year>\u003CRecNum>3351\u003C/RecNum>\u003CDisplayText>\u003Cstyle face=\"superscript\">4\u003C/style>\u003C/DisplayText>\u003Crecord>\u003Crec-number>3351\u003C/rec-number>\u003Cforeign-keys>\u003Ckey app=\"EN\" db-id=\"f9arva0tlwwezbewzd8prsrtvefxvzesw2w2\" timestamp=\"1622631512\">3351\u003C/key>\u003C/foreign-keys>\u003Cref-type name=\"Journal Article\">17\u003C/ref-type>\u003Ccontributors>\u003Cauthors>\u003Cauthor>Kobayashi, Tsuneyuki\u003C/author>\u003Cauthor>Ohmiya, Hirohisa\u003C/author>\u003Cauthor>Yorimitsu, Hideki\u003C/author>\u003Cauthor>Oshima, Koichiro\u003C/author>\u003C/authors>\u003C/contributors>\u003Ctitles>\u003Ctitle>Cobalt-Catalyzed Regioselective Dehydrohalogenation of Alkyl Halides with Dimethylphenylsilylmethylmagnesium Chloride\u003C/title>\u003Csecondary-title>Journal of the American Chemical Society\u003C/secondary-title>\u003C/titles>\u003Cperiodical>\u003Cfull-title>Journal of the American Chemical Society\u003C/full-title>\u003Cabbr-1>J. Am. Chem. Soc.\u003C/abbr-1>\u003C/periodical>\u003Cpages>11276-11277\u003C/pages>\u003Cvolume>130\u003C/volume>\u003Cnumber>34\u003C/number>\u003Cdates>\u003Cyear>2008\u003C/year>\u003Cpub-dates>\u003Cdate>2008/08/27\u003C/date>\u003C/pub-dates>\u003C/dates>\u003Cpublisher>American Chemical Society\u003C/publisher>\u003Cisbn>0002-7863\u003C/isbn>\u003Curls>\u003Crelated-urls>\u003Curl>https://doi.org/10.1021/ja804277x\u003C/url>\u003C/related","cbCaiml9UV4595ZT","https://ap.wps.com/l/cbCaiml9UV4595ZT","docx",2322534,10,"English","# Abstract\n# Introduction\n## Background: classical E2 elimination\n## Challenges: forcing conditions and substrate limitations\n## Milder approaches: cobalt-mediated strategies","[{\"question\":\"What does the strategy combine to control E2-type elimination selectivity?\",\"answer\":\"It merges α-aminoalkyl radical-mediated halogen-atom transfer (XAT) with desaturative cobalt catalysis to drive E2-type eliminations with improved selectivity.\"},{\"question\":\"How does this method differ from thermal E2 eliminations for unsymmetrical substrates?\",\"answer\":\"Thermal E2 eliminations typically produce regioisomeric mixtures, whereas cobalt-catalyst tuning enables high olefin positional selectivity.\"},{\"question\":\"Why is the cobalt catalyst important for enabling contra-thermodynamic olefins?\",\"answer\":\"Fine-tuning the catalyst’s electronic and steric properties governs olefin positioning, making access to contra-thermodynamic olefins possible despite their elusiveness to conventional E2 routes.\"}]","Merging Halogen-Atom Transfer (XAT) and Cobalt Catalysis to Override E2-Selectivity in the Elimination of Alkyl Halides | DOCX"]