{"id":447,"date":"2025-02-20T18:40:51","date_gmt":"2025-02-20T09:40:51","guid":{"rendered":"http:\/\/achem.okayama-u.ac.jp\/bioorgchem\/?p=447"},"modified":"2025-06-13T11:03:41","modified_gmt":"2025-06-13T02:03:41","slug":"%e3%80%90%e6%96%b0%e7%9d%80%e8%ab%96%e6%96%87%e3%80%91rapid-construction-of-a-diterpene-inspired-tetracyclic-skeleton-bearing-bicyclo3-2-1octane-rings-based-on-desymmetrization-of-13-diketones","status":"publish","type":"post","link":"http:\/\/achem.okayama-u.ac.jp\/bioorgchem\/archives\/447","title":{"rendered":"\u3010\u65b0\u7740\u8ad6\u6587\u3011Rapid construction of a diterpene-inspired tetracyclic skeleton bearing bicyclo[3.2.1]octane rings based on desymmetrization of 1,3-diketones"},"content":{"rendered":"\n<p>\u30d3\u30b7\u30af\u30ed[3.2.1]\u30aa\u30af\u30bf\u30f3\u74b0\u3092\u6709\u3059\u308b\u5929\u7136\u7269\u985e\u4f3c\u591a\u74b0\u6027\u9aa8\u683c\u306e\u8fc5\u901f\u5408\u6210\u306b\u95a2\u3059\u308b\u938c\u7530\u304f\u3093\u306e\u8ad6\u6587\u304c\u30a2\u30af\u30bb\u30d7\u30c8\u3055\u308c\u307e\u3057\u305f\uff01<\/p>\n\n\n\n<p>Hidetoshi\u00a0Kamada,\u00a0Haruki\u00a0Mizoguchi*,\u00a0Akira\u00a0Sakakura*<br>Tetrahedron Letters <strong>2024<\/strong>, <em>157<\/em>, 155470<\/p>\n\n\n\n<p>A synthetic methodology for constructing\u00a0<em>ent<\/em>-kaurane-like tetracyclic skeletons possessing a bicyclo[3.2.1]octane moiety has been developed by employing a desymmetrizing sequential cyclization strategy. Using a symmetric diketone as a key branching point, the sequence of desymmetric Friedel\u2013Crafts cyclization and Pd-catalyzed intramolecular \u03b1-vinylation of ketone allowed us to construct the\u00a0<em>ent<\/em>-kaurane-like tetracyclic skeleton from 1,3-cyclohexanedione in four steps. In contrast, reversing the order of the cyclization steps yielded a pseudo-symmetric tetracyclic skeleton, which is also reminiscent of the kaurane framework.<\/p>\n\n\n\n<p><a href=\"https:\/\/www.sciencedirect.com\/science\/article\/pii\/S004040392500019X\">https:\/\/www.sciencedirect.com\/science\/article\/pii\/S004040392500019X<\/a><\/p>\n","protected":false},"excerpt":{"rendered":"<p>\u30d3\u30b7\u30af\u30ed[3.2.1]\u30aa\u30af\u30bf\u30f3\u74b0\u3092\u6709\u3059\u308b\u5929\u7136\u7269\u985e\u4f3c\u591a\u74b0\u6027\u9aa8\u683c\u306e\u8fc5\u901f\u5408\u6210\u306b\u95a2\u3059\u308b\u938c\u7530\u304f\u3093\u306e\u8ad6\u6587\u304c\u30a2\u30af\u30bb\u30d7\u30c8\u3055\u308c\u307e\u3057\u305f\uff01 Hidetoshi\u00a0Kamada,\u00a0Haruki\u00a0Mizoguchi*,\u00a0Akira\u00a0Sakakura [&hellip;]<\/p>\n","protected":false},"author":1,"featured_media":457,"comment_status":"closed","ping_status":"closed","sticky":false,"template":"","format":"standard","meta":{"vkexunit_cta_each_option":"","footnotes":""},"categories":[4,6],"tags":[],"class_list":["post-447","post","type-post","status-publish","format-standard","has-post-thumbnail","hentry","category-news","category-publications"],"_links":{"self":[{"href":"http:\/\/achem.okayama-u.ac.jp\/bioorgchem\/wp-json\/wp\/v2\/posts\/447","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=447"}],"version-history":[{"count":1,"href":"http:\/\/achem.okayama-u.ac.jp\/bioorgchem\/wp-json\/wp\/v2\/posts\/447\/revisions"}],"predecessor-version":[{"id":448,"href":"http:\/\/achem.okayama-u.ac.jp\/bioorgchem\/wp-json\/wp\/v2\/posts\/447\/revisions\/448"}],"wp:featuredmedia":[{"embeddable":true,"href":"http:\/\/achem.okayama-u.ac.jp\/bioorgchem\/wp-json\/wp\/v2\/media\/457"}],"wp:attachment":[{"href":"http:\/\/achem.okayama-u.ac.jp\/bioorgchem\/wp-json\/wp\/v2\/media?parent=447"}],"wp:term":[{"taxonomy":"category","embeddable":true,"href":"http:\/\/achem.okayama-u.ac.jp\/bioorgchem\/wp-json\/wp\/v2\/categories?post=447"},{"taxonomy":"post_tag","embeddable":true,"href":"http:\/\/achem.okayama-u.ac.jp\/bioorgchem\/wp-json\/wp\/v2\/tags?post=447"}],"curies":[{"name":"wp","href":"https:\/\/api.w.org\/{rel}","templated":true}]}}