{"id":138,"date":"2021-11-25T15:44:47","date_gmt":"2021-11-25T06:44:47","guid":{"rendered":"http:\/\/achem.okayama-u.ac.jp\/bioorgchem\/WordPress\/?p=138"},"modified":"2021-11-25T15:55:51","modified_gmt":"2021-11-25T06:55:51","slug":"regioselective-dmad-insertion-reaction-of-silyl-dienol-ether-of-%ce%b3-pyrone-under-catalyst-and-heating-free-conditions","status":"publish","type":"post","link":"http:\/\/achem.okayama-u.ac.jp\/bioorgchem\/archives\/138","title":{"rendered":"Regioselective DMAD-insertion Reaction of Silyl Dienol Ether of \u03b3-Pyrone under Catalyst- and Heating-Free Conditions"},"content":{"rendered":"\n<p>Ichiro Hayakawa,* Yuji Yamanaka, Koichi Mitsudo, Hiromi Ota, Akira Sakakura*&nbsp;<br><em>Heterocycles<\/em><strong>2017<\/strong>,&nbsp;<em>94<\/em>&nbsp;(12), 2299\u20132306.&nbsp; (Published online: Oct 26, 2017)&nbsp;<br><a href=\"https:\/\/doi.org\/10.3987\/COM-17-13820\">DOI: 10.3987\/COM-17-13820&nbsp;<img decoding=\"async\" src=\"http:\/\/www.cc.okayama-u.ac.jp\/~sakakura\/bioorgchem\/_src\/9140\/img20180629093542651479.png\" alt=\"LinkIcon\"><\/a><\/p>\n\n\n\n<figure class=\"wp-block-image size-full\"><img loading=\"lazy\" decoding=\"async\" width=\"400\" height=\"172\" src=\"http:\/\/achem.okayama-u.ac.jp\/bioorgchem\/WordPress\/wp-content\/uploads\/2021\/07\/com_17_13820ga.png\" alt=\"\" class=\"wp-image-139\" srcset=\"http:\/\/achem.okayama-u.ac.jp\/bioorgchem\/WordPress\/wp-content\/uploads\/2021\/07\/com_17_13820ga.png 400w, http:\/\/achem.okayama-u.ac.jp\/bioorgchem\/WordPress\/wp-content\/uploads\/2021\/07\/com_17_13820ga-300x129.png 300w\" sizes=\"auto, (max-width: 400px) 100vw, 400px\" \/><\/figure>\n\n\n\n<p>The reaction of silyl dienol ether of \u03b3-pyrone with dimethyl acetylenedicarboxylate (DMAD) gives the regioselective insertion product in 66% yield. &nbsp;This DMAD-insertion reaction is thought to include a three-step sequence: (1) thermal [2+2]-type cycloaddition reaction of silyl dienol ether of \u03b3-pyrone with DMAD, (2) ring-opening electrocyclic reaction of the cyclobutene skeleton, and (3) hydrolysis of the silyl dienol ether. &nbsp;The present reaction proceeds under mild conditions without any catalysts or heating. &nbsp;In addition, the [2+2]-type cycloaddition reaction proceeds regioselectively at the C3\u2013C4 double bond in the silyl dienol ether of \u03b3-pyrone.<\/p>\n","protected":false},"excerpt":{"rendered":"<p>Ichiro Hayakawa,* Yuji Yamanaka, Koichi Mitsudo, Hiromi Ota, Akira Sakakura*&nbsp;Heterocycles2017,&nbsp;94&#038;nb [&hellip;]<\/p>\n","protected":false},"author":1,"featured_media":139,"comment_status":"closed","ping_status":"closed","sticky":false,"template":"","format":"standard","meta":{"vkexunit_cta_each_option":"","footnotes":""},"categories":[6],"tags":[],"class_list":["post-138","post","type-post","status-publish","format-standard","has-post-thumbnail","hentry","category-publications"],"_links":{"self":[{"href":"http:\/\/achem.okayama-u.ac.jp\/bioorgchem\/wp-json\/wp\/v2\/posts\/138","targetHints":{"allow":["GET"]}}],"collection":[{"href":"http:\/\/achem.okayama-u.ac.jp\/bioorgchem\/wp-json\/wp\/v2\/posts"}],"about":[{"href":"http:\/\/achem.okayama-u.ac.jp\/bioorgchem\/wp-json\/wp\/v2\/types\/post"}],"author":[{"embeddable":true,"href":"http:\/\/achem.okayama-u.ac.jp\/bioorgchem\/wp-json\/wp\/v2\/users\/1"}],"replies":[{"embeddable":true,"href":"http:\/\/achem.okayama-u.ac.jp\/bioorgchem\/wp-json\/wp\/v2\/comments?post=138"}],"version-history":[{"count":2,"href":"http:\/\/achem.okayama-u.ac.jp\/bioorgchem\/wp-json\/wp\/v2\/posts\/138\/revisions"}],"predecessor-version":[{"id":257,"href":"http:\/\/achem.okayama-u.ac.jp\/bioorgchem\/wp-json\/wp\/v2\/posts\/138\/revisions\/257"}],"wp:featuredmedia":[{"embeddable":true,"href":"http:\/\/achem.okayama-u.ac.jp\/bioorgchem\/wp-json\/wp\/v2\/media\/139"}],"wp:attachment":[{"href":"http:\/\/achem.okayama-u.ac.jp\/bioorgchem\/wp-json\/wp\/v2\/media?parent=138"}],"wp:term":[{"taxonomy":"category","embeddable":true,"href":"http:\/\/achem.okayama-u.ac.jp\/bioorgchem\/wp-json\/wp\/v2\/categories?post=138"},{"taxonomy":"post_tag","embeddable":true,"href":"http:\/\/achem.okayama-u.ac.jp\/bioorgchem\/wp-json\/wp\/v2\/tags?post=138"}],"curies":[{"name":"wp","href":"https:\/\/api.w.org\/{rel}","templated":true}]}}