{"id":15135,"date":"2017-08-07T07:07:39","date_gmt":"2017-08-06T23:07:39","guid":{"rendered":"\/\/www.gsbet888.com\/?p=15135"},"modified":"2019-08-02T18:52:54","modified_gmt":"2019-08-02T10:52:54","slug":"%e6%b2%b3%e8%b1%9a%e6%af%92%e7%b4%a0tetrodotoxin-%e7%9a%84%e5%85%a8%e5%90%88%e6%88%90-y-kishi-vs-j-du-bois","status":"publish","type":"post","link":"\/\/www.gsbet888.com\/%e5%8c%96%e5%ad%a6%e6%9d%82%e8%ae%b0\/2017\/08\/%e6%b2%b3%e8%b1%9a%e6%af%92%e7%b4%a0tetrodotoxin-%e7%9a%84%e5%85%a8%e5%90%88%e6%88%90-y-kishi-vs-j-du-bois.html","title":{"rendered":"\u6cb3\u8c5a\u6bd2\u7d20(Tetrodotoxin) \u7684\u5168\u5408\u6210 Y. Kishi VS J. du Bois"},"content":{"rendered":"<p><strong>\u672c\u6587\u6295\u7a3f\u4f5c\u8005 alberto-caeiro<\/strong><\/p>\n<p>\u6cb3\u8c5a\u9c7c\u4f5c\u4e3a\u4e00\u79cd\u65e5\u672c\u7279\u522b\u7684\u70f9\u996a\u98df\u6750\u800c\u95fb\u540d\u3002\u4f46\u5982\u679c\u5904\u7406\u4e0d\u5f53\uff0c\u4e00\u9910\u7684\u6cb3\u8c5a\u9c7c\u8db3\u4ee5\u4f7f\u9910\u684c\u4e0a\u7684\u5404\u4f4d\u98df\u5ba2\u4e27\u547d\u3002\u4e8e\u662f\u5728\u65e5\u672c\uff0c\u80fd\u591f\u70f9\u996a\u6cb3\u8c5a\u9c7c\u7684\u5927\u53a8\u90fd\u9700\u8981\u5b66\u4e60\u8003\u8bd5\uff0c\u4ee5\u83b7\u5f97\u7279\u6b8a\u7684\u8bb8\u53ef\u8bc1\u3002<\/p>\n<p>19\u4e16\u7eaa\u5f00\u59cb\uff0c\u65e5\u672c\u5c31\u6709\u8bb8\u591a\u751f\u7269\u5b66\u5bb6\u5f00\u59cb\u7814\u7a76\u8fd9\u79cd\u5267\u6bd2\u7684\u7269\u8d28\u30021911\u5e74\uff0cTahara\u62a5\u9053\u4e86\u8fd9\u79cd\u5267\u6bd2\u7684\u63d0\u7eaf\u7269\uff0c\u5e76\u5c06\u5176\u547d\u540d\u4e3atetrodotoxin<sup>[1]<\/sup>\u3002\u867d\u7136\u5728\u540e\u6765\u8bc1\u660e\u5176\u4e2d\u53ea\u542b\u6709\u5c11\u91cf\u7684tetrodotoxin\uff0c\u4f46\u5176\u5173\u952e\u6027\u7684\u5206\u79bb\u4e3a\u65e5\u540e\u7684\u5de5\u4f5c\u63d0\u4f9b\u4e86\u8bb8\u591a\u5e2e\u52a9\uff0c\u5e76\u5728\u5f53\u65f6\u7684\u836f\u5b66\u7814\u7a76\u63d0\u4f9b\u4e86\u57fa\u7840\u3002\u57281952\u5e74\uff0c\u6d25\u7530\u548c\u5ddd\u6751\u4e5f\u5206\u79bb\u51fa\u8fd9\u79cd\u5316\u5408\u7269\uff0c\u5e76\u4e14\u6cbf\u7528\u4e86tetrodotoxin<sup> [2]<\/sup>\u3002\u5728\u7b2c\u4e09\u5c4aIUPAC\uff08Kyoto Japan\uff09\u4e0a\uff0cTsuda<sup>[3]<\/sup>\uff0cGoto<sup>[4]<\/sup>\uff0c<a href=\"\/\/www.gsbet888.com\/chemists\/2014\/06\/%e7%bd%97%e4%bc%af%e7%89%b9%c2%b7%e4%bc%af%e6%81%a9%e6%96%af%c2%b7%e4%bc%8d%e5%be%b7%e6%b2%83%e5%be%b7-robert-burns-woodward.html\">Woodward<\/a><sup>[5]<\/sup>\u90fd\u5c55\u793a\u4e86\u5404\u81ea\u5f97\u5230\u6cb3\u8c5a\u6bd2\u7d20\u7684\u7ed3\u6784\u5f0f\uff0c\u4e09\u8005\u540c\u65f6\u4e14\u72ec\u7acb\u7684\u5f97\u5230\u4e86\u6cb3\u8c5a\u6bd2\u7d20\u7684\u7ed3\u6784\u5f0f\uff0c\u5982\u4e0b\u56fe1\u6240\u793a\u3002<\/p>\n<p><a href=\"https:\/\/assets.www.gsbet888.com\/uploads\/2017\/07\/1-4.jpg\"><img loading=\"lazy\" decoding=\"async\" class=\"aligncenter wp-image-15136 size-full\" src=\"https:\/\/assets.www.gsbet888.com\/uploads\/2017\/07\/1-4.jpg\" alt=\"\" width=\"557\" height=\"187\" srcset=\"https:\/\/assets.www.gsbet888.com\/uploads\/2017\/07\/1-4.jpg 557w, https:\/\/assets.www.gsbet888.com\/uploads\/2017\/07\/1-4-300x101.jpg 300w\" sizes=\"(max-width: 557px) 100vw, 557px\" \/><\/a><\/p>\n<p style=\"text-align: center\"><em>\u56fe1\uff1atetrodotoxin\u4e09\u79cd\u5f62\u5f0f<\/em><\/p>\n<p>\u6cb3\u8c5a\u6bd2\u7d20\u662f\u4e00\u79cd\u795e\u7ecf\u6bd2\u7d20\uff0c\u5bf9\u94a0\u79bb\u5b50\u901a\u9053\u6709\u6291\u5236\u4f5c\u7528\u3002\u6cb3\u8c5a\u6bd2\u7d20\u80fd\u591f\u6291\u5236\u94a0\u79bb\u5b50\u901a\u9053\u7684\u5f00\u653e\uff0c\u6545\u53ef\u4ee5\u9ad8\u6548\u7684\u5173\u95ed\u5468\u56f4\u795e\u7ecf\u7cfb\u7edf\u3002\u6839\u636e\u98df\u7528\u91cf\u7684\u4e0d\u540c\uff0c\u75c7\u72b6\u4ece\u9ebb\u75f9\u3001\u660f\u8ff7\u3001\u547c\u5438\u8870\u5f31\u3001\u6b7b\u4ea1\u4f9d\u6b21\u9012\u589e\u3002\u6709\u8da3\u7684\u662f\uff0c\u6cb3\u8c5a\u6bd2\u7d20\u5bf9\u5927\u8111\u795e\u7ecf\u6ca1\u6709\u76f4\u63a5\u4f5c\u7528\uff0c\u4e2d\u6bd2\u8005\u76f4\u81f3\u6b7b\u4ea1\u65f6\u624d\u6709\u610f\u8bc6\u5230\u4e2d\u6bd2\u3002\u5176\u9009\u62e9\u6027\u7684\u4f5c\u7528\u673a\u5236\u4f7f\u5f97\u5176\u5728\u836f\u5b66\u548c\u751f\u7269\u5316\u5b66\u4e0a\u6709\u8bb8\u591a\u7814\u7a76\u3002<\/p>\n<p>&nbsp;<\/p>\n<h4>Kishi\u7684\u5168\u5408\u6210\u7814\u7a76<sup>[6,7]<\/sup><\/h4>\n<p><strong><em>1<\/em><\/strong><strong><em>\uff09\u9006\u5408\u6210\u5206\u6790<\/em><\/strong><\/p>\n<p>\u5f97\u76ca\u4e8e\u5728Goto\u7ec4\u5173\u4e8e\u6cb3\u8c5a\u6bd2\u7d20\u7ed3\u6784\u7684\u7814\u7a76\uff0cY. Kishi\u5f97\u5230\u8bb8\u591a\u6cb3\u8c5a\u6bd2\u7d20\u7269\u7406\u548c\u5316\u5b66\u6027\u8d28\u7684\u7b2c\u4e00\u624b\u8d44\u6599\uff0c\u8fd9\u4e9b\u90fd\u88ab\u6709\u6548\u7684\u8fd0\u7528\u5230\u5176\u5408\u6210\u7b56\u7565\u4e2d\u3002\u4e0b\u56fe2\u4e3aY. Kishi\u7ec4\u7684\u9006\u5408\u6210\u5206\u6790\u3002<\/p>\n<p><a href=\"https:\/\/assets.www.gsbet888.com\/uploads\/2017\/07\/2-5.jpg\"><img loading=\"lazy\" decoding=\"async\" class=\"aligncenter wp-image-15137 size-large\" src=\"https:\/\/assets.www.gsbet888.com\/uploads\/2017\/07\/2-5-680x460.jpg\" alt=\"\" width=\"680\" height=\"460\" srcset=\"https:\/\/assets.www.gsbet888.com\/uploads\/2017\/07\/2-5-680x460.jpg 680w, https:\/\/assets.www.gsbet888.com\/uploads\/2017\/07\/2-5-300x203.jpg 300w, https:\/\/assets.www.gsbet888.com\/uploads\/2017\/07\/2-5.jpg 687w\" sizes=\"(max-width: 680px) 100vw, 680px\" \/><\/a><\/p>\n<p style=\"text-align: center\"><em>\u56fe2\uff1aKishi\u2019s retrosynthesis of Tetrodotoxin<\/em><\/p>\n<p>\u56e0\u6cb3\u8c5a\u6bd2\u7d20\u6613\u6eb6\u4e8e\u6c34\u800c\u96be\u6eb6\u4e8e\u6709\u673a\u6eb6\u5242\uff0c\u4e8e\u662f\u6784\u60f3\u5207\u6389\u80cd\u57fa\u540e\u7684\u7269\u8d28\u518d\u7ecf\u4e59\u9170\u57fa\u4fee\u9970\u540e\u5f97\u5230102\u8fd9\u79cd\u65b9\u6848\uff0c\u800c\u5728Goto\u7ec4\u5df2\u5f97\u5230\u8bc1\u660e\uff0c\u867d\u7136\u6cb3\u8c5a\u6bd2\u7d20\u78b1\u6027\u6761\u4ef6\u4e0b\u4e0d\u7a33\u5b9a\uff0c\u4f46\u4e59\u9170\u57fa\u4fdd\u62a4\u7684\u884d\u751f\u7269\u53ef\u4ee5\u5728\u6e29\u548c\u6761\u4ef6\u4e0b\u53ef\u4ee5\u53bb\u4fdd\u62a4\u3002<\/p>\n<p><strong><em>2<\/em><\/strong><strong><em>\uff09Tetrodotoxin\u7684\u5168\u5408\u6210<\/em><\/strong><\/p>\n<p>\u5e95\u7269113\u4e0e\u4e01\u4e8c\u70ef\u76f4\u63a5\u53d1\u751fD-A\u53cd\u5e94\u65f6\uff0c\u809f\u57fa\u662f\u7ed9\u7535\u5b50\u57fa\u56e2\uff0c\u53cd\u5e94\u53ea\u4f1a\u5f97\u5230\u70ed\u529b\u5b66\u63a7\u5236\u7684\u4ea7\u7269114\u3002\u4e8e\u662f\uff0cY. Kishi\u901a\u8fc7\u52a0\u5165Lewis\u9178\u4e8c\u6c2f\u5316\u9521\uff0c\u5f97\u5230\u540c\u9762\u53cd\u5e94\u7684\u4ea7\u7269116\u3002\u5176\u4e2d\u53ef\u80fd\u7ecf\u8fc7115\u8fd9\u79cd\u4e2d\u95f4\u4ea7\u7269\uff0c\u91d1\u5c5e\u9521\u4e0e\u809f\u57fa\u548c\u7fb0\u57fa\u5f62\u6210\u516d\u5143\u73af\u4e2d\u95f4\u4ea7\u7269\uff0c\u6b64\u65f6\u7684\u809f\u57fa\u53d8\u6210\u7ed9\u7535\u5b50\u57fa\u56e2\uff0c\u4ece\u800c\u5f97\u5230\u9700\u8981\u7684116\u3002<\/p>\n<p><a href=\"https:\/\/assets.www.gsbet888.com\/uploads\/2017\/07\/3-3.jpg\"><img loading=\"lazy\" decoding=\"async\" class=\"aligncenter wp-image-15138 size-full\" src=\"https:\/\/assets.www.gsbet888.com\/uploads\/2017\/07\/3-3.jpg\" alt=\"\" width=\"420\" height=\"350\" srcset=\"https:\/\/assets.www.gsbet888.com\/uploads\/2017\/07\/3-3.jpg 420w, https:\/\/assets.www.gsbet888.com\/uploads\/2017\/07\/3-3-300x250.jpg 300w\" sizes=\"(max-width: 420px) 100vw, 420px\" \/><\/a><\/p>\n<p style=\"text-align: center\"><em>\u56fe3\uff1aKishi\u2019s D-A model studies<\/em><\/p>\n<p>117\u5148\u4e0e\u7f9f\u80fa\u5f62\u6210\u809f\u540e\u7ecf\u6c27\u5316\u94f6\u6c27\u5316\u5f62\u6210\u82ef\u918c\u884d\u751f\u7269112\uff1b112\u7ecflewis-acid promoted D-A\u53cd\u5e94\u5f97\u5230119\uff1b110\u7ecf<a href=\"\/\/www.gsbet888.com\/reactions\/2014\/02\/post-458.html\">Beckmann rearrangement<\/a>\u5f97\u5230121\uff0c\u5e76\u4e14\u6784\u578b\u5f97\u5230\u4fdd\u6301\uff1b121\u7ecf\u9009\u62e9\u6027\u8fd8\u539f\u7fb0\u57fa\u5f97\u5230109\uff1b109\u4e2d\u53cc\u952e\u5f97\u73af\u6c27\u540e\u540c\u65f6\u53d1\u751f\u5206\u5b50\u5185\u7684\u53e6\u4e00\u4e2a\u73af\u6c27\u5f00\u73af\u4e0e\u73af\u6c27\u5316\u7684\u4e32\u8054\u53cd\u5e94\u5f97\u5230117\u3002<\/p>\n<p><a href=\"https:\/\/assets.www.gsbet888.com\/uploads\/2017\/07\/4-3.jpg\"><img loading=\"lazy\" decoding=\"async\" class=\"aligncenter wp-image-15139 size-full\" src=\"https:\/\/assets.www.gsbet888.com\/uploads\/2017\/07\/4-3.jpg\" alt=\"\" width=\"676\" height=\"266\" srcset=\"https:\/\/assets.www.gsbet888.com\/uploads\/2017\/07\/4-3.jpg 676w, https:\/\/assets.www.gsbet888.com\/uploads\/2017\/07\/4-3-300x118.jpg 300w\" sizes=\"(max-width: 676px) 100vw, 676px\" \/><\/a><\/p>\n<p style=\"text-align: center\"><em>\u56fe4\uff1aKishi\u2019s synthesis of cis\u00ad-decaliin system 107<\/em><\/p>\n<p>107\u4e2d\u6e38\u79bb\u7684\u7f9f\u57fa\u7ecf\u6c27\u5316\u6210\u7fb0\u57fa\u540e\u7528\u4e59\u4e8c\u9187\u4fdd\u62a4\u5f97122\uff1b122\u4e2d\u53e6\u4e00\u4e2a\u7fb0\u57fa\u7ecf<a href=\"\/\/www.gsbet888.com\/reactions\/%e8%bf%98%e5%8e%9f%e5%8f%8d%e5%ba%94\/2014\/06\/%e7%b1%b3%e5%b0%94%e6%b8%a9-%e5%ba%9e%e5%a4%9a%e5%a4%ab-%e9%9f%a6%e5%b0%94%e8%8e%b1%e8%bf%98%e5%8e%9f%e5%8f%8d%e5%ba%94-meerwein-ponndorf-verley-mpv-reduction.html\">Meerwein-Ponndorf-Verley<em> Reduction<\/em><\/a>\u540e\uff0c\u7528\u4e59\u9170\u57fa\u4fdd\u62a4\u5f97\u5355\u4e00\u6784\u578b\u7684123\uff1b123\u4e2d\u53cc\u952e\u4e0a\u7684\u7532\u57fa\u7ecf\u4e8c\u6c27\u5316\u7852\u6c27\u5316\u5f97\u03b1, \u03b2-\u4e0d\u9971\u548c\u919b<sup>[8]<\/sup>(a review on selenium dioxide oxidation)\uff0c\u540e\u7ecf\u8fd8\u539f\u5f97\u5230\u70ef\u4e19\u57fa\u9187124\uff1b124\u4e2d\u53cc\u952e\u73af\u6c27\u5316\u5f97126\uff0c\u4f46\u5728\u5176\u4e2d\uff0c\u6b64\u53cc\u952e\u975e\u5e38\u96be\u4ee5\u53cd\u5e94\uff0c\u9700\u8981\u5347\u9ad8\u6e29\u5ea6\uff0c\u800c\u5347\u9ad8\u6e29\u5ea6\u4f1a\u5bfc\u81f4m-CPBA\u7684\u5206\u89e3\uff0c\u4e3a\u6b64Kishi\u7b5b\u9009\u4e86\u8bb8\u591a\u81ea\u7531\u57fa\u6291\u5236\u5242\uff0c\u6700\u7ec8\u9009\u62e9\u4e86125\uff0c\u5e76\u4e14\u5f97\u5230\u4e0d\u9519\u7684\u6536\u7387\uff1b126\u4e2d\u7fb0\u57fa\u6362\u6210\u7528\u4e59\u9187\u4fdd\u62a4\u5f97128\uff1b\u4e8c\u4e59\u6c27\u57fa\u7f29\u916e128\u5728180\u2103\u4e0b\u5206\u89e3\u5f97129\u3002<\/p>\n<p><a href=\"https:\/\/assets.www.gsbet888.com\/uploads\/2017\/07\/5-2.jpg\"><img loading=\"lazy\" decoding=\"async\" class=\"aligncenter wp-image-15140 size-full\" src=\"https:\/\/assets.www.gsbet888.com\/uploads\/2017\/07\/5-2.jpg\" alt=\"\" width=\"561\" height=\"420\" srcset=\"https:\/\/assets.www.gsbet888.com\/uploads\/2017\/07\/5-2.jpg 561w, https:\/\/assets.www.gsbet888.com\/uploads\/2017\/07\/5-2-300x225.jpg 300w, https:\/\/assets.www.gsbet888.com\/uploads\/2017\/07\/5-2-265x197.jpg 265w\" sizes=\"(max-width: 561px) 100vw, 561px\" \/><\/a><\/p>\n<p style=\"text-align: center\"><em>\u56fe5\uff1aKishi\u2019s synthesis of enol ether 129<\/em><\/p>\n<p>129\u7ecf\u73af\u6c27\u5316\u5f97130\uff1b130\u7ecf\u4e59\u9178\u50ac\u5316\u5f97\u4e32\u8054\u53cd\u5e94\u5f97\u5230106\uff1b106\u7ecf<a href=\"\/\/www.gsbet888.com\/reactions\/%e9%87%8d%e6%8e%92%e5%8f%8d%e5%ba%94\/2014\/02\/%e6%8b%9c%e8%80%b3%ef%bc%8d%e7%bb%b4%e7%ab%8b%e6%a0%bc%e6%b0%a7%e5%8c%96%e5%8f%8d%e5%ba%94baeyer-villiger-oxidation-reaction.html\">Baeyer-Villiger oxidation<\/a> \u5f97105\uff1b105\u5728\u9178\u6027\u6761\u4ef6\u4e0b\u5148\u5f62\u6210\u6c27\u9393\u79bb\u5b50\uff0c\u6253\u5f007\u5143\u73af\u5185\u916f\uff0c\u540e\u4e0e\u53e6\u4e00\u4e2a\u73af\u6c27\u5316\u5408\u7269\u53d1\u751f\u73af\u6c27\u5f00\u73af\u53cd\u5e94\u5f97\u5230\u53e6\u5916\u4e00\u4e2a\u73af\u5185\u916f135\uff1b135\u4e2d\u7f9f\u57fa\u7528\u4e59\u9170\u57fa\u4fdd\u62a4\u540e\uff0c\u52a0\u70ed\u8131\u53bb\u4e00\u5206\u5b50\u4e59\u9178\u5f97\u5230\u4e59\u9170\u57fa\u4fdd\u62a4\u7684tetrodamine 102\u3002\u81f3\u6b64\uff0ctetrodotoxin\u7684\u57fa\u672c\u73af\u9aa8\u67b6\u5df2\u5f97\u5230\u6784\u5efa\u3002<\/p>\n<p><a href=\"https:\/\/assets.www.gsbet888.com\/uploads\/2017\/07\/6-2.jpg\"><img loading=\"lazy\" decoding=\"async\" class=\"aligncenter wp-image-15141 size-full\" src=\"https:\/\/assets.www.gsbet888.com\/uploads\/2017\/07\/6-2.jpg\" alt=\"\" width=\"620\" height=\"413\" srcset=\"https:\/\/assets.www.gsbet888.com\/uploads\/2017\/07\/6-2.jpg 620w, https:\/\/assets.www.gsbet888.com\/uploads\/2017\/07\/6-2-300x200.jpg 300w\" sizes=\"(max-width: 620px) 100vw, 620px\" \/><\/a><\/p>\n<p style=\"text-align: center\"><em>\u56fe6\uff1aKishi\u2019s synthesis of masked tetrodamine<\/em><\/p>\n<p>102\u5728\u70f7\u57fa\u5316\u8bd5\u5242<em>Meerwein\u2019s salt<\/em> \u4f5c\u7528\u4e0b\uff0c\u751f\u6210136\uff0c\u540e\u5728\u9178\u6027\u6761\u4ef6\u4e0b\u6c34\u89e3\u5f97137\uff1b137\u4e0e138\u53cd\u5e94\u751f\u6210139\u540e\u7ee7\u7eed\u4e0e\u4e59\u9170\u80fa\u53cd\u5e94\u751f\u6210\u80cd\u57fa\u5316\u5408\u7269140\uff1b140\u4e0e\u6c28\u6c14\u53d1\u751f\u80fa\u4ea4\u6362\u751f\u6210141\uff1b141\u7ecf<a href=\"\/\/www.gsbet888.com\/reactions\/%e6%b0%a7%e5%8c%96%e5%8f%8d%e5%ba%94\/2014\/03\/%e5%9b%9b%e6%b0%a7%e5%8c%96%e9%94%87%ef%bc%88%e6%b0%a7%e5%8c%96%ef%bc%89.html\">\u56db\u6c27\u5316\u9507\u6c27\u5316<\/a>\u751f\u6210\u90bb\u4e8c\u7f9f\u57fa\u5316\u5408\u7269142\uff0c\u540e\u7ecf\u9ad8\u7898\u9178\u6c27\u5316\u5f97101\uff0c\u5f31\u78b1\u6027\u6761\u4ef6\u4e0b\u53d1\u751f\u4eb2\u548c\u53cd\u5e94\u6210\u6700\u540e\u4e00\u4e2a\u542b\u6c2e\u73af\u5e76\u4e14\u6c34\u89e3\u53bb\u4e59\u9170\u57fa\u4fdd\u62a4\uff0c\u4ee525%\u76844\u6b65\u6536\u7387\uff0c\u5f97\u5230\u6700\u7ec8\u7684tetrodotoxin\u3002<\/p>\n<p><a href=\"https:\/\/assets.www.gsbet888.com\/uploads\/2017\/07\/7-2.jpg\"><img loading=\"lazy\" decoding=\"async\" class=\"aligncenter wp-image-15142 size-full\" src=\"https:\/\/assets.www.gsbet888.com\/uploads\/2017\/07\/7-2.jpg\" alt=\"\" width=\"616\" height=\"478\" srcset=\"https:\/\/assets.www.gsbet888.com\/uploads\/2017\/07\/7-2.jpg 616w, https:\/\/assets.www.gsbet888.com\/uploads\/2017\/07\/7-2-300x233.jpg 300w\" sizes=\"(max-width: 616px) 100vw, 616px\" \/><\/a><\/p>\n<p style=\"text-align: center\"><em>\u56fe7\uff1aKishi\u2018s total synthesis of (<u>+<\/u>) tetrodotoxin<\/em><\/p>\n<h4 style=\"text-align: left\">J. du Bois\u7684\u5168\u5408\u6210\u7814\u7a76<sup>[9]<\/sup><\/h4>\n<p><strong><em>1) <\/em><\/strong><strong><em>\u9006\u5408\u6210\u5206\u6790<\/em><\/strong><\/p>\n<p>\u5728\u8fdb\u884ctetrodotoxin\u7684\u5168\u5408\u6210\u7814\u7a76\u4e4b\u524d\uff0cDu Bois\u5c0f\u7ec4\u5df2\u7ecf\u53d1\u5c55\u4e86\u4e00\u5957Rh\u6c2e\u5361\u5bbe\uff08Rh nitrenoid\uff09\u63d2\u5165\u7684\u65b9\u6cd5\u5b66<sup>[10]<\/sup>\uff08a review on carbene and nitrene C-H insertion reaction\uff09\uff0c\u4e8e\u662f\u5728\u6b64\u5de5\u4f5c\u4e2d\u591a\u6b21\u7528\u5230\u6b64\u65b9\u6cd5\u5bf9C-H\u952e\u8fdb\u884c\u5b98\u80fd\u56e2\u5316\u3002<\/p>\n<p><a href=\"https:\/\/assets.www.gsbet888.com\/uploads\/2017\/07\/8-2.jpg\"><img loading=\"lazy\" decoding=\"async\" class=\"aligncenter wp-image-15143 size-full\" src=\"https:\/\/assets.www.gsbet888.com\/uploads\/2017\/07\/8-2.jpg\" alt=\"\" width=\"666\" height=\"323\" srcset=\"https:\/\/assets.www.gsbet888.com\/uploads\/2017\/07\/8-2.jpg 666w, https:\/\/assets.www.gsbet888.com\/uploads\/2017\/07\/8-2-300x145.jpg 300w\" sizes=\"(max-width: 666px) 100vw, 666px\" \/><\/a><\/p>\n<p style=\"text-align: center\"><em>\u56fe8\uff1aDu Bois\u2019s retrosynthetic analysis<\/em><\/p>\n<p><strong><em>2<\/em><\/strong><strong><em>\uff09Tetrodotoxin\u7684\u5168\u5408\u6210<\/em><\/strong><\/p>\n<p>152\u5148\u73af\u6c27\u5316\u540e\u53d1\u751f\u4eb2\u548c\u7684\u4e32\u8054\u53cd\u5e94\uff0c\u540e\u7ecf\u7682\u5316\u5f97\u5230156\uff1b156\u5148\u5f00\u5185\u916f\u73af\u5f97\u9170\u80fa\u540e\uff0c\u518d\u7528\u4e8c\u7532\u6c27\u57fa\u7f29\u4e19\u916e\u4fdd\u62a4\u90bb\u4f4d\u4e8c\u9187\u5f97157\uff0c157\u518d\u7528TBSCl\u4fdd\u62a4\u4e8c\u7ea7\u7fb0\u57fa\u5f97158\uff1b\u5728158\u8fd8\u539f\u65f6\uff0c\u5bb9\u6613\u53d1\u751f160\u6240\u793a\u5f97\u65ad\u952e\u65b9\u5f0f\uff0c\u5f97\u5230\u4e09\u7ea7\u80fa\uff0c\u6700\u7ec8Du Bois\u91c7\u7528\u52a0\u5165<em>n<\/em>-BuLi\u5f62\u6210159\u6240\u793a\u7ed3\u6784\uff0c\u540e\u6210\u529f\u5f97\u5230\u919b150\uff1b<\/p>\n<p><a href=\"https:\/\/assets.www.gsbet888.com\/uploads\/2017\/07\/9-1.jpg\"><img loading=\"lazy\" decoding=\"async\" class=\"aligncenter wp-image-15144 size-full\" src=\"https:\/\/assets.www.gsbet888.com\/uploads\/2017\/07\/9-1.jpg\" alt=\"\" width=\"665\" height=\"363\" srcset=\"https:\/\/assets.www.gsbet888.com\/uploads\/2017\/07\/9-1.jpg 665w, https:\/\/assets.www.gsbet888.com\/uploads\/2017\/07\/9-1-300x164.jpg 300w\" sizes=\"(max-width: 665px) 100vw, 665px\" \/><\/a><\/p>\n<p style=\"text-align: center\"><em>\u56fe9\uff1aDu Bois\u2019s synthesis of 150<\/em><\/p>\n<p>150\u4e0e151\u53d1\u751faldol\u53cd\u5e94\u5f97\u5230\u4e2d\u95f4\u4ea7\u7269162\uff0c\u5f62\u6210\u5f97\u6c27\u8d1f\u79bb\u5b50\u7acb\u523b\u53d1\u751f\u73af\u5185\u916f\u5316\u5f97\u5230\u73af\u5185\u916f163\uff0c\u5176\u4e2d\uff0c\u5f97\u76ca\u4e8eFelkin-Ahn control<sup>[11]<\/sup>\u53cd\u5e94\u6761\u4ef6\uff0c163\u7684<em>dr<\/em>\u503c\u4e3a12\uff1a1\uff1b164\u7ecf\u8fc7\u94af\u78b3\u6c22\u8fd8\u539f\u540e\uff0c8a\u4f4d\u4e0a\u7684\u916f\u57fa\u53d8\u6210\u7fa7\u57fa\u540e\uff0c\u5728\u8349\u9170\u6c2f\u7684\u50ac\u5316\u4e0b\u4e0e\u91cd\u6c2e\u7532\u70f7\u53d1\u751f\u4eb2\u6838\u53d6\u4ee3\u53cd\u5e94\u5f97\u5230148\uff1b\u518d\u7528Du Bois\u7ec4\u53d1\u5c55\u7684\u65b9\u6cd5\u5b66\uff0c\u8fdb\u884c\u7279\u5b9a\u7684\u5361\u5bbeC-H\u952e\u63d2\u5165\u53cd\u5e94\uff0c\u5f97\u5230147\uff1b147\u518d\u8fd8\u539f\u5f97\u5230165\u3002<\/p>\n<p><a href=\"https:\/\/assets.www.gsbet888.com\/uploads\/2017\/07\/10-1.jpg\"><img loading=\"lazy\" decoding=\"async\" class=\"aligncenter wp-image-15145 size-full\" src=\"https:\/\/assets.www.gsbet888.com\/uploads\/2017\/07\/10-1.jpg\" alt=\"\" width=\"679\" height=\"286\" srcset=\"https:\/\/assets.www.gsbet888.com\/uploads\/2017\/07\/10-1.jpg 679w, https:\/\/assets.www.gsbet888.com\/uploads\/2017\/07\/10-1-300x126.jpg 300w\" sizes=\"(max-width: 679px) 100vw, 679px\" \/><\/a><\/p>\n<p style=\"text-align: center\"><em>\u56fe10\uff1aDu Bois\u2019s synthesis of 165 through a C-H insertion<\/em><\/p>\n<p>\u867d\u71364\u53d6\u4ee3\u53cc\u952e\u5f88\u96be\u88ab\u8fd8\u539f\uff0c\u4f46\u5728\u94d1\u78b3\u6c22\u3001\u9ad8\u538b\u548cTFA\u7684\u4f5c\u7528\u4e0b\uff0c\u4f9d\u7136\u53ef\u4ee5\u5f97\u5230\u540c\u9762\u52a0\u6210\u7684\u4ea7\u7269166\uff0c166\u7acb\u523b\u53d1\u751f\u916f\u4ea4\u6362\u53cd\u5e94\uff0c\u5f97\u5230\u5f20\u529b\u66f4\u5c0f\u7684167\uff0c\u518d\u91cd\u65b0\u4e0a\u4fdd\u62a4\u57fa\u5f97168\uff1b168\u5148\u5f00\u73af\u751f\u6210\u7f9f\u57fa\u540e\u88abNMO\u6c27\u5316\u5f97\u5230\u7fb0\u57fa<sup>[12]<\/sup>\uff0c\u4e4b\u540e\u53d1\u751f<em>Takai methylenation<\/em>\u5f97\u5230170<sup>[13]<\/sup>\uff1b\u540e\u5728171\u5f97\u50ac\u5316\u4e0b\uff0c\u6c27\u5316\u5f97\u5230\u03b1, \u03b2-\u4e0d\u9971\u548c\u916e<sup>[14]<\/sup>\uff1b172\u4e0e\u4e59\u70ef\u57fa\u683c\u6c0f\u8bd5\u5242\u53cd\u540e\uff0c\u8fd8\u539f\u5f97\u5230146\uff1b146\u63a5\u7740\u53d1\u751f\u5206\u5b50\u5185\u916f\u5316\u53cd\u5e94\uff0c\u540e\u8131\u9664\u7f9f\u57fa\u4fdd\u62a4\u5f97174\u3002<\/p>\n<p><a href=\"https:\/\/assets.www.gsbet888.com\/uploads\/2017\/07\/11-1.jpg\"><img loading=\"lazy\" decoding=\"async\" class=\"aligncenter wp-image-15146 size-full\" src=\"https:\/\/assets.www.gsbet888.com\/uploads\/2017\/07\/11-1.jpg\" alt=\"\" width=\"664\" height=\"467\" srcset=\"https:\/\/assets.www.gsbet888.com\/uploads\/2017\/07\/11-1.jpg 664w, https:\/\/assets.www.gsbet888.com\/uploads\/2017\/07\/11-1-300x211.jpg 300w\" sizes=\"(max-width: 664px) 100vw, 664px\" \/><\/a><\/p>\n<p style=\"text-align: center\"><em>\u56fe11\uff1aDu Bois\u2019s synthesis of lactone 174<\/em><\/p>\n<p>174\u4e2d\u81ea\u7531\u7684\u7f9f\u57fa\u5148\u4e0e\u5f02\u6c30\u9178\u916f175\u53cd\u5e94\u751f\u6210\u916f\u9170\u80fa\uff0c\u518d\u5728\u950c\u7684\u4f5c\u7528\u4e0b\u6d88\u9664\u4e09\u6c2f\u4e59\u9170\u57fa\u5f97176\uff1b176\u5148\u81ed\u6c27\u5316\u540e\u8fd8\u539f\u5f97\u5230\u5f97\u7f9f\u57fa\u518d\u4e0eMsCl\uff0c\u5421\u5576\u53cd\u5e94\u5f97145\uff1b145\u53d1\u751f\u53e6\u4e00\u6b21\u94d1\u5361\u5bbeC-H\u952e\u63d2\u5165\u5f97179\uff1b179\u5148\u53d1\u751f<em>S<sub>N<\/sub>2<\/em>\u751f\u6210\u7852\u919a\uff0c\u518d\u53d1\u751f\u6c27\u5316\u6d88\u9664\u5f97\u5230144\uff1b180\u53d1\u751f\u6c34\u89e3\u53cd\u5e94\u5373\u53ef\u5f97\u5230181\uff1b184\u5148\u81ed\u6c27\u5316\u5f97\u5230\u919b\u57fa\u540e\uff0c\u5728TFA\u7684\u4f5c\u7528\u4e0b\u53ef\u4ee5\u5f97\u5230\u6700\u7ec8\u4ea7\u7269\uff0c\u4f46\u662f\u4ea7\u7269\u4e3a1\u548c2\u7684\u6df7\u5408\u7269\uff0c\u6bd4\u4f8b\u4e3a1\uff1a1\u3002<\/p>\n<p><a href=\"https:\/\/assets.www.gsbet888.com\/uploads\/2017\/07\/12-1.jpg\"><img loading=\"lazy\" decoding=\"async\" class=\"aligncenter wp-image-15147 size-full\" src=\"https:\/\/assets.www.gsbet888.com\/uploads\/2017\/07\/12-1.jpg\" alt=\"\" width=\"663\" height=\"411\" srcset=\"https:\/\/assets.www.gsbet888.com\/uploads\/2017\/07\/12-1.jpg 663w, https:\/\/assets.www.gsbet888.com\/uploads\/2017\/07\/12-1-300x186.jpg 300w, https:\/\/assets.www.gsbet888.com\/uploads\/2017\/07\/12-1-233x144.jpg 233w\" sizes=\"(max-width: 663px) 100vw, 663px\" \/><\/a><\/p>\n<p style=\"text-align: center\"><em>\u56fe11\uff1aDu Bois\u2019s total synthesis of tetrodotoxin<\/em><\/p>\n<h4>\u5199\u5728\u6700\u540e\u7684\u8bdd<\/h4>\n<p>1972\u5e74\uff0cKishi\u5bf9tetrodotoxin\u7684\u5408\u6210\u662f\u4e00\u9879\u5353\u8d8a\u7684\u5de5\u4f5c\uff0c\u4ed6\u4eec\u5bf9\u7acb\u4f53\u5316\u5b66\u7684\u7cbe\u51c6\u63a7\u5236\u4ee5\u53ca\u5bf9\u5316\u5b66\u53cd\u5e94\u7684\u51c6\u786e\u5e94\u7528\uff0c\u4ee4\u4eba\u53f9\u4e3a\u89c2\u6b62\u3002\u53e6\u4e00\u65b9\u9762\uff0c\u7b2c\u4e00\u624b\u6587\u732e\u77e5\u8bc6\u7684\u91cd\u8981\u6027\u5728\u8fd9\u91cc\u4e5f\u6709\u4f53\u73b0\u30022003\u5e74Du Bois\u901a\u8fc7C-H\u952e\u5b98\u80fd\u56e2\u5316\u91cd\u65b0\u5b8c\u6210\u4e86\u6b64\u5168\u5408\u6210\u5de5\u4f5c\uff0c\u5230\u73b0\u5728\uff0cC-H\u952e\u5b98\u80fd\u56e2\u8bdd\u5728\u5168\u5408\u6210\u4e2d\u5360\u636e\u7740\u91cd\u8981\u7684\u4f5c\u7528\u3002<\/p>\n<h4>\u53c2\u8003\u6587\u732e<\/h4>\n<ol>\n<li>Tahara, <em>et. al.<\/em> <em>Biochem. Z<\/em>.<em>,<\/em> 1911, <em>30<\/em>, 255;<\/li>\n<li>Tsuda, <em>et. al. J. Pharm. Soc. Jpn<\/em>.<em>,<\/em> 1952, <em>72<\/em>, 711;<\/li>\n<li>Tsuda, <em>et. al. Chem. Pharm. Bull.,<\/em> 1964, <em>12<\/em>, 1357;<\/li>\n<li>Goto, <em>et. al. Tetrahedron,<\/em> 1965, <em>21<\/em>, 2059;<\/li>\n<li>B. Woodward, <em>Pure Appl. Chem.,<\/em> 1964, <em>9<\/em>, 49;<\/li>\n<li>Kishi,<em> et. al. J. Am. Chem. Soc.,<\/em> 1972, <em>94<\/em>, 9217;<\/li>\n<li>Kishi, <em>et. al. J. Am. Chem. Soc.,<\/em> 1972, <em>94<\/em>, 9219;<\/li>\n<li>Rabjohn, <em>Org. React.,<\/em> 1976, <em>24<\/em>, 261;<\/li>\n<li>Du Bois,<em> et. al. J. Am. Chem. Soc.,<\/em> 2003, <em>125<\/em>, 11510;<\/li>\n<li>a) M. A. Mckervey,<em> al. Chem. Rev.,<\/em> 1994, <em>94<\/em>, 1091;<\/li>\n<li>b) R. E. J. Beckwith, <em> al. Chem. Rev., <\/em>2003, <em>103<\/em>, 2861;<\/li>\n<li>Reiser, <em>et. al.<\/em> <em>Chem<\/em>. <em>Rev<\/em>.<em>,<\/em> 1999, <em>99<\/em>, 1191;<\/li>\n<li>P. Marsden, <em>et. al. synthesis,<\/em> 1994, 639;<\/li>\n<li>Takai, <em>et. al. Tetrahedron<\/em> <em>Lett<\/em>.<em>,<\/em> 1978, <em>19<\/em>, 2417;<\/li>\n<li>Crich,<em> et. al. Tetrahedron,<\/em> 1985, <em>41<\/em>, 4359;<\/li>\n<\/ol>\n<p>\u672c\u6587\u7248\u6743\u5c5e\u4e8e\u00a0<a href=\"\/\/www.gsbet888.com\/\">Chem-Station\u5316\u5b66\u7a7a\u95f4<\/a>\uff0c \u6b22\u8fce\u70b9\u51fb\u6309\u94ae\u5206\u4eab\uff0c\u672a\u7ecf\u8bb8\u53ef\uff0c\u8c22\u7edd\u8f6c\u8f7d\uff01 <\/p>\n","protected":false},"excerpt":{"rendered":"\u672c\u6587\u6295\u7a3f\u4f5c\u8005 alberto-caeiro \u6cb3\u8c5a\u9c7c\u4f5c\u4e3a\u4e00\u79cd\u65e5\u672c\u7279\u522b\u7684\u70f9\u996a\u98df\u6750\u800c\u95fb\u540d\u3002\u4f46\u5982\u679c\u5904\u7406\u4e0d\u5f53\uff0c\u4e00\u9910\u7684\u6cb3\u8c5a\u9c7c\u8db3\u4ee5\u4f7f\u9910\u684c\u4e0a\u7684\u5404\u4f4d\u98df\u5ba2\u4e27\u547d\u3002\u4e8e\u662f\u5728\u65e5\u672c\uff0c\u80fd\u591f\u70f9\u996a\u6cb3\u8c5a\u9c7c\u7684\u5927\u53a8\u90fd\u9700\u8981\u5b66\u4e60\u8003\u8bd5\uff0c\u4ee5\u83b7\u5f97\u7279\u6b8a\u7684\u8bb8\u53ef\u8bc1\u3002 19\u4e16\u7eaa\u5f00\u59cb\uff0c\u65e5\u672c\u5c31\u6709\u8bb8\u591a\u751f\u7269\u5b66\u5bb6\u5f00\u59cb\u7814\u7a76\u8fd9\u79cd\u5267\u6bd2\u7684\u7269\u8d28\u30021911\u5e74\uff0cTahara\u62a5\u9053\u4e86\u8fd9\u79cd\u5267\u6bd2\u7684\u63d0\u7eaf\u7269\uff0c\u5e76\u5c06\u5176\u547d\u540d\u4e3atetrodotoxin[1]\u3002\u867d\u7136\u5728\u540e\u6765\u8bc1\u660e\u5176\u4e2d\u53ea\u542b\u6709\u5c11\u91cf\u7684tetrodotoxin\uff0c\u4f46\u5176\u5173\u952e\u6027\u7684\u5206\u79bb\u4e3a\u65e5\u540e\u7684\u5de5\u4f5c\u63d0\u4f9b\u4e86\u8bb8\u591a\u5e2e\u52a9\uff0c\u5e76\u5728\u5f53\u65f6\u7684\u836f\u5b66\u7814\u7a76\u63d0\u4f9b\u4e86\u57fa\u7840\u3002\u57281952\u5e74\uff0c\u6d25\u7530\u548c\u5ddd\u6751\u4e5f\u5206\u79bb\u51fa\u8fd9\u79cd\u5316\u5408\u7269\uff0c\u5e76\u4e14\u6cbf\u7528\u4e86tetrodotoxin [2]\u3002\u5728\u7b2c\u4e09\u5c4aIUPAC\uff08Kyoto Japan\uff09\u4e0a\uff0cTsuda[3]\uff0cGoto[4]\uff0cWoodward[5]\u90fd\u5c55\u793a\u4e86\u5404\u81ea\u5f97\u5230\u6cb3\u8c5a\u6bd2\u7d20\u7684\u7ed3\u6784\u5f0f\uff0c\u4e09\u8005\u540c\u65f6\u4e14\u72ec\u7acb\u7684\u5f97\u5230\u4e86\u6cb3\u8c5a\u6bd2\u7d20\u7684\u7ed3\u6784\u5f0f\uff0c\u5982\u4e0b\u56fe1\u6240\u793a\u3002 \u56fe1\uff1atetrodotoxin\u4e09\u79cd\u5f62\u5f0f \u6cb3\u8c5a\u6bd2\u7d20\u662f\u4e00\u79cd\u795e\u7ecf\u6bd2\u7d20\uff0c\u5bf9\u94a0\u79bb\u5b50\u901a\u9053\u6709\u6291\u5236\u4f5c\u7528\u3002\u6cb3\u8c5a\u6bd2\u7d20\u80fd\u591f\u6291\u5236\u94a0\u79bb\u5b50\u901a\u9053\u7684\u5f00\u653e\uff0c\u6545\u53ef\u4ee5\u9ad8\u6548\u7684\u5173\u95ed\u5468\u56f4\u795e\u7ecf\u7cfb\u7edf\u3002\u6839\u636e\u98df\u7528\u91cf\u7684\u4e0d\u540c\uff0c\u75c7\u72b6\u4ece\u9ebb\u75f9\u3001\u660f\u8ff7\u3001\u547c\u5438\u8870\u5f31\u3001\u6b7b\u4ea1\u4f9d\u6b21\u9012\u589e\u3002\u6709\u8da3\u7684\u662f\uff0c\u6cb3\u8c5a\u6bd2\u7d20\u5bf9\u5927\u8111\u795e\u7ecf\u6ca1\u6709\u76f4\u63a5\u4f5c\u7528\uff0c\u4e2d\u6bd2\u8005\u76f4\u81f3\u6b7b\u4ea1\u65f6\u624d\u6709\u610f\u8bc6\u5230\u4e2d\u6bd2\u3002\u5176\u9009\u62e9\u6027\u7684\u4f5c\u7528\u673a\u5236\u4f7f\u5f97\u5176\u5728\u836f\u5b66\u548c\u751f\u7269\u5316\u5b66\u4e0a\u6709\u8bb8\u591a\u7814\u7a76\u3002 &nbsp; Kishi\u7684\u5168\u5408\u6210\u7814\u7a76[6,7] 1\uff09\u9006\u5408\u6210\u5206\u6790 \u5f97\u76ca\u4e8e\u5728Goto\u7ec4\u5173\u4e8e\u6cb3\u8c5a\u6bd2\u7d20\u7ed3\u6784\u7684\u7814\u7a76\uff0cY. Kishi\u5f97\u5230\u8bb8\u591a\u6cb3\u8c5a\u6bd2\u7d20\u7269\u7406\u548c\u5316\u5b66\u6027\u8d28\u7684\u7b2c\u4e00\u624b\u8d44\u6599\uff0c\u8fd9\u4e9b\u90fd\u88ab\u6709\u6548\u7684\u8fd0\u7528\u5230\u5176\u5408\u6210\u7b56\u7565\u4e2d\u3002\u4e0b\u56fe2\u4e3aY. Kishi\u7ec4\u7684\u9006\u5408\u6210\u5206\u6790\u3002 \u56fe2\uff1aKishi\u2019s retrosynthesis of Tetrodotoxin \u56e0\u6cb3\u8c5a\u6bd2\u7d20\u6613\u6eb6\u4e8e\u6c34\u800c\u96be\u6eb6\u4e8e\u6709\u673a\u6eb6\u5242\uff0c\u4e8e\u662f\u6784\u60f3\u5207\u6389\u80cd\u57fa\u540e\u7684\u7269\u8d28\u518d\u7ecf\u4e59\u9170\u57fa\u4fee\u9970\u540e\u5f97\u5230102\u8fd9\u79cd\u65b9\u6848\uff0c\u800c\u5728Goto\u7ec4\u5df2\u5f97\u5230\u8bc1\u660e\uff0c\u867d\u7136\u6cb3\u8c5a\u6bd2\u7d20\u78b1\u6027\u6761\u4ef6\u4e0b\u4e0d\u7a33\u5b9a\uff0c\u4f46\u4e59\u9170\u57fa\u4fdd\u62a4\u7684\u884d\u751f\u7269\u53ef\u4ee5\u5728\u6e29\u548c\u6761\u4ef6\u4e0b\u53ef\u4ee5\u53bb\u4fdd\u62a4\u3002 2\uff09Tetrodotoxin\u7684\u5168\u5408\u6210 \u5e95\u7269113\u4e0e\u4e01\u4e8c\u70ef\u76f4\u63a5\u53d1\u751fD-A\u53cd\u5e94\u65f6\uff0c\u809f\u57fa\u662f\u7ed9\u7535\u5b50\u57fa\u56e2\uff0c\u53cd\u5e94\u53ea\u4f1a\u5f97\u5230\u70ed\u529b\u5b66\u63a7\u5236\u7684\u4ea7\u7269114\u3002\u4e8e\u662f\uff0cY. Kishi\u901a\u8fc7\u52a0\u5165Lewis\u9178\u4e8c\u6c2f\u5316\u9521\uff0c\u5f97\u5230\u540c\u9762\u53cd\u5e94\u7684\u4ea7\u7269116\u3002\u5176\u4e2d\u53ef\u80fd\u7ecf\u8fc7115\u8fd9\u79cd\u4e2d\u95f4\u4ea7\u7269\uff0c\u91d1\u5c5e\u9521\u4e0e\u809f\u57fa\u548c\u7fb0\u57fa\u5f62\u6210\u516d\u5143\u73af\u4e2d\u95f4\u4ea7\u7269\uff0c\u6b64\u65f6\u7684\u809f\u57fa\u53d8\u6210\u7ed9\u7535\u5b50\u57fa\u56e2\uff0c\u4ece\u800c\u5f97\u5230\u9700\u8981\u7684116\u3002 \u56fe3\uff1aKishi\u2019s D-A model studies 117\u5148\u4e0e\u7f9f\u80fa\u5f62\u6210\u809f\u540e\u7ecf\u6c27\u5316\u94f6\u6c27\u5316\u5f62\u6210\u82ef\u918c\u884d\u751f\u7269112\uff1b112\u7ecflewis-acid promoted D-A\u53cd\u5e94\u5f97\u5230119\uff1b110\u7ecfBeckmann rearrangement\u5f97\u5230121\uff0c\u5e76\u4e14\u6784\u578b\u5f97\u5230\u4fdd\u6301\uff1b121\u7ecf\u9009\u62e9\u6027\u8fd8\u539f\u7fb0\u57fa\u5f97\u5230109\uff1b109\u4e2d\u53cc\u952e\u5f97\u73af\u6c27\u540e\u540c\u65f6\u53d1\u751f\u5206\u5b50\u5185\u7684\u53e6\u4e00\u4e2a\u73af\u6c27\u5f00\u73af\u4e0e\u73af\u6c27\u5316\u7684\u4e32\u8054\u53cd\u5e94\u5f97\u5230117\u3002 \u56fe4\uff1aKishi\u2019s synthesis of cis\u00ad-decaliin system 107 107\u4e2d\u6e38\u79bb\u7684\u7f9f\u57fa\u7ecf\u6c27\u5316\u6210\u7fb0\u57fa\u540e\u7528\u4e59\u4e8c\u9187\u4fdd\u62a4\u5f97122\uff1b122\u4e2d\u53e6\u4e00\u4e2a\u7fb0\u57fa\u7ecfMeerwein-Ponndorf-Verley Reduction\u540e\uff0c\u7528\u4e59\u9170\u57fa\u4fdd\u62a4\u5f97\u5355\u4e00\u6784\u578b\u7684123\uff1b123\u4e2d\u53cc\u952e\u4e0a\u7684\u7532\u57fa\u7ecf\u4e8c\u6c27\u5316\u7852\u6c27\u5316\u5f97\u03b1, \u03b2-\u4e0d\u9971\u548c\u919b[8](a review on selenium dioxide oxidation)\uff0c\u540e\u7ecf\u8fd8\u539f\u5f97\u5230\u70ef\u4e19\u57fa\u9187124\uff1b124\u4e2d\u53cc\u952e\u73af\u6c27\u5316\u5f97126\uff0c\u4f46\u5728\u5176\u4e2d\uff0c\u6b64\u53cc\u952e\u975e\u5e38\u96be\u4ee5\u53cd\u5e94\uff0c\u9700\u8981\u5347\u9ad8\u6e29\u5ea6\uff0c\u800c\u5347\u9ad8\u6e29\u5ea6\u4f1a\u5bfc\u81f4m-CPBA\u7684\u5206\u89e3\uff0c\u4e3a\u6b64Kishi\u7b5b\u9009\u4e86\u8bb8\u591a\u81ea\u7531\u57fa\u6291\u5236\u5242\uff0c\u6700\u7ec8\u9009\u62e9\u4e86125\uff0c\u5e76\u4e14\u5f97\u5230\u4e0d\u9519\u7684\u6536\u7387\uff1b126\u4e2d\u7fb0\u57fa\u6362\u6210\u7528\u4e59\u9187\u4fdd\u62a4\u5f97128\uff1b\u4e8c\u4e59\u6c27\u57fa\u7f29\u916e128\u5728180\u2103\u4e0b\u5206\u89e3\u5f97129\u3002 \u56fe5\uff1aKishi\u2019s synthesis of enol ether 129 129\u7ecf\u73af\u6c27\u5316\u5f97130\uff1b130\u7ecf\u4e59\u9178\u50ac\u5316\u5f97\u4e32\u8054\u53cd\u5e94\u5f97\u5230106\uff1b106\u7ecfBaeyer-Villiger oxidation \u5f97105\uff1b105\u5728\u9178\u6027\u6761\u4ef6\u4e0b\u5148\u5f62\u6210\u6c27\u9393\u79bb\u5b50\uff0c\u6253\u5f007\u5143\u73af\u5185\u916f\uff0c\u540e\u4e0e\u53e6\u4e00\u4e2a\u73af\u6c27\u5316\u5408\u7269\u53d1\u751f\u73af\u6c27\u5f00\u73af\u53cd\u5e94\u5f97\u5230\u53e6\u5916\u4e00\u4e2a\u73af\u5185\u916f135\uff1b135\u4e2d\u7f9f\u57fa\u7528\u4e59\u9170\u57fa\u4fdd\u62a4\u540e\uff0c\u52a0\u70ed\u8131\u53bb\u4e00\u5206\u5b50\u4e59\u9178\u5f97\u5230\u4e59\u9170\u57fa\u4fdd\u62a4\u7684tetrodamine 102\u3002\u81f3\u6b64\uff0ctetrodotoxin\u7684\u57fa\u672c\u73af\u9aa8\u67b6\u5df2\u5f97\u5230\u6784\u5efa\u3002 \u56fe6\uff1aKishi\u2019s synthesis of masked tetrodamine 102\u5728\u70f7\u57fa\u5316\u8bd5\u5242Meerwein\u2019s salt \u4f5c\u7528\u4e0b\uff0c\u751f\u6210136\uff0c\u540e\u5728\u9178\u6027\u6761\u4ef6\u4e0b\u6c34\u89e3\u5f97137\uff1b137\u4e0e138\u53cd\u5e94\u751f\u6210139\u540e\u7ee7\u7eed\u4e0e\u4e59\u9170\u80fa\u53cd\u5e94\u751f\u6210\u80cd\u57fa\u5316\u5408\u7269140\uff1b140\u4e0e\u6c28\u6c14\u53d1\u751f\u80fa\u4ea4\u6362\u751f\u6210141\uff1b141\u7ecf\u56db\u6c27\u5316\u9507\u6c27\u5316\u751f\u6210\u90bb\u4e8c\u7f9f\u57fa\u5316\u5408\u7269142\uff0c\u540e\u7ecf\u9ad8\u7898\u9178\u6c27\u5316\u5f97101\uff0c\u5f31\u78b1\u6027\u6761\u4ef6\u4e0b\u53d1\u751f\u4eb2\u548c\u53cd\u5e94\u6210\u6700\u540e\u4e00\u4e2a\u542b\u6c2e\u73af\u5e76\u4e14\u6c34\u89e3\u53bb\u4e59\u9170\u57fa\u4fdd\u62a4\uff0c\u4ee525%\u76844\u6b65\u6536\u7387\uff0c\u5f97\u5230\u6700\u7ec8\u7684tetrodotoxin\u3002 \u56fe7\uff1aKishi\u2018s total synthesis of (+) tetrodotoxin J. du Bois\u7684\u5168\u5408\u6210\u7814\u7a76[9] 1) \u9006\u5408\u6210\u5206\u6790 \u5728\u8fdb\u884ctetrodotoxin\u7684\u5168\u5408\u6210\u7814\u7a76\u4e4b\u524d\uff0cDu Bois\u5c0f\u7ec4\u5df2\u7ecf\u53d1\u5c55\u4e86\u4e00\u5957Rh\u6c2e\u5361\u5bbe\uff08Rh nitrenoid\uff09\u63d2\u5165\u7684\u65b9\u6cd5\u5b66[10]\uff08a review on carbene and nitrene C-H insertion reaction\uff09\uff0c\u4e8e\u662f\u5728\u6b64\u5de5\u4f5c\u4e2d\u591a\u6b21\u7528\u5230\u6b64\u65b9\u6cd5\u5bf9C-H\u952e\u8fdb\u884c\u5b98\u80fd\u56e2\u5316\u3002 \u56fe8\uff1aDu Bois\u2019s retrosynthetic analysis 2\uff09Tetrodotoxin\u7684\u5168\u5408\u6210 152\u5148\u73af\u6c27\u5316\u540e\u53d1\u751f\u4eb2\u548c\u7684\u4e32\u8054\u53cd\u5e94\uff0c\u540e\u7ecf\u7682\u5316\u5f97\u5230156\uff1b156\u5148\u5f00\u5185\u916f\u73af\u5f97\u9170\u80fa\u540e\uff0c\u518d\u7528\u4e8c\u7532\u6c27\u57fa\u7f29\u4e19\u916e\u4fdd\u62a4\u90bb\u4f4d\u4e8c\u9187\u5f97157\uff0c157\u518d\u7528TBSCl\u4fdd\u62a4\u4e8c\u7ea7\u7fb0\u57fa\u5f97158\uff1b\u5728158\u8fd8\u539f\u65f6\uff0c\u5bb9\u6613\u53d1\u751f160\u6240\u793a\u5f97\u65ad\u952e\u65b9\u5f0f\uff0c\u5f97\u5230\u4e09\u7ea7\u80fa\uff0c\u6700\u7ec8Du Bois\u91c7\u7528\u52a0\u5165n-BuLi\u5f62\u6210159\u6240\u793a\u7ed3\u6784\uff0c\u540e\u6210\u529f\u5f97\u5230\u919b150\uff1b \u56fe9\uff1aDu Bois\u2019s synthesis of 150 150\u4e0e151\u53d1\u751faldol\u53cd\u5e94\u5f97\u5230\u4e2d\u95f4\u4ea7\u7269162\uff0c\u5f62\u6210\u5f97\u6c27\u8d1f\u79bb\u5b50\u7acb\u523b\u53d1\u751f\u73af\u5185\u916f\u5316\u5f97\u5230\u73af\u5185\u916f163\uff0c\u5176\u4e2d\uff0c\u5f97\u76ca\u4e8eFelkin-Ahn 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