{"id":2131,"date":"2014-07-11T08:51:14","date_gmt":"2014-07-11T00:51:14","guid":{"rendered":"\/\/www.gsbet888.com\/?p=2131"},"modified":"2019-08-02T18:56:32","modified_gmt":"2019-08-02T10:56:32","slug":"%e4%ba%9a%e7%a0%9c%e6%b0%a7%e5%8c%96%e7%a1%92%e7%9a%84syn-%ce%b2%e6%b6%88%e9%99%a4-syn-%ce%b2-elimination-of-sulfoxideselenoxide","status":"publish","type":"post","link":"\/\/www.gsbet888.com\/reactions\/%e6%b6%88%e9%99%a4%e5%8f%8d%e5%ba%94\/2014\/07\/%e4%ba%9a%e7%a0%9c%e6%b0%a7%e5%8c%96%e7%a1%92%e7%9a%84syn-%ce%b2%e6%b6%88%e9%99%a4-syn-%ce%b2-elimination-of-sulfoxideselenoxide.html","title":{"rendered":"\u4e9a\u781c\/\u6c27\u5316\u7852\u7684syn-\u03b2\u6d88\u9664 Syn-\u03b2-elimination of Sulfoxide\/Selenoxide"},"content":{"rendered":"<ul>\n<li><strong>\u6982\u8981<\/strong><\/li>\n<\/ul>\n<p>\u5bf9\u4e8e\u62e5\u6709\u03b2-H\u7684\u4e9a\u781c\u6216\u8005\u6c27\u5316\u7852\u5e95\u7269\u8fdb\u884c\u52a0\u70ed\u7684\u8bdd\uff0c\u4f1a\u5f15\u8d77<strong><span style=\"color: #ff6600\"><em>syn<\/em><\/span><span style=\"color: #ff6600\">\uff0d\u03b2\u6d88\u9664<\/span><\/strong>\u53cd\u5e94\uff0c\u6700\u7ec8\u5f62\u6210\u70ef\u70c3\u4ea7\u7269\u3002<\/p>\n<p>\u4e9a\u781c\u5e95\u7269\u867d\u7136\u6bd4\u8f83\u5bb9\u6613\u83b7\u5f97\uff0c\u4f46\u662f\u5982\u679c\u8981\u8fdb\u884c\u8be5\u53cd\u5e94\u7684\u8bdd\uff0c\u9ad8\u6e29(&gt;80\u2103)\u662f\u5fc5\u987b\u7684\u3002\u800c\u53e6\u4e00\u65b9\u9762\uff0c\u5982\u679c\u662f\u6c27\u5316\u7852\u5316\u5408\u7269\u7684\u8bdd\uff0c\u57280\uff5e25\u2103\u5c31\u884c\u8fdb\u884c\u6d88\u9664\u53cd\u5e94\u3002\u7c7b\u4f3c\u7684\uff0c\u6c27\u5316\u80fa\u7684\u8be5\u7c7b\u6d88\u9664\u53cd\u5e94\u88ab\u79f0\u4e3a<a href=\"http:\/\/www.chem-station.com\/user-cgi-bin\/odoos\/ps_search.cgi?act=jump&amp;access=1&amp;url=http%3a%2f%2fwww%2echem%2dstation%2ecom%2fodoos%2fdata%2fn%2dene%2d1%2ehtm\"><span style=\"color: #336600\">Cope\u6d88\u9664<\/span><\/a>\u3002<\/p>\n<p>\u9187\u7c7b\u5e95\u7269\u5148\u5f62\u6210\u6c27\u5316\u7852\u4e2d\u95f4\u4f53\uff0c\u518d\u6d88\u9664\u5f62\u6210\u70ef\u70c3\u7684<span style=\"color: #ff6600\"><strong>\u897f\u6ca2\u30fbGrieco\u6cd5<\/strong><\/span>\uff0c\u53ef\u4ee5\u5728\u6781\u5176\u6e29\u548c\u7684\u6761\u4ef6\u4e0b\u8fdb\u884c\uff0c\u6240\u4ee5\u8be5\u65b9\u6cd5\u53ef\u4ee5\u7528\u6765\u5408\u6210\u66f4\u590d\u6742\u7684\u6240\u9700\u5316\u5408\u7269\u3002\u4f46\u662f\u503c\u5f97\u6ce8\u610f\u7684\u662f\uff0c\u5728\u8be5\u65b9\u6cd5\u4e2d\uff0c\u5fc5\u987b\u4f7f\u7528\u8fc7\u91cf\u7684\u7852\u5316\u5408\u7269\u3002<\/p>\n<p><a href=\"https:\/\/assets.www.gsbet888.com\/uploads\/2014\/06\/grieco_se_1.gif\"><img loading=\"lazy\" decoding=\"async\" class=\"aligncenter size-full wp-image-2135\" src=\"https:\/\/assets.www.gsbet888.com\/uploads\/2014\/06\/grieco_se_1.gif\" alt=\"grieco_se_1\" width=\"472\" height=\"78\" \/><\/a><\/p>\n<p>&nbsp;<\/p>\n<ul>\n<li><strong>\u57fa\u672c\u6587\u732e<\/strong><\/li>\n<\/ul>\n<p>\u30fbClive, D. L. <em>Tetrahedron<\/em> <strong><span style=\"color: #ff6600\">1978<\/span><\/strong>, <em>34<\/em>, 1049. doi:<a href=\"http:\/\/dx.doi.org\/10.1016\/0040-4020(78)80135-5\"><span style=\"color: #336600\">10.1016\/0040-4020(78)80135-5<\/span><\/a><br \/>\n\u30fbNishizawa-Grieco Method: Grieco, P. A.; Gilman,\u00a0S.; Nishizawa, M. <em>J. Org. Chem.<\/em> <strong><span style=\"color: #ff6600\">1976<\/span><\/strong>, <em>41<\/em>, 1485. DOI: <a href=\"http:\/\/dx.doi.org\/10.1021\/jo00870a052\"><span style=\"color: #336600\">10.1021\/jo00870a052<\/span><\/a><\/p>\n<p>&nbsp;<\/p>\n<ul>\n<li><strong>\u53cd\u5e94\u673a\u7406<\/strong><\/li>\n<\/ul>\n<p><a href=\"https:\/\/assets.www.gsbet888.com\/uploads\/2014\/06\/s-ene-4.gif\"><img loading=\"lazy\" decoding=\"async\" class=\"aligncenter size-full wp-image-2136\" src=\"https:\/\/assets.www.gsbet888.com\/uploads\/2014\/06\/s-ene-4.gif\" alt=\"s-ene-4\" width=\"341\" height=\"88\" \/><\/a><\/p>\n<p>Grieco\u6cd5\u7684\u673a\u7406\uff1a<\/p>\n<p><a href=\"https:\/\/assets.www.gsbet888.com\/uploads\/2014\/06\/grieco_se_2.gif\"><img loading=\"lazy\" decoding=\"async\" class=\"aligncenter size-full wp-image-2137\" src=\"https:\/\/assets.www.gsbet888.com\/uploads\/2014\/06\/grieco_se_2.gif\" alt=\"grieco_se_2\" width=\"428\" height=\"129\" \/><\/a><\/p>\n<p>&nbsp;<\/p>\n<ul>\n<li><strong>\u53cd\u5e94\u5b9e\u4f8b<\/strong><\/li>\n<\/ul>\n<p>\u03b1<span class=\"atn\">&#8211;<\/span>\u7fb0\u57fa\u5316\u5408\u7269\u53ef\u4ee5\u7531\u70ef\u9187\u8ddfPhSeBr\u7b49\u53cd\u5e94\u83b7\u5f97\u3002\u8fd9\u662f\u5408\u6210\u03b1,\u03b2-\u4e0d\u9971\u548c\u7fb0\u57fa\u5316\u5408\u7269\u7684\u4e00\u822c\u65b9\u6cd5\u3002[1]\n<p><img loading=\"lazy\" decoding=\"async\" class=\"aligncenter size-full wp-image-2138\" src=\"https:\/\/assets.www.gsbet888.com\/uploads\/2014\/06\/s-ene-1.gif\" alt=\"s-ene-1\" width=\"236\" height=\"83\" \/><\/p>\n<p>\u6c27\u5316\u7852\u57fa\u56e2\u5728\u70ef\u4e19\u57fa\u4f4d\u7684\u60c5\u51b5\u4e0b\u3001\u76f8\u6bd4\u4e8e\u6d88\u9664\u53cd\u5e94\uff0c\u7c7b\u4f3c\u4e8e<a href=\"http:\/\/www.chem-station.com\/user-cgi-bin\/odoos\/ps_search.cgi?act=jump&amp;access=1&amp;url=http%3a%2f%2fwww%2echem%2dstation%2ecom%2fodoos%2fdata%2fmislow_evans_rearr%2ehtm\"><span style=\"color: #336600\">Mislow-Evans\u91cd\u6392<\/span><\/a>[2,3]\u03c3\u91cd\u6392\u53cd\u5e94\u4f18\u5148\u53d1\u751f\u3002\u7531\u4e8e\u91cd\u6392\u540e\u7684O-Se\u952e\u5bb9\u6613\u65ad\u94fe\uff0c\u6240\u4ee5\u53ef\u4ee5\u7528\u6765\u5408\u6210\u70ef\u4e19\u9187\u5316\u5408\u7269\u3002[2]<a href=\"https:\/\/assets.www.gsbet888.com\/uploads\/2014\/06\/s-ene-2.gif\"><img loading=\"lazy\" decoding=\"async\" class=\"aligncenter size-full wp-image-2139\" src=\"https:\/\/assets.www.gsbet888.com\/uploads\/2014\/06\/s-ene-2.gif\" alt=\"s-ene-2\" width=\"335\" height=\"125\" \/><\/a><\/p>\n<p>Gelsemine\u7684\u5408\u6210 [3]\n<p><a href=\"https:\/\/assets.www.gsbet888.com\/uploads\/2014\/06\/grieco_se_3.gif\"><img loading=\"lazy\" decoding=\"async\" class=\"aligncenter size-full wp-image-2140\" src=\"https:\/\/assets.www.gsbet888.com\/uploads\/2014\/06\/grieco_se_3.gif\" alt=\"grieco_se_3\" width=\"395\" height=\"123\" \/><\/a><\/p>\n<p>Merrilactone A\u7684\u5408\u6210 [4]\n<p><a href=\"https:\/\/assets.www.gsbet888.com\/uploads\/2014\/06\/grieco_se_4.gif\"><img loading=\"lazy\" decoding=\"async\" class=\"aligncenter size-full wp-image-2141\" src=\"https:\/\/assets.www.gsbet888.com\/uploads\/2014\/06\/grieco_se_4.gif\" alt=\"grieco_se_4\" width=\"512\" height=\"207\" \/><\/a><\/p>\n<ul>\n<li><strong>\u5b9e\u9a8c\u6b65\u9aa4<\/strong><\/li>\n<\/ul>\n<p>&nbsp;<\/p>\n<ul>\n<li><strong>\u5b9e\u9a8c\u6280\u5de7<\/strong><\/li>\n<\/ul>\n<p>&nbsp;<\/p>\n<ul>\n<li><strong>\u53c2\u8003\u6587\u732e<\/strong><\/li>\n<\/ul>\n[1] Renga, J. M. <em>Org. Synth.<\/em> <strong><span style=\"color: #ff6600\">1988<\/span><\/strong>, <em>6<\/em>, 23.<br \/>\n[2] Vedejs, E.: Duncan, S. M. <em>J. Org. Chem.<\/em> <strong><span style=\"color: #ff6600\">2000<\/span><\/strong>, <em>65<\/em>, 6073. DOI: <a href=\"http:\/\/dx.doi.org\/10.1021\/jo000533q\"><span style=\"color: #336600\">10.1021\/jo000533q<\/span><\/a><br \/>\n[3] Yokoshima, S.; Tokuyama, H.; Fukuyama, T. <em>Angew. Chem. Int. Ed.<\/em> <strong><span style=\"color: #ff6600\">2000<\/span><\/strong>, <em>39<\/em>, 4073. <a href=\"http:\/\/www3.interscience.wiley.com\/journal\/75502324\/abstract\"><span style=\"color: #336600\">[abstract]<\/span><\/a><br \/>\n[4] (a) Birman, V. B.; Danishefsky, S. J. <em>J. Am. Chem. Soc.<\/em> <strong><span style=\"color: #ff6600\">2002<\/span><\/strong>, <em>124<\/em>, 2080.DOI: <a href=\"http:\/\/dx.doi.org\/10.1021\/ja012495d\"><span style=\"color: #336600\">10.1021\/ja012495d<\/span><\/a> (b) Meng, Z.; Danishefsky, S. J. <em>Angew. Chem. Int. Ed.<\/em> <strong><span style=\"color: #ff6600\">2005<\/span><\/strong>, <em>44<\/em>, 1511. DOI: <a href=\"http:\/\/dx.doi.org\/10.1002\/anie.200462509\"><span style=\"color: #336600\">10.1002\/anie.200462509<\/span><\/a> <\/p>\n","protected":false},"excerpt":{"rendered":"\u6982\u8981 \u5bf9\u4e8e\u62e5\u6709\u03b2-H\u7684\u4e9a\u781c\u6216\u8005\u6c27\u5316\u7852\u5e95\u7269\u8fdb\u884c\u52a0\u70ed\u7684\u8bdd\uff0c\u4f1a\u5f15\u8d77syn\uff0d\u03b2\u6d88\u9664\u53cd\u5e94\uff0c\u6700\u7ec8\u5f62\u6210\u70ef\u70c3\u4ea7\u7269\u3002 \u4e9a\u781c\u5e95\u7269\u867d\u7136\u6bd4\u8f83\u5bb9\u6613\u83b7\u5f97\uff0c\u4f46\u662f\u5982\u679c\u8981\u8fdb\u884c\u8be5\u53cd\u5e94\u7684\u8bdd\uff0c\u9ad8\u6e29(&gt;80\u2103)\u662f\u5fc5\u987b\u7684\u3002\u800c\u53e6\u4e00\u65b9\u9762\uff0c\u5982\u679c\u662f\u6c27\u5316\u7852\u5316\u5408\u7269\u7684\u8bdd\uff0c\u57280\uff5e25\u2103\u5c31\u884c\u8fdb\u884c\u6d88\u9664\u53cd\u5e94\u3002\u7c7b\u4f3c\u7684\uff0c\u6c27\u5316\u80fa\u7684\u8be5\u7c7b\u6d88\u9664\u53cd\u5e94\u88ab\u79f0\u4e3aCope\u6d88\u9664\u3002 \u9187\u7c7b\u5e95\u7269\u5148\u5f62\u6210\u6c27\u5316\u7852\u4e2d\u95f4\u4f53\uff0c\u518d\u6d88\u9664\u5f62\u6210\u70ef\u70c3\u7684\u897f\u6ca2\u30fbGrieco\u6cd5\uff0c\u53ef\u4ee5\u5728\u6781\u5176\u6e29\u548c\u7684\u6761\u4ef6\u4e0b\u8fdb\u884c\uff0c\u6240\u4ee5\u8be5\u65b9\u6cd5\u53ef\u4ee5\u7528\u6765\u5408\u6210\u66f4\u590d\u6742\u7684\u6240\u9700\u5316\u5408\u7269\u3002\u4f46\u662f\u503c\u5f97\u6ce8\u610f\u7684\u662f\uff0c\u5728\u8be5\u65b9\u6cd5\u4e2d\uff0c\u5fc5\u987b\u4f7f\u7528\u8fc7\u91cf\u7684\u7852\u5316\u5408\u7269\u3002 &nbsp; \u57fa\u672c\u6587\u732e \u30fbClive, D. L. Tetrahedron 1978, 34, 1049. doi:10.1016\/0040-4020(78)80135-5 \u30fbNishizawa-Grieco Method: Grieco, P. A.; Gilman,\u00a0S.; Nishizawa, M. J. Org. Chem. 1976, 41, 1485. DOI: 10.1021\/jo00870a052 &nbsp; \u53cd\u5e94\u673a\u7406 Grieco\u6cd5\u7684\u673a\u7406\uff1a &nbsp; \u53cd\u5e94\u5b9e\u4f8b \u03b1&#8211;\u7fb0\u57fa\u5316\u5408\u7269\u53ef\u4ee5\u7531\u70ef\u9187\u8ddfPhSeBr\u7b49\u53cd\u5e94\u83b7\u5f97\u3002\u8fd9\u662f\u5408\u6210\u03b1,\u03b2-\u4e0d\u9971\u548c\u7fb0\u57fa\u5316\u5408\u7269\u7684\u4e00\u822c\u65b9\u6cd5\u3002[1] \u6c27\u5316\u7852\u57fa\u56e2\u5728\u70ef\u4e19\u57fa\u4f4d\u7684\u60c5\u51b5\u4e0b\u3001\u76f8\u6bd4\u4e8e\u6d88\u9664\u53cd\u5e94\uff0c\u7c7b\u4f3c\u4e8eMislow-Evans\u91cd\u6392[2,3]\u03c3\u91cd\u6392\u53cd\u5e94\u4f18\u5148\u53d1\u751f\u3002\u7531\u4e8e\u91cd\u6392\u540e\u7684O-Se\u952e\u5bb9\u6613\u65ad\u94fe\uff0c\u6240\u4ee5\u53ef\u4ee5\u7528\u6765\u5408\u6210\u70ef\u4e19\u9187\u5316\u5408\u7269\u3002[2] Gelsemine\u7684\u5408\u6210 [3] Merrilactone A\u7684\u5408\u6210 [4] \u5b9e\u9a8c\u6b65\u9aa4 &nbsp; \u5b9e\u9a8c\u6280\u5de7 &nbsp; \u53c2\u8003\u6587\u732e [1] Renga, J. M. Org. Synth. 1988, 6, 23. [2] Vedejs, E.: Duncan, S. M. J. Org. Chem. 2000, 65, 6073. DOI: 10.1021\/jo000533q [3] Yokoshima, S.; Tokuyama, H.; Fukuyama, T. Angew. Chem. Int. Ed. 2000, 39, 4073. [abstract] [4] (a) Birman, V. B.; Danishefsky, S. J. J. Am. Chem. Soc. 2002, 124, 2080.DOI: 10.1021\/ja012495d (b) Meng, Z.; Danishefsky, S. J. Angew. Chem. Int. [&hellip;]","protected":false},"author":5,"featured_media":2132,"comment_status":"closed","ping_status":"closed","sticky":false,"template":"","format":"standard","meta":{"jetpack_post_was_ever_published":false,"_jetpack_newsletter_access":"","_jetpack_dont_email_post_to_subs":false,"_jetpack_newsletter_tier_id":0,"_jetpack_memberships_contains_paywalled_content":false,"_jetpack_memberships_contains_paid_content":false,"footnotes":"","jetpack_publicize_message":"","jetpack_publicize_feature_enabled":true,"jetpack_social_post_already_shared":true,"jetpack_social_options":{"image_generator_settings":{"template":"highway","enabled":false},"version":2}},"categories":[315],"tags":[351,352],"jetpack_publicize_connections":[],"jetpack_featured_media_url":"https:\/\/assets.www.gsbet888.com\/uploads\/2014\/06\/s-ene-24.gif","jetpack_shortlink":"https:\/\/wp.me\/p96op1-yn","jetpack_sharing_enabled":true,"_links":{"self":[{"href":"\/\/www.gsbet888.com\/wp-json\/wp\/v2\/posts\/2131"}],"collection":[{"href":"\/\/www.gsbet888.com\/wp-json\/wp\/v2\/posts"}],"about":[{"href":"\/\/www.gsbet888.com\/wp-json\/wp\/v2\/types\/post"}],"author":[{"embeddable":true,"href":"\/\/www.gsbet888.com\/wp-json\/wp\/v2\/users\/5"}],"replies":[{"embeddable":true,"href":"\/\/www.gsbet888.com\/wp-json\/wp\/v2\/comments?post=2131"}],"version-history":[{"count":2,"href":"\/\/www.gsbet888.com\/wp-json\/wp\/v2\/posts\/2131\/revisions"}],"predecessor-version":[{"id":28134,"href":"\/\/www.gsbet888.com\/wp-json\/wp\/v2\/posts\/2131\/revisions\/28134"}],"wp:featuredmedia":[{"embeddable":true,"href":"\/\/www.gsbet888.com\/wp-json\/wp\/v2\/media\/2132"}],"wp:attachment":[{"href":"\/\/www.gsbet888.com\/wp-json\/wp\/v2\/media?parent=2131"}],"wp:term":[{"taxonomy":"category","embeddable":true,"href":"\/\/www.gsbet888.com\/wp-json\/wp\/v2\/categories?post=2131"},{"taxonomy":"post_tag","embeddable":true,"href":"\/\/www.gsbet888.com\/wp-json\/wp\/v2\/tags?post=2131"}],"curies":[{"name":"wp","href":"https:\/\/api.w.org\/{rel}","templated":true}]}}