{"id":2140,"date":"2021-09-03T09:09:48","date_gmt":"2021-09-03T07:09:48","guid":{"rendered":"https:\/\/site.uit.no\/nordco2\/?p=2140"},"modified":"2024-10-11T12:21:13","modified_gmt":"2024-10-11T10:21:13","slug":"research-article-helsinki-university-finland-and-uit-norway","status":"publish","type":"post","link":"https:\/\/site.uit.no\/nordco2\/2021\/09\/03\/research-article-helsinki-university-finland-and-uit-norway\/","title":{"rendered":"Research Article: Helsinki University (Finland) and UiT (Norway)"},"content":{"rendered":"<p>A nice collaboration between UiT and Helsinki University\u00a0 on the mechanism of carbamate formation from CO<sub>2<\/sub>\u00a0and amines. Congratulations to all authors!<\/p>\n<p><img fetchpriority=\"high\" decoding=\"async\" class=\"size-full wp-image-1862 aligncenter\" src=\"https:\/\/site.uit.no\/choco\/wp-content\/uploads\/sites\/274\/2021\/09\/D1CY01433A.jpg\" alt=\"\" width=\"704\" height=\"547\" \/><\/p>\n<p><strong>Abstract:<\/strong><br \/>\nCapture of CO<small><sub>2<\/sub><\/small>\u00a0by amines is an attractive synthetic strategy for the formation of carbamates. Such reactions can be mediated by superbases, such as 1,1,3,3,-tetramethylguanidine (TMG), with previous implications that zwitterionic superbase\u2013CO<small><sub>2<\/sub><\/small>\u00a0adducts are able to actively transfer the carboxylate group to various substrates. Here we report a detailed investigation of zwitterionic TMG\u2013CO<small><sub>2<\/sub><\/small>, including isolation, NMR behavior, reactivity, and mechanistic consequences in carboxylation of aniline-derivatives. Our computational and experimental mechanistic analysis shows that the reversible TMG\u2013CO<small><sub>2<\/sub><\/small>\u00a0zwitterion is not a direct carboxylation agent. Instead, CO<small><sub>2<\/sub><\/small>\u00a0dissociates from TMG\u2013CO<small><sub>2<\/sub><\/small>\u00a0before concerted low energy carboxylation occurs, where the role of the TMG is to deprotonate the amine as it is attacking a free CO<small><sub>2<\/sub><\/small>. This insight is significant, as it opens a rational way to design new synthesis strategies. As shown here, nucleophiles otherwise inert towards CO<small><sub>2<\/sub><\/small>\u00a0can be carboxylated, even without a CO<small><sub>2<\/sub><\/small>\u00a0atmosphere, using TMG\u2013CO<small><sub>2<\/sub><\/small>\u00a0as a stoichiometric source of CO<small><sub>2<\/sub><\/small>. We also show natural abundance 15N NMR is sensitive for zwitterion formation, complementing variable-temperature NMR studies.<\/p>\n<p style=\"text-align: center\"><strong>Read at:<\/strong><\/p>\n<p><a href=\"https:\/\/doi.org\/10.1039\/D1CY01433A\"><img decoding=\"async\" class=\"aligncenter wp-image-1864\" src=\"https:\/\/site.uit.no\/choco\/wp-content\/uploads\/sites\/274\/2021\/09\/rsc-logo.png\" alt=\"\" width=\"300\" height=\"84\" \/><\/a><\/p>\n<p>For a list of publications by members of NordCO<small><sub>2<\/sub><\/small>, see our\u00a0<a href=\"https:\/\/site.uit.no\/nordco2\/publications\/\">Publications<\/a>\u00a0page\u00a0\ud83d\ude42<\/p>\n","protected":false},"excerpt":{"rendered":"<p>A nice collaboration between UiT and Helsinki University\u00a0 on the mechanism of carbamate formation from CO2\u00a0and amines. Congratulations to all authors! Abstract: Capture of CO2\u00a0by &hellip;<\/p>\n","protected":false},"author":514,"featured_media":0,"comment_status":"closed","ping_status":"closed","sticky":false,"template":"","format":"standard","meta":{"ngg_post_thumbnail":0,"footnotes":""},"categories":[8],"tags":[],"class_list":["post-2140","post","type-post","status-publish","format-standard","hentry","category-research"],"_links":{"self":[{"href":"https:\/\/site.uit.no\/nordco2\/wp-json\/wp\/v2\/posts\/2140","targetHints":{"allow":["GET"]}}],"collection":[{"href":"https:\/\/site.uit.no\/nordco2\/wp-json\/wp\/v2\/posts"}],"about":[{"href":"https:\/\/site.uit.no\/nordco2\/wp-json\/wp\/v2\/types\/post"}],"author":[{"embeddable":true,"href":"https:\/\/site.uit.no\/nordco2\/wp-json\/wp\/v2\/users\/514"}],"replies":[{"embeddable":true,"href":"https:\/\/site.uit.no\/nordco2\/wp-json\/wp\/v2\/comments?post=2140"}],"version-history":[{"count":2,"href":"https:\/\/site.uit.no\/nordco2\/wp-json\/wp\/v2\/posts\/2140\/revisions"}],"predecessor-version":[{"id":2142,"href":"https:\/\/site.uit.no\/nordco2\/wp-json\/wp\/v2\/posts\/2140\/revisions\/2142"}],"wp:attachment":[{"href":"https:\/\/site.uit.no\/nordco2\/wp-json\/wp\/v2\/media?parent=2140"}],"wp:term":[{"taxonomy":"category","embeddable":true,"href":"https:\/\/site.uit.no\/nordco2\/wp-json\/wp\/v2\/categories?post=2140"},{"taxonomy":"post_tag","embeddable":true,"href":"https:\/\/site.uit.no\/nordco2\/wp-json\/wp\/v2\/tags?post=2140"}],"curies":[{"name":"wp","href":"https:\/\/api.w.org\/{rel}","templated":true}]}}