{"id":3488,"date":"2015-03-30T16:31:20","date_gmt":"2015-03-30T15:31:20","guid":{"rendered":"http:\/\/lewin.ch.pw.edu.pl\/?p=3488"},"modified":"2015-04-20T23:14:22","modified_gmt":"2015-04-20T22:14:22","slug":"zinc-alkylair-systems-as-radical-initiators-for-organic-reactions","status":"publish","type":"post","link":"https:\/\/lewin.ch.pw.edu.pl\/?p=3488","title":{"rendered":"Zinc alkyl\/air systems as radical initiators for organic reactions"},"content":{"rendered":"
Chem. Sci.<\/i>, 2015<\/b>, 6<\/i>, 3102\u20133108.<\/div>\n
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Development of zinc alkyl\/air systems as radical initiators for organic reactions<\/span><\/strong><\/div>\n

Marcin Kubisiak<\/a>,a<\/sup>\u00a0\u00a0Karolina Zelga<\/a>,a<\/sup>\u00a0\u00a0Wojciech Bury<\/a>,a<\/sup>\u00a0 Iwona Justyniak<\/a>,b<\/sup>\u00a0\u00a0 Krzysztof Budny<\/a>,a<\/sup>\u00a0\u00a0 Zbigniew Ochala<\/sup> and\u00a0 Janusz Lewi\u0144ski<\/a>*a<\/sup>b<\/sup><\/strong><\/p>\n

a\u00a0<\/sup>Faculty of Chemistry, Warsaw University of Technology, Noakowskiego 3, 00-664 Warsaw, Poland<\/em>
\nb\u00a0<\/sup>Institute of Physical Chemistry, Polish Academy of Sciences, Kasprzaka 44\/52, 01-224 Warsaw, Poland<\/em><\/p>\n

DOI: <\/strong> 10.1039\/C5SC00600G.
\nReceived 16 Feb 2014, Accepted 19 Mar 2015
\nFirst published online 19 Mar 2015<\/p>\n

This paper reports a series of comparative experiments on the activity of carbon- and oxygen-centred radical species in a model reaction of radical addition of THF to imines mediated by a series of zinc alkyl\/O2<\/sub> reaction systems. The study strongly contradicts the notion that generally R\u2022 radicals are the initiating species in organic reactions mediated by Rn<\/sub>M\/O2<\/sub> systems and simultaneously demonstrates that oxygen-centred radical species are the key intermediates responsible for the initiation process. In addition, a new efficient RZn(L)\/O2<\/sub> initiating system for radical organic reactions exampled by a model reaction of radical addition of THF to imines is developed. Moreover, the isolation and structure characterization of the first zinc alkylperoxide supported by a carboxylate ligand, [Zn4<\/sub>(\u03bc3<\/sub>-OOt<\/i>Bu)3<\/sub>(\u03bc4<\/sub>-O)(O2<\/sub>CEt)3<\/sub>]2<\/sub>, as well as the novel octanuclear zinc oxo(alkoxide) aggregate with entrapped O\u2013THF species, [Zn4<\/sub>(\u03bc4<\/sub>-O)(\u03bc3<\/sub>-2-O\u2013THF)(O2<\/sub>CEt)5<\/sub>]2<\/sub>, provide clear mechanistic signatures for the mode of the RZn(O2<\/sub>CR\u2019)\/O2<\/sub> system\u2019s function.<\/p>\n

\"chemsci2015radicals\"<\/p>\n

Paper on RSC website<\/a><\/p>\n

Full-text PDF<\/a><\/p>\n","protected":false},"excerpt":{"rendered":"

Chem. Sci., 2015, 6, 3102\u20133108.   Development of zinc alkyl\/air systems as radical initiators for organic reactions Marcin Kubisiak,a\u00a0\u00a0Karolina Zelga,a\u00a0\u00a0Wojciech Bury,a\u00a0 Iwona Justyniak,b\u00a0\u00a0 Krzysztof Budny,a\u00a0\u00a0 Zbigniew Ochala and\u00a0 Janusz Lewi\u0144ski*ab a\u00a0Faculty of Chemistry, Warsaw University of Technology, Noakowskiego 3, 00-664 Warsaw, Poland b\u00a0Institute of Physical Chemistry, Polish Academy of Sciences, Kasprzaka 44\/52, 01-224 Warsaw, Poland […]<\/p>\n","protected":false},"author":2,"featured_media":3499,"comment_status":"closed","ping_status":"closed","sticky":false,"template":"","format":"standard","meta":{"inline_featured_image":false,"footnotes":""},"categories":[19],"tags":[],"class_list":["post-3488","post","type-post","status-publish","format-standard","has-post-thumbnail","hentry","category-paper"],"_links":{"self":[{"href":"https:\/\/lewin.ch.pw.edu.pl\/index.php?rest_route=\/wp\/v2\/posts\/3488","targetHints":{"allow":["GET"]}}],"collection":[{"href":"https:\/\/lewin.ch.pw.edu.pl\/index.php?rest_route=\/wp\/v2\/posts"}],"about":[{"href":"https:\/\/lewin.ch.pw.edu.pl\/index.php?rest_route=\/wp\/v2\/types\/post"}],"author":[{"embeddable":true,"href":"https:\/\/lewin.ch.pw.edu.pl\/index.php?rest_route=\/wp\/v2\/users\/2"}],"replies":[{"embeddable":true,"href":"https:\/\/lewin.ch.pw.edu.pl\/index.php?rest_route=%2Fwp%2Fv2%2Fcomments&post=3488"}],"version-history":[{"count":17,"href":"https:\/\/lewin.ch.pw.edu.pl\/index.php?rest_route=\/wp\/v2\/posts\/3488\/revisions"}],"predecessor-version":[{"id":3545,"href":"https:\/\/lewin.ch.pw.edu.pl\/index.php?rest_route=\/wp\/v2\/posts\/3488\/revisions\/3545"}],"wp:featuredmedia":[{"embeddable":true,"href":"https:\/\/lewin.ch.pw.edu.pl\/index.php?rest_route=\/wp\/v2\/media\/3499"}],"wp:attachment":[{"href":"https:\/\/lewin.ch.pw.edu.pl\/index.php?rest_route=%2Fwp%2Fv2%2Fmedia&parent=3488"}],"wp:term":[{"taxonomy":"category","embeddable":true,"href":"https:\/\/lewin.ch.pw.edu.pl\/index.php?rest_route=%2Fwp%2Fv2%2Fcategories&post=3488"},{"taxonomy":"post_tag","embeddable":true,"href":"https:\/\/lewin.ch.pw.edu.pl\/index.php?rest_route=%2Fwp%2Fv2%2Ftags&post=3488"}],"curies":[{"name":"wp","href":"https:\/\/api.w.org\/{rel}","templated":true}]}}