{"id":40799,"date":"2021-12-15T08:00:11","date_gmt":"2021-12-15T00:00:11","guid":{"rendered":"\/\/www.gsbet888.com\/?p=40799"},"modified":"2021-12-10T16:04:56","modified_gmt":"2021-12-10T08:04:56","slug":"org-lett-%ef%bc%9a%e9%87%91%e5%82%ac%e5%8c%96%e7%9a%84%e7%82%94%e9%86%87%e4%b8%8e%e7%83%af%e5%9f%ba%e5%8c%96%e5%90%88%e7%89%a9%e4%b9%8b%e9%97%b4%e7%9a%8422%e7%8e%af%e5%8a%a0%e6%88%90%e5%8f%8d","status":"publish","type":"post","link":"\/\/www.gsbet888.com\/%e5%8c%96%e5%ad%a6%e6%9d%82%e8%ae%b0\/recentpaper\/2021\/12\/org-lett-%ef%bc%9a%e9%87%91%e5%82%ac%e5%8c%96%e7%9a%84%e7%82%94%e9%86%87%e4%b8%8e%e7%83%af%e5%9f%ba%e5%8c%96%e5%90%88%e7%89%a9%e4%b9%8b%e9%97%b4%e7%9a%8422%e7%8e%af%e5%8a%a0%e6%88%90%e5%8f%8d.html","title":{"rendered":"Org. Lett.\uff1a\u91d1\u50ac\u5316\u7684\u7094\u9187\u4e0e\u70ef\u57fa\u5316\u5408\u7269\u4e4b\u95f4\u7684[2+2]\u73af\u52a0\u6210\u53cd\u5e94\u65b9\u6cd5\u5b66"},"content":{"rendered":"

\u672c\u6587\u4f5c\u8005\uff1a\u6749\u6749<\/strong><\/p>\n

\u5bfc\u8bfb<\/h4>\n

\u8fd1\u65e5\uff0c\u897f\u73ed\u7259ICIQ (Institut Catal\u00e0 d’Investigaci\u00f3 Qu\u00edmica)\u7684A.\u00a0M. Echavarren\u8bfe\u9898\u7ec4\u5728Org. Lett.<\/em>\u4e2d\u53d1\u8868\u8bba\u6587\uff0c\u62a5\u9053\u4e00\u79cd\u901a\u8fc7\u91d1(I)\u50ac\u5316\u5242\u4fc3\u8fdb\u7684\u7094\u9187\u919a (ynol ethers)\u4e0e\u70ef\u57fa\u5316\u5408\u7269\u4e4b\u95f4\u7684[2+2]\u73af\u52a0\u6210\u53cd\u5e94\u65b9\u6cd5\u5b66\uff0c\u8fdb\u800c\u6210\u529f\u5b9e\u73b0\u4e00\u7cfb\u5217\u73af\u4e01\u916e\u884d\u751f\u7269\u7684\u6784\u5efa\u3002\u540c\u65f6\uff0c\u8be5\u5c0f\u7ec4\u53d1\u73b0\uff0c\u5185\u82b3\u57fa\u7094\u9187\u919a\u4e0e\u5bcc\u7535\u5b50\u7684\u82ef\u4e59\u70ef\u5206\u5b50\u4e4b\u95f4\uff0c\u5219\u4f18\u5148\u8fdb\u884c\u76f8\u5e94\u7684[4+2]\u73af\u52a0\u6210\u8fc7\u7a0b\uff0c\u8fdb\u800c\u987a\u5229\u5b9e\u73b0\u5404\u7c7b\u8272\u70f7\u5206\u5b50\u7684\u6784\u5efa\u3002<\/p>\n

Synthesis of Cyclobutanones by Gold(I)-Catalyzed [2+2] Cycloaddition of Ynol Ethers with Alkenes
\nM. Zanini, A. Cataffo, A. M. Echavarren, Org. Lett<\/em>. 2021<\/strong>, ASAP doi: 10.1021\/acs.orglett.1c03499<\/u><\/a>.<\/u><\/p><\/blockquote>\n

\"\"<\/a><\/p>\n

\u6b63\u6587<\/h4>\n

\u4f5c\u4e3a\u73af\u7fb0\u57fa\u5316\u5408\u7269\u4e2d\u80fd\u591f\u7a33\u5b9a\u5b58\u5728\u7684\u6700\u5c0f\u9aa8\u67b6\u5355\u5143\uff0c\u73af\u4e01\u916e\u7c7b\u5316\u5408\u7269\u5df2\u7ecf\u6210\u4e3a\u6709\u673a\u5408\u6210\u65b9\u6cd5\u5b66\u7814\u7a76\u4e2d\u6781\u4e3a\u5173\u952e\u7684\u780c\u5757\u3002\u56e0\u6b64\uff0c\u6784\u5efa\u73af\u4e01\u916e\u5206\u5b50\u7684\u76f8\u5173\u7b56\u7565\u7814\u7a76\uff0c\u4e00\u76f4\u4ee5\u6765\u5907\u53d7\u5408\u6210\u5316\u5b66\u5bb6\u7684\u5e7f\u6cdb\u5173\u6ce8\u3002\u76ee\u524d\uff0c\u76f8\u5173\u7684\u53cd\u5e94\u7b56\u7565\u4e3b\u8981\u6d89\u53ca\uff1a\u70ef\u916e\u4e0e\u70ef\u57fa\u5316\u5408\u7269\u4e4b\u95f4\u7684[2+2]\u73af\u52a0\u6210[1]-[2] <\/sup>(Scheme 1A)\u3001\u53d6\u4ee3\u73af\u4e19\u70f7\u6216\u73af\u4e19\u9187\u7684\u6269\u73af\u53cd\u5e94[3]<\/sup>\u3001\u5f62\u5f0f[3+1]\u73af\u52a0\u6210\u53cd\u5e94[4]<\/sup>\u3001\u91d1-\u5361\u5bbe\u524d\u4f53\u7684C-H\u63d2\u5165\u53cd\u5e94[5]<\/sup>\u3001Co(II)\u50ac\u5316\u7684\u81ea\u7531\u57fa1,4-C-H\u70f7\u57fa\u5316\u53cd\u5e94[6]<\/sup>\u3001\u73af\u4e01\u916e\u884d\u751f\u7269\u7684\u5b98\u80fd\u56e2\u5316\u53cd\u5e94[7]<\/sup>\u4ee5\u53ca\u91d1\u6216\u94c2\u50ac\u5316\u7684\u70ef-\u7094\u9170\u80fa\u73af\u5f02\u6784\u5316\u53cd\u5e94\u65b9\u6cd5\u5b66[8]-[9]<\/sup>\u3002<\/p>\n

\u8fd9\u91cc\uff0c\u4f5c\u8005\u53d7\u5230Kozmin\u8bfe\u9898\u7ec4\u5bf9\u4e8e\u94f6\u50ac\u5316\u7684\u7845\u57fa\u7094\u9187\u919a\u4e0e\u03b1<\/em>,\u03b2<\/em>-\u4e0d\u9971\u548c\u916e\u4e4b\u95f4\u7684[2+2]\u73af\u52a0\u6210\u53cd\u5e94\u65b9\u6cd5\u5b66[10]<\/sup>\u00a0(Scheme 1B)\u4ee5\u53ca\u672c\u8bfe\u9898\u7ec4\u524d\u671f\u5bf9\u4e8e\u91d1\u50ac\u5316\u7684\u7094\u57fa\u4e0e\u70ef\u57fa\u5316\u5408\u7269\u4e4b\u95f4\u7684[2+2]\u73af\u52a0\u6210\u53cd\u5e94\u65b9\u6cd5\u5b66[11]-[14]<\/sup>\u76f8\u5173\u7814\u7a76\u7684\u542f\u53d1\uff0c\u672c\u6587\u4e2d\uff0c\u4f5c\u8005\u6210\u529f\u8bbe\u8ba1\u51fa\u4e00\u79cd\u901a\u8fc7\u91d1\u50ac\u5316\u5242\u4fc3\u8fdb\u7684\u82b3\u57fa\u7094\u9187\u919a\u4e0e\u70ef\u57fa\u5316\u5408\u7269\u4e4b\u95f4\u7684[2+2]\u73af\u52a0\u6210\u53cd\u5e94\u65b9\u6cd5\u5b66\uff0c\u8fdb\u800c\u6709\u6548\u5730\u5b9e\u73b0\u4e00\u7cfb\u5217\u73af\u4e01\u916e\u5206\u5b50\u7684\u6784\u5efa (Scheme 1B)\u3002\u540c\u65f6\uff0c\u7814\u7a76\u53d1\u73b0\uff0c\u5185\u82b3\u57fa\u7094\u9187\u919a\u4e0e\u70ef\u57fa\u5316\u5408\u7269\u4e4b\u95f4\uff0c\u5219\u4f18\u5148\u8fdb\u884c\u76f8\u5e94\u7684[4+2]\u73af\u52a0\u6210\u8fc7\u7a0b\uff0c\u8fdb\u800c\u83b7\u5f97\u4e00\u7cfb\u5217\u91cd\u8981\u7684\u8272\u70f7\u5206\u5b50\u3002<\/p>\n

\"\"<\/a><\/p>\n

\u9996\u5148\uff0c\u4f5c\u8005\u91c7\u7528\u82ef\u57fa\u7094\u9187\u919a1a<\/strong>\u4e0e\u03b1<\/em>-\u7532\u57fa\u82ef\u4e59\u70ef2a<\/strong>\u4f5c\u4e3a\u6a21\u578b\u5e95\u7269\uff0c\u8fdb\u884c\u76f8\u5173\u73af\u52a0\u6210\u53cd\u5e94\u6761\u4ef6\u7684\u4f18\u5316\u7b5b\u9009 (Table 1)\u3002\u8fdb\u800c\u786e\u5b9a\u6700\u4f73\u7684\u53cd\u5e94\u6761\u4ef6\u4e3a\uff1a\u91c7\u7528\u91d1\u914d\u5408\u7269B<\/strong>\u4f5c\u4e3a\u50ac\u5316\u5242\uff0c\u4e8c\u6c2f\u7532\u70f7\u4f5c\u4e3a\u53cd\u5e94\u6eb6\u5242\uff0c\u53cd\u5e94\u6e29\u5ea6\u4e3a23\u00a0o<\/sup>C\uff0c\u6700\u7ec8\u83b7\u5f9787%\u6536\u7387\u7684\u73af\u52a0\u6210\u4ea7\u72693a<\/strong>\u3002<\/p>\n

\"\"<\/a><\/p>\n

\u5728\u4e0a\u8ff0\u7684\u6700\u4f73\u53cd\u5e94\u6761\u4ef6\u4e0b\uff0c\u4f5c\u8005\u9996\u5148\u5bf9\u4e00\u7cfb\u5217\u7094\u9187\u919a\u5e95\u7269\u7684\u5e94\u7528\u8303\u56f4\u8fdb\u884c\u8003\u5bdf (Scheme 2)\u3002\u7814\u7a76\u8868\u660e\uff0c\u4e0a\u8ff0\u7684\u6807\u51c6\u53cd\u5e94\u6761\u4ef6\u5bf9\u4e8e\u672b\u7aef\u65e0\u53d6\u4ee3\u7684\u7094\u9187\u919a\u5e95\u7269\uff0c\u5747\u80fd\u591f\u826f\u597d\u5730\u517c\u5bb9\uff0c\u5e76\u83b7\u5f97\u8f83\u9ad8\u6536\u7387\u7684\u73af\u52a0\u6210\u4ea7\u72693a<\/strong>\u4e0e3b<\/strong>\u3002\u7136\u800c\uff0c\u5bf9\u4e8eO<\/i><\/em>-\u82ef\u57fa\u4e2d\u5177\u6709\u4f9b\u7535\u5b50\u57fa\u56e2\u53d6\u4ee3\u7684\u7094\u9187\u919a\u5e95\u7269\uff0c\u5219\u89c2\u5bdf\u5230\u53cd\u5e94\u6536\u7387\u51fa\u73b0\u663e\u8457\u964d\u4f4e (3c<\/strong>\u4e0e3d<\/strong>)\u3002\u63a5\u4e0b\u6765\uff0c\u4f5c\u8005\u8fdb\u4e00\u6b65\u5bf9\u4e00\u7cfb\u5217\u70ef\u57fa\u5316\u5408\u7269\u7684\u5e94\u7528\u8303\u56f4\u8fdb\u884c\u6df1\u5165\u7814\u7a76\u3002\u8be5\u5c0f\u7ec4\u53d1\u73b0\uff0c\u4e0a\u8ff0\u7684\u6807\u51c6\u53cd\u5e94\u4f53\u7cfb\u5bf9\u4e8e\u5404\u7c7b\u53d6\u4ee3\u7684\u03b1<\/em>-\u7532\u57fa\u82ef\u4e59\u70ef\u5e95\u7269\uff0c\u5747\u80fd\u591f\u4ee5\u826f\u597d\u7684\u53cd\u5e94\u6536\u7387 (67-90%)\uff0c\u83b7\u5f97\u9884\u671f\u7684\u73af\u52a0\u6210\u4ea7\u72693e<\/strong>–3g<\/strong>\u3002\u7136\u800c\uff0c\u7814\u7a76\u8868\u660e\uff0c\u589e\u5927\u03b1<\/em>-\u53d6\u4ee3\u57fa\u7684\u7acb\u4f53\u4f4d\u963b\uff0c\u5219\u80fd\u591f\u89c2\u5bdf\u5230\u73af\u52a0\u6210\u4ea7\u72693h<\/strong>\u7684\u6536\u7387\u51fa\u73b0\u663e\u8457\u964d\u4f4e\u3002\u4e4b\u540e\uff0c\u4f5c\u8005\u53d1\u73b0\uff0c\u5404\u7c7b\u82ef\u4e59\u70ef (3k<\/strong>–3o<\/strong>)\u4ee5\u53ca\u70ef\u4e19\u57fa\u4e09\u7532\u57fa\u7845\u70f7 (3p<\/strong>–3r<\/strong>)\u5e95\u7269\uff0c\u540c\u6837\u65e0\u6cd5\u83b7\u5f97\u8f83\u9ad8\u7684\u53cd\u5e94\u6536\u7387\u3002\u5e76\u4e14\uff0c\u4f5c\u8005\u8fdb\u4e00\u6b65\u53d1\u73b0\uff0c\u5bf9\u4e8e\u672a\u53d6\u4ee3\u7684\u7094\u9187\u919a\u4e0e\u975e\u73af\u70ef\u57fa\u5e95\u7269\u4e4b\u95f4\u7684\u73af\u52a0\u6210\u8fc7\u7a0b\uff0c\u5219\u4ec5\u67093ee<\/strong>\u80fd\u591f\u83b7\u5f97\u826f\u597d\u7684\u53cd\u5e94\u6536\u7387\u4e0e\u533a\u57df\u9009\u62e9\u6027\u3002\u800c\u73af\u5e9a\u70ef\u3001\u73af\u8f9b\u70ef\u4ee5\u53ca1,5-\u73af\u8f9b\u4e8c\u70ef\u5e95\u7269\uff0c\u5219\u83b7\u5f97\u76f8\u5e94\u7684\u53cc\u73af\u884d\u751f\u72693s<\/strong>–3x<\/strong>\u3002\u4e4b\u540e\uff0c\u4f5c\u8005\u53d1\u73b0\uff0c\u5728\u4e0a\u8ff0\u7684\u6807\u51c6\u53cd\u5e94\u6761\u4ef6\u4e0b\uff0c\u73af\u5df1\u70ef\u5e95\u7269\u5219\u8868\u73b0\u51fa\u8f83\u4f4e\u7684\u53cd\u5e94\u6d3b\u6027\uff0c\u800c(+)-\u8488\u70ef\u5374\u80fd\u591f\u83b7\u5f97\u9884\u671f\u7684[2+2]\u73af\u52a0\u6210\u4ea7\u72693y<\/strong>\u4e0e3z<\/strong>\u3002\u800c\u5728\u03b2<\/em>-\u77f3\u7af9\u70ef (\u03b2<\/em>-caryophyllene)\u53c2\u4e0e\u7684[2+2]\u73af\u52a0\u6210\u53cd\u5e94\u4e2d\uff0c\u5219\u89c2\u5bdf\u5230\u53cd\u5e94\u80fd\u591f\u533a\u57df\u9009\u62e9\u6027\u5730\u5728\u70ef\u57fa\u5e95\u7269\u4e2d\u7684\u4e09\u53d6\u4ee3\u53cc\u952e\u4f4d\u7f6e\u8fdb\u884c\uff0c\u5e76\u83b7\u5f97\u76f8\u5e94\u7684\u76ee\u6807\u4ea7\u72693hh<\/strong>\u00a0(57% \u6536\u7387, 3:1 rr)\uff0c\u540c\u65f6\uff0c\u8868\u73b0\u51fa\u9ad8\u5ea6\u7684\u7acb\u4f53\u4e13\u4e00\u6027\u3002\u6b64\u5916\uff0c\u7814\u7a76\u53d1\u73b0\uff0c\u5177\u6709\u8f83\u9ad8\u7acb\u4f53\u4f4d\u963b\u7684\u70ef\u9187\u919a\u5e95\u7269\uff0c\u540c\u6837\u80fd\u591f\u4e0e\u4e0a\u8ff0\u7684\u6807\u51c6\u53cd\u5e94\u6761\u4ef6\u826f\u597d\u5730\u517c\u5bb9\uff0c\u5e76\u5206\u522b\u4ee579%\u4ee5\u53ca92%\u7684\u53cd\u5e94\u6536\u7387\uff0c\u83b7\u5f97\u9884\u671f\u7684\u53d6\u4ee3\u73af\u4e01\u57fa\u70ef\u9187\u919a\u4ea7\u72693ii<\/strong>\u4e0e3jj<\/strong>\u3002\u540c\u65f6\uff0c\u4f5c\u8005\u53d1\u73b0\uff0c\u5728\u50ac\u5316\u5242A<\/strong>\u5b58\u5728\u7684\u6761\u4ef6\u4e0b\uff0c\u5404\u7c7b\u5185\u7094\u9187\u919a1e<\/strong>–1h<\/strong>\u4e0e\u8102\u80aa\u65cf\u70ef\u57fa\u5316\u5408\u7269 (3kk<\/strong>–3nn<\/strong>\uff0c3rr<\/strong>\uff0c3ss<\/strong>)\u6216\u975e\u6d3b\u5316\u82ef\u4e59\u70ef (3oo<\/strong>\uff0c3pp<\/strong>)\u4e4b\u95f4\u7684[2+2]\u73af\u52a0\u6210\u8fc7\u7a0b\uff0c\u540c\u6837\u80fd\u591f\u83b7\u5f97\u4e2d\u7b49\u81f3\u4f18\u826f\u53cd\u5e94\u6536\u7387\u7684\u9884\u671f\u4ea7\u7269\u3002\u503c\u5f97\u6ce8\u610f\u7684\u662f\uff0c\u5728\u73af\u52a0\u6210\u4ea7\u72693qq<\/strong>\u4e2d\uff0c\u5219\u89c2\u5bdf\u5230\u76f8\u53cd\u7684\u533a\u57df\u9009\u62e9\u6027\u3002\u63a5\u4e0b\u6765\uff0c\u8be5\u5c0f\u7ec4\u8fdb\u4e00\u6b65\u53d1\u73b0\uff0c\u5bcc\u7535\u5b50\u7684\u82ef\u4e59\u70ef\u5e95\u7269\u4e0e\u5185\u7094\u9187\u919a\u4e4b\u95f4\uff0c\u5219\u4f18\u5148\u8fdb\u884c\u76f8\u5e94\u7684\u5f62\u5f0f[4+2]\u73af\u52a0\u6210\u8fc7\u7a0b\uff0c\u8fdb\u800c\u83b7\u5f97\u5404\u7c7b\u53cc\u73af\u4ea7\u72694a<\/strong>–4f<\/strong>\u3002<\/p>\n

\"\"<\/a><\/p>\n

\u63a5\u4e0b\u6765\uff0c\u4f5c\u8005\u8fdb\u4e00\u6b65\u901a\u8fc7\u9178\u6027\u6761\u4ef6\u4e0b (p-TSA\u2022H2<\/sub>O\u6216HCl)\u7684\u6c34\u89e3\u8fc7\u7a0b\uff0c\u5c06\u4e0a\u8ff0\u7684\u73af\u70ef\u9187\u919a\u4ea7\u7269\u8f6c\u5316\u4e3a\u76f8\u5e94\u7684\u73af\u4e01\u916e\u4ea7\u72695a<\/strong>–5e<\/strong>\u00a0<\/strong>(41-75%\u00a0\u6536\u7387)\u00a0(Scheme 3A)\u3002\u540c\u65f6\uff0c\u7814\u7a76\u53d1\u73b0\uff0c\u5728Br2<\/sub>\u6216NCS\u5b58\u5728\u65f6\uff0c\u4e0a\u8ff0\u7684\u70ef\u9187\u919a\u4ea7\u72693ab<\/strong>\u4ee5\u53ca3af<\/strong>\u5219\u80fd\u591f\u901a\u8fc7\u03b1<\/em>-\u5364\u5316\u4ee5\u53ca\u540e\u7eed\u7684\u6c34\u89e3\u8fc7\u7a0b\uff0c\u8f6c\u5316\u4e3a\u76f8\u5e94\u7684\u03b1<\/em>-\u5364\u4ee3\u73af\u4e01\u916e\u4ea7\u72696a<\/strong>\u30016b<\/strong>\u4ee5\u53ca6c<\/strong>\u00a0(Scheme 3B)\u3002<\/p>\n

\"\"<\/a><\/p>\n

\u63a5\u4e0b\u6765\uff0c\u57fa\u4e8eDFT\u8ba1\u7b97\uff0c\u4f5c\u8005\u63d0\u51fa\u4e00\u79cd\u5408\u7406\u7684\u53cd\u5e94\u673a\u7406 (Scheme 4)\u3002\u9996\u5148\uff0c\u901a\u8fc7\u70ef\u57fa\u5316\u5408\u7269\u5bf9\u4e8e\u91d1(I)\u6d3b\u5316\u7684\u7094\u57fa\u919aI<\/strong>\u7684\u8fdb\u653b\uff0c\u5f62\u6210\u73af\u4e19\u57fa\u91d1(I)\u5361\u5bbe\u4e2d\u95f4\u4f53II<\/strong>\u4e0eIV<\/strong>\u3002\u4e4b\u540e\uff0c\u901a\u8fc7\u4e2d\u95f4\u4f53II<\/strong>\u7684\u6269\u73af\u8fc7\u7a0b\uff0c\u5f62\u6210\u4e2d\u95f4\u4f53III<\/strong>\uff0c\u5e76\u901a\u8fc7\u914d\u4f53\u53d6\u4ee3\u8fc7\u7a0b\uff0c\u5f62\u6210\u76f8\u5e94\u7684\u73af\u70ef\u9187\u919a\u4ea7\u72693a<\/strong>\u3002\u76f8\u53cd\u5730\uff0c\u82ef\u57fa\u53d6\u4ee3\u7684\u73af\u4e19\u57fa\u91d1\u5361\u5bbe\u4e2d\u95f4\u4f53IV<\/strong>\u7684\u7ed3\u6784\u5219\u66f4\u52a0\u7c7b\u4f3c\u4e8e\u901a\u8fc7\u9ad8\u70ef\u4e19\u57fa\u91d1(I)\u7a33\u5b9a\u5316\u7684\u78b3\u6b63\u79bb\u5b50\u3002\u63a5\u4e0b\u6765\uff0c\u4e2d\u95f4\u4f53IV<\/strong>\u7ecf\u5386\u540e\u7eed\u7684Friedel-Crafts\u8fc7\u7a0b\uff0c\u4f18\u5148\u5f62\u6210\u76f8\u5e94\u7684Wheland\u4e2d\u95f4\u4f53V<\/strong>\u3002\u518d\u901a\u8fc7V<\/strong>\u7684\u53bb\u8d28\u5b50\u5316\u8fc7\u7a0b\uff0c\u8f6c\u5316\u4e3a\u4e2d\u95f4\u4f53VI<\/strong>\uff0c\u5e76\u8fdb\u4e00\u6b65\u7ecf\u5386\u540e\u7eed\u7684\u8d28\u5b50\u53bb\u91d1\u5316 (protodeauration)\u4ee5\u53ca\u914d\u4f53\u4ea4\u6362\u6b65\u9aa4\uff0c\u6700\u7ec8\u83b7\u5f97\u76f8\u5e94\u7684\u73af\u4e01\u70ef\u916e\u4ea7\u72694a<\/strong>\u3002\u5176\u4e2d\uff0c\u533a\u5206\u4e0a\u8ff0\u4e24\u79cd\u4e0d\u540c\u673a\u7406\u8def\u5f84\u7684\u5173\u952e\u5219\u5728\u4e8e\u70ef\u952eC1\u4f4d\u7f6e\u4e2d\u76f8\u5173\u53d6\u4ee3\u57fa\u7684\u7a33\u5b9a\u5316\u4f5c\u7528\u3002<\/p>\n

\"\"<\/a><\/p>\n

\u603b\u7ed3<\/h4>\n

\u897f\u73ed\u7259ICIQ\u7684A. M. Echavarren\u8bfe\u9898\u7ec4\u6210\u529f\u8bbe\u8ba1\u51fa\u4e00\u79cd\u91c7\u7528\u91d1\u50ac\u5316\u5242\u4fc3\u8fdb\u7684\u82b3\u57fa\u7094\u9187\u919a\u4e0e\u70ef\u57fa\u5316\u5408\u7269\u4e4b\u95f4\u7684\u533a\u57df\u9009\u62e9\u6027[2+2]\u73af\u52a0\u6210\u53cd\u5e94\u65b9\u6cd5\u5b66\uff0c\u8fdb\u800c\u6210\u529f\u5b8c\u6210\u4e00\u7cfb\u5217\u73af\u4e01\u916e\u5206\u5b50\u7684\u6784\u5efa\u3002\u540c\u65f6\uff0c\u4f5c\u8005\u8fdb\u4e00\u6b65\u53d1\u73b0\uff0c\u5185\u7094\u9187\u919a\u4e0e\u5404\u7c7b\u5bcc\u7535\u5b50\u7684\u82ef\u4e59\u70ef\u5e95\u7269\u4e4b\u95f4\uff0c\u5219\u4f18\u5148\u8fdb\u884c\u76f8\u5e94\u7684\u5f62\u5f0f[4+2]\u73af\u52a0\u6210\u8fc7\u7a0b\u3002<\/p>\n

\u53c2\u8003\u6587\u732e<\/b><\/strong><\/h4>\n[1]\u00a0B. B.\u00a0Snider, Chem. Rev.<\/em>\u00a01988<\/strong>, 88<\/em>,\u00a0793.\u00a0doi:\u00a010.1021\/cr00087a005<\/u><\/a>.<\/u><\/p>\n[2]\u00a0Y.\u00a0Wang, Z. Zheng, L. Zhang, Angew.<\/em>\u00a0<\/em>Chem.<\/em>\u00a0<\/em>Int. Ed.<\/em>\u00a02014<\/strong>, 53<\/em>, 9572.\u00a0doi:\u00a010.1002\/anie.201403796<\/u><\/a>.<\/u><\/p>\n[3]\u00a0B. M.\u00a0Trost, J. Xie, N. \u00a0Maulide, J. Am. Chem. Soc. <\/em>2008<\/strong>, 130<\/em>, 17258.\u00a0doi:\u00a010.1021\/ja807894t<\/u><\/a>.<\/u><\/p>\n[4]\u00a0Y.\u00a0Deng, L. A.\u00a0Massey, P. Y. Zavalij, M. P. Doyle,\u00a0Angew.<\/em>\u00a0<\/em>Chem. Int. Ed.<\/em>\u00a0<\/em>2017<\/strong>, 56<\/em>, 7479.\u00a0doi:\u00a010.1002\/anie.201704069<\/u><\/a>.<\/u><\/p>\n[5]\u00a0Z.\u00a0Zheng, Y. Wang, X. Ma, Y. Li, L. Zhang, Angew.<\/em>\u00a0<\/em>Chem. Int. Ed.<\/em>\u00a02020<\/strong>, 59<\/em>, 17398.\u00a0doi:\u00a010.1002\/anie.202003698<\/u><\/a>.<\/u><\/p>\n[6]\u00a0J.\u00a0Xie, P. Xu, Y. Zhu, J. Wang, W.\u00a0C. C. Lee, X. P.\u00a0Zhang, J. Am.<\/em>\u00a0<\/em>Chem. Soc. <\/em>2021<\/strong>, 143<\/em>, 11670.\u00a0doi:\u00a010.1021\/jacs.1c04968<\/u><\/a>.<\/u><\/p>\n[7]\u00a0J.\u00a0Koudelka, T. Tobrman, Eur. J. Org. Chem.<\/em>\u00a02021<\/strong>, 2021<\/em>, 3260.\u00a0doi:\u00a010.1002\/ejoc.202100464<\/u><\/a>.<\/u><\/p>\n[8]\u00a0(a) F. Marion, J. Coulomb, C. Courillon, L. Fensterbank, M.\u00a0Malacria, Org. Lett. <\/em>2004<\/strong>, 6<\/em>, 1509.\u00a0doi:\u00a010.1021\/ol049530g<\/u><\/a>.<\/u><\/p>\n

(b) S.\u00a0Couty, C. Meyer, J. Cossy, Angew.<\/em>\u00a0<\/em>Chem. Int. Ed.<\/em>\u00a02006<\/strong>, 45<\/em>, 6726.\u00a0doi:\u00a010.1002\/anie.200602270<\/u><\/a>.<\/u><\/p>\n[9]\u00a0R. B.\u00a0Dateer, B. S. Shaibu, R. S. Liu, Angew.<\/em>\u00a0<\/em>Chem. Int. Ed.<\/em>\u00a02012<\/strong>, 51<\/em>, 113.\u00a0doi:\u00a010.1002\/anie.201105921<\/u><\/a>.<\/u><\/p>\n[10]\u00a0R. F.\u00a0Sweis, M. P. Schramm, S. A. Kozmin, J. Am. Chem. Soc.<\/em>\u00a02004<\/strong>, 126<\/em>,\u00a07442.\u00a0doi:\u00a010.1021\/ja048251l<\/u><\/a>.<\/u><\/p>\n[11]\u00a0V.\u00a0L\u00f3pez-Carrillo, A. M. Echavarren, J. Am.<\/em>\u00a0<\/em>Chem. Soc.<\/em>\u00a02010<\/strong>, 132<\/em>, 9292.\u00a0doi:\u00a010.1021\/ja104177w<\/u><\/a>.<\/u><\/p>\n[12]\u00a0Y.\u00a0B.\u00a0Bai, Z. Luo, Y.\u00a0Wang, J.\u00a0M. Gao, L. Zhang, J. Am. Chem. Soc. <\/em>2018<\/strong>, 140<\/em>,\u00a05860.\u00a0doi:\u00a010.1021\/jacs.8b01813<\/u><\/a>.<\/u><\/p>\n[13]\u00a0M.\u00a0Kreuzahler, G. Haberhauer, J. Org. Chem.<\/em>\u00a02019<\/strong>, 84<\/em>, 8210.\u00a0doi:\u00a010.1021\/acs.joc.9b01371<\/u><\/a>.<\/u><\/p>\n[14] M. E.\u00a0de Orbe, M. Zanini, O. Quinonero, A.\u00a0M. Echavarren,\u00a0ACS Catal.<\/em>\u00a02019<\/strong>, 9<\/em>, 7817. doi:\u00a010.1021\/acscatal.9b02314<\/u><\/a>.<\/u><\/p>\n

 <\/p>\n","protected":false},"excerpt":{"rendered":"\u672c\u6587\u4f5c\u8005\uff1a\u6749\u6749 \u5bfc\u8bfb \u8fd1\u65e5\uff0c\u897f\u73ed\u7259ICIQ (Institut Catal\u00e0 d’Investigaci\u00f3 Qu\u00edmica)\u7684A.\u00a0M. Echavarren\u8bfe\u9898\u7ec4\u5728Org. Lett.\u4e2d\u53d1\u8868\u8bba\u6587\uff0c\u62a5\u9053\u4e00\u79cd\u901a\u8fc7\u91d1(I)\u50ac\u5316\u5242\u4fc3\u8fdb\u7684\u7094\u9187\u919a (ynol ethers)\u4e0e\u70ef\u57fa\u5316\u5408\u7269\u4e4b\u95f4\u7684[2+2]\u73af\u52a0\u6210\u53cd\u5e94\u65b9\u6cd5\u5b66\uff0c\u8fdb\u800c\u6210\u529f\u5b9e\u73b0\u4e00\u7cfb\u5217\u73af\u4e01\u916e\u884d\u751f\u7269\u7684\u6784\u5efa\u3002\u540c\u65f6\uff0c\u8be5\u5c0f\u7ec4\u53d1\u73b0\uff0c\u5185\u82b3\u57fa\u7094\u9187\u919a\u4e0e\u5bcc\u7535\u5b50\u7684\u82ef\u4e59\u70ef\u5206\u5b50\u4e4b\u95f4\uff0c\u5219\u4f18\u5148\u8fdb\u884c\u76f8\u5e94\u7684[4+2]\u73af\u52a0\u6210\u8fc7\u7a0b\uff0c\u8fdb\u800c\u987a\u5229\u5b9e\u73b0\u5404\u7c7b\u8272\u70f7\u5206\u5b50\u7684\u6784\u5efa\u3002 Synthesis of Cyclobutanones by Gold(I)-Catalyzed [2+2] Cycloaddition of Ynol Ethers with Alkenes M. Zanini, A. Cataffo, A. M. Echavarren, Org. Lett. 2021, ASAP doi: 10.1021\/acs.orglett.1c03499. \u6b63\u6587 \u4f5c\u4e3a\u73af\u7fb0\u57fa\u5316\u5408\u7269\u4e2d\u80fd\u591f\u7a33\u5b9a\u5b58\u5728\u7684\u6700\u5c0f\u9aa8\u67b6\u5355\u5143\uff0c\u73af\u4e01\u916e\u7c7b\u5316\u5408\u7269\u5df2\u7ecf\u6210\u4e3a\u6709\u673a\u5408\u6210\u65b9\u6cd5\u5b66\u7814\u7a76\u4e2d\u6781\u4e3a\u5173\u952e\u7684\u780c\u5757\u3002\u56e0\u6b64\uff0c\u6784\u5efa\u73af\u4e01\u916e\u5206\u5b50\u7684\u76f8\u5173\u7b56\u7565\u7814\u7a76\uff0c\u4e00\u76f4\u4ee5\u6765\u5907\u53d7\u5408\u6210\u5316\u5b66\u5bb6\u7684\u5e7f\u6cdb\u5173\u6ce8\u3002\u76ee\u524d\uff0c\u76f8\u5173\u7684\u53cd\u5e94\u7b56\u7565\u4e3b\u8981\u6d89\u53ca\uff1a\u70ef\u916e\u4e0e\u70ef\u57fa\u5316\u5408\u7269\u4e4b\u95f4\u7684[2+2]\u73af\u52a0\u6210[1]-[2] (Scheme 1A)\u3001\u53d6\u4ee3\u73af\u4e19\u70f7\u6216\u73af\u4e19\u9187\u7684\u6269\u73af\u53cd\u5e94[3]\u3001\u5f62\u5f0f[3+1]\u73af\u52a0\u6210\u53cd\u5e94[4]\u3001\u91d1-\u5361\u5bbe\u524d\u4f53\u7684C-H\u63d2\u5165\u53cd\u5e94[5]\u3001Co(II)\u50ac\u5316\u7684\u81ea\u7531\u57fa1,4-C-H\u70f7\u57fa\u5316\u53cd\u5e94[6]\u3001\u73af\u4e01\u916e\u884d\u751f\u7269\u7684\u5b98\u80fd\u56e2\u5316\u53cd\u5e94[7]\u4ee5\u53ca\u91d1\u6216\u94c2\u50ac\u5316\u7684\u70ef-\u7094\u9170\u80fa\u73af\u5f02\u6784\u5316\u53cd\u5e94\u65b9\u6cd5\u5b66[8]-[9]\u3002 \u8fd9\u91cc\uff0c\u4f5c\u8005\u53d7\u5230Kozmin\u8bfe\u9898\u7ec4\u5bf9\u4e8e\u94f6\u50ac\u5316\u7684\u7845\u57fa\u7094\u9187\u919a\u4e0e\u03b1,\u03b2-\u4e0d\u9971\u548c\u916e\u4e4b\u95f4\u7684[2+2]\u73af\u52a0\u6210\u53cd\u5e94\u65b9\u6cd5\u5b66[10]\u00a0(Scheme 1B)\u4ee5\u53ca\u672c\u8bfe\u9898\u7ec4\u524d\u671f\u5bf9\u4e8e\u91d1\u50ac\u5316\u7684\u7094\u57fa\u4e0e\u70ef\u57fa\u5316\u5408\u7269\u4e4b\u95f4\u7684[2+2]\u73af\u52a0\u6210\u53cd\u5e94\u65b9\u6cd5\u5b66[11]-[14]\u76f8\u5173\u7814\u7a76\u7684\u542f\u53d1\uff0c\u672c\u6587\u4e2d\uff0c\u4f5c\u8005\u6210\u529f\u8bbe\u8ba1\u51fa\u4e00\u79cd\u901a\u8fc7\u91d1\u50ac\u5316\u5242\u4fc3\u8fdb\u7684\u82b3\u57fa\u7094\u9187\u919a\u4e0e\u70ef\u57fa\u5316\u5408\u7269\u4e4b\u95f4\u7684[2+2]\u73af\u52a0\u6210\u53cd\u5e94\u65b9\u6cd5\u5b66\uff0c\u8fdb\u800c\u6709\u6548\u5730\u5b9e\u73b0\u4e00\u7cfb\u5217\u73af\u4e01\u916e\u5206\u5b50\u7684\u6784\u5efa (Scheme 1B)\u3002\u540c\u65f6\uff0c\u7814\u7a76\u53d1\u73b0\uff0c\u5185\u82b3\u57fa\u7094\u9187\u919a\u4e0e\u70ef\u57fa\u5316\u5408\u7269\u4e4b\u95f4\uff0c\u5219\u4f18\u5148\u8fdb\u884c\u76f8\u5e94\u7684[4+2]\u73af\u52a0\u6210\u8fc7\u7a0b\uff0c\u8fdb\u800c\u83b7\u5f97\u4e00\u7cfb\u5217\u91cd\u8981\u7684\u8272\u70f7\u5206\u5b50\u3002 \u9996\u5148\uff0c\u4f5c\u8005\u91c7\u7528\u82ef\u57fa\u7094\u9187\u919a1a\u4e0e\u03b1-\u7532\u57fa\u82ef\u4e59\u70ef2a\u4f5c\u4e3a\u6a21\u578b\u5e95\u7269\uff0c\u8fdb\u884c\u76f8\u5173\u73af\u52a0\u6210\u53cd\u5e94\u6761\u4ef6\u7684\u4f18\u5316\u7b5b\u9009 (Table 1)\u3002\u8fdb\u800c\u786e\u5b9a\u6700\u4f73\u7684\u53cd\u5e94\u6761\u4ef6\u4e3a\uff1a\u91c7\u7528\u91d1\u914d\u5408\u7269B\u4f5c\u4e3a\u50ac\u5316\u5242\uff0c\u4e8c\u6c2f\u7532\u70f7\u4f5c\u4e3a\u53cd\u5e94\u6eb6\u5242\uff0c\u53cd\u5e94\u6e29\u5ea6\u4e3a23\u00a0oC\uff0c\u6700\u7ec8\u83b7\u5f9787%\u6536\u7387\u7684\u73af\u52a0\u6210\u4ea7\u72693a\u3002 \u5728\u4e0a\u8ff0\u7684\u6700\u4f73\u53cd\u5e94\u6761\u4ef6\u4e0b\uff0c\u4f5c\u8005\u9996\u5148\u5bf9\u4e00\u7cfb\u5217\u7094\u9187\u919a\u5e95\u7269\u7684\u5e94\u7528\u8303\u56f4\u8fdb\u884c\u8003\u5bdf (Scheme 2)\u3002\u7814\u7a76\u8868\u660e\uff0c\u4e0a\u8ff0\u7684\u6807\u51c6\u53cd\u5e94\u6761\u4ef6\u5bf9\u4e8e\u672b\u7aef\u65e0\u53d6\u4ee3\u7684\u7094\u9187\u919a\u5e95\u7269\uff0c\u5747\u80fd\u591f\u826f\u597d\u5730\u517c\u5bb9\uff0c\u5e76\u83b7\u5f97\u8f83\u9ad8\u6536\u7387\u7684\u73af\u52a0\u6210\u4ea7\u72693a\u4e0e3b\u3002\u7136\u800c\uff0c\u5bf9\u4e8eO-\u82ef\u57fa\u4e2d\u5177\u6709\u4f9b\u7535\u5b50\u57fa\u56e2\u53d6\u4ee3\u7684\u7094\u9187\u919a\u5e95\u7269\uff0c\u5219\u89c2\u5bdf\u5230\u53cd\u5e94\u6536\u7387\u51fa\u73b0\u663e\u8457\u964d\u4f4e (3c\u4e0e3d)\u3002\u63a5\u4e0b\u6765\uff0c\u4f5c\u8005\u8fdb\u4e00\u6b65\u5bf9\u4e00\u7cfb\u5217\u70ef\u57fa\u5316\u5408\u7269\u7684\u5e94\u7528\u8303\u56f4\u8fdb\u884c\u6df1\u5165\u7814\u7a76\u3002\u8be5\u5c0f\u7ec4\u53d1\u73b0\uff0c\u4e0a\u8ff0\u7684\u6807\u51c6\u53cd\u5e94\u4f53\u7cfb\u5bf9\u4e8e\u5404\u7c7b\u53d6\u4ee3\u7684\u03b1-\u7532\u57fa\u82ef\u4e59\u70ef\u5e95\u7269\uff0c\u5747\u80fd\u591f\u4ee5\u826f\u597d\u7684\u53cd\u5e94\u6536\u7387 (67-90%)\uff0c\u83b7\u5f97\u9884\u671f\u7684\u73af\u52a0\u6210\u4ea7\u72693e–3g\u3002\u7136\u800c\uff0c\u7814\u7a76\u8868\u660e\uff0c\u589e\u5927\u03b1-\u53d6\u4ee3\u57fa\u7684\u7acb\u4f53\u4f4d\u963b\uff0c\u5219\u80fd\u591f\u89c2\u5bdf\u5230\u73af\u52a0\u6210\u4ea7\u72693h\u7684\u6536\u7387\u51fa\u73b0\u663e\u8457\u964d\u4f4e\u3002\u4e4b\u540e\uff0c\u4f5c\u8005\u53d1\u73b0\uff0c\u5404\u7c7b\u82ef\u4e59\u70ef (3k–3o)\u4ee5\u53ca\u70ef\u4e19\u57fa\u4e09\u7532\u57fa\u7845\u70f7 (3p–3r)\u5e95\u7269\uff0c\u540c\u6837\u65e0\u6cd5\u83b7\u5f97\u8f83\u9ad8\u7684\u53cd\u5e94\u6536\u7387\u3002\u5e76\u4e14\uff0c\u4f5c\u8005\u8fdb\u4e00\u6b65\u53d1\u73b0\uff0c\u5bf9\u4e8e\u672a\u53d6\u4ee3\u7684\u7094\u9187\u919a\u4e0e\u975e\u73af\u70ef\u57fa\u5e95\u7269\u4e4b\u95f4\u7684\u73af\u52a0\u6210\u8fc7\u7a0b\uff0c\u5219\u4ec5\u67093ee\u80fd\u591f\u83b7\u5f97\u826f\u597d\u7684\u53cd\u5e94\u6536\u7387\u4e0e\u533a\u57df\u9009\u62e9\u6027\u3002\u800c\u73af\u5e9a\u70ef\u3001\u73af\u8f9b\u70ef\u4ee5\u53ca1,5-\u73af\u8f9b\u4e8c\u70ef\u5e95\u7269\uff0c\u5219\u83b7\u5f97\u76f8\u5e94\u7684\u53cc\u73af\u884d\u751f\u72693s–3x\u3002\u4e4b\u540e\uff0c\u4f5c\u8005\u53d1\u73b0\uff0c\u5728\u4e0a\u8ff0\u7684\u6807\u51c6\u53cd\u5e94\u6761\u4ef6\u4e0b\uff0c\u73af\u5df1\u70ef\u5e95\u7269\u5219\u8868\u73b0\u51fa\u8f83\u4f4e\u7684\u53cd\u5e94\u6d3b\u6027\uff0c\u800c(+)-\u8488\u70ef\u5374\u80fd\u591f\u83b7\u5f97\u9884\u671f\u7684[2+2]\u73af\u52a0\u6210\u4ea7\u72693y\u4e0e3z\u3002\u800c\u5728\u03b2-\u77f3\u7af9\u70ef (\u03b2-caryophyllene)\u53c2\u4e0e\u7684[2+2]\u73af\u52a0\u6210\u53cd\u5e94\u4e2d\uff0c\u5219\u89c2\u5bdf\u5230\u53cd\u5e94\u80fd\u591f\u533a\u57df\u9009\u62e9\u6027\u5730\u5728\u70ef\u57fa\u5e95\u7269\u4e2d\u7684\u4e09\u53d6\u4ee3\u53cc\u952e\u4f4d\u7f6e\u8fdb\u884c\uff0c\u5e76\u83b7\u5f97\u76f8\u5e94\u7684\u76ee\u6807\u4ea7\u72693hh\u00a0(57% \u6536\u7387, 3:1 rr)\uff0c\u540c\u65f6\uff0c\u8868\u73b0\u51fa\u9ad8\u5ea6\u7684\u7acb\u4f53\u4e13\u4e00\u6027\u3002\u6b64\u5916\uff0c\u7814\u7a76\u53d1\u73b0\uff0c\u5177\u6709\u8f83\u9ad8\u7acb\u4f53\u4f4d\u963b\u7684\u70ef\u9187\u919a\u5e95\u7269\uff0c\u540c\u6837\u80fd\u591f\u4e0e\u4e0a\u8ff0\u7684\u6807\u51c6\u53cd\u5e94\u6761\u4ef6\u826f\u597d\u5730\u517c\u5bb9\uff0c\u5e76\u5206\u522b\u4ee579%\u4ee5\u53ca92%\u7684\u53cd\u5e94\u6536\u7387\uff0c\u83b7\u5f97\u9884\u671f\u7684\u53d6\u4ee3\u73af\u4e01\u57fa\u70ef\u9187\u919a\u4ea7\u72693ii\u4e0e3jj\u3002\u540c\u65f6\uff0c\u4f5c\u8005\u53d1\u73b0\uff0c\u5728\u50ac\u5316\u5242A\u5b58\u5728\u7684\u6761\u4ef6\u4e0b\uff0c\u5404\u7c7b\u5185\u7094\u9187\u919a1e–1h\u4e0e\u8102\u80aa\u65cf\u70ef\u57fa\u5316\u5408\u7269 (3kk–3nn\uff0c3rr\uff0c3ss)\u6216\u975e\u6d3b\u5316\u82ef\u4e59\u70ef (3oo\uff0c3pp)\u4e4b\u95f4\u7684[2+2]\u73af\u52a0\u6210\u8fc7\u7a0b\uff0c\u540c\u6837\u80fd\u591f\u83b7\u5f97\u4e2d\u7b49\u81f3\u4f18\u826f\u53cd\u5e94\u6536\u7387\u7684\u9884\u671f\u4ea7\u7269\u3002\u503c\u5f97\u6ce8\u610f\u7684\u662f\uff0c\u5728\u73af\u52a0\u6210\u4ea7\u72693qq\u4e2d\uff0c\u5219\u89c2\u5bdf\u5230\u76f8\u53cd\u7684\u533a\u57df\u9009\u62e9\u6027\u3002\u63a5\u4e0b\u6765\uff0c\u8be5\u5c0f\u7ec4\u8fdb\u4e00\u6b65\u53d1\u73b0\uff0c\u5bcc\u7535\u5b50\u7684\u82ef\u4e59\u70ef\u5e95\u7269\u4e0e\u5185\u7094\u9187\u919a\u4e4b\u95f4\uff0c\u5219\u4f18\u5148\u8fdb\u884c\u76f8\u5e94\u7684\u5f62\u5f0f[4+2]\u73af\u52a0\u6210\u8fc7\u7a0b\uff0c\u8fdb\u800c\u83b7\u5f97\u5404\u7c7b\u53cc\u73af\u4ea7\u72694a–4f\u3002 \u63a5\u4e0b\u6765\uff0c\u4f5c\u8005\u8fdb\u4e00\u6b65\u901a\u8fc7\u9178\u6027\u6761\u4ef6\u4e0b (p-TSA\u2022H2O\u6216HCl)\u7684\u6c34\u89e3\u8fc7\u7a0b\uff0c\u5c06\u4e0a\u8ff0\u7684\u73af\u70ef\u9187\u919a\u4ea7\u7269\u8f6c\u5316\u4e3a\u76f8\u5e94\u7684\u73af\u4e01\u916e\u4ea7\u72695a–5e\u00a0(41-75%\u00a0\u6536\u7387)\u00a0(Scheme 3A)\u3002\u540c\u65f6\uff0c\u7814\u7a76\u53d1\u73b0\uff0c\u5728Br2\u6216NCS\u5b58\u5728\u65f6\uff0c\u4e0a\u8ff0\u7684\u70ef\u9187\u919a\u4ea7\u72693ab\u4ee5\u53ca3af\u5219\u80fd\u591f\u901a\u8fc7\u03b1-\u5364\u5316\u4ee5\u53ca\u540e\u7eed\u7684\u6c34\u89e3\u8fc7\u7a0b\uff0c\u8f6c\u5316\u4e3a\u76f8\u5e94\u7684\u03b1-\u5364\u4ee3\u73af\u4e01\u916e\u4ea7\u72696a\u30016b\u4ee5\u53ca6c\u00a0(Scheme 3B)\u3002 \u63a5\u4e0b\u6765\uff0c\u57fa\u4e8eDFT\u8ba1\u7b97\uff0c\u4f5c\u8005\u63d0\u51fa\u4e00\u79cd\u5408\u7406\u7684\u53cd\u5e94\u673a\u7406 (Scheme 4)\u3002\u9996\u5148\uff0c\u901a\u8fc7\u70ef\u57fa\u5316\u5408\u7269\u5bf9\u4e8e\u91d1(I)\u6d3b\u5316\u7684\u7094\u57fa\u919aI\u7684\u8fdb\u653b\uff0c\u5f62\u6210\u73af\u4e19\u57fa\u91d1(I)\u5361\u5bbe\u4e2d\u95f4\u4f53II\u4e0eIV\u3002\u4e4b\u540e\uff0c\u901a\u8fc7\u4e2d\u95f4\u4f53II\u7684\u6269\u73af\u8fc7\u7a0b\uff0c\u5f62\u6210\u4e2d\u95f4\u4f53III\uff0c\u5e76\u901a\u8fc7\u914d\u4f53\u53d6\u4ee3\u8fc7\u7a0b\uff0c\u5f62\u6210\u76f8\u5e94\u7684\u73af\u70ef\u9187\u919a\u4ea7\u72693a\u3002\u76f8\u53cd\u5730\uff0c\u82ef\u57fa\u53d6\u4ee3\u7684\u73af\u4e19\u57fa\u91d1\u5361\u5bbe\u4e2d\u95f4\u4f53IV\u7684\u7ed3\u6784\u5219\u66f4\u52a0\u7c7b\u4f3c\u4e8e\u901a\u8fc7\u9ad8\u70ef\u4e19\u57fa\u91d1(I)\u7a33\u5b9a\u5316\u7684\u78b3\u6b63\u79bb\u5b50\u3002\u63a5\u4e0b\u6765\uff0c\u4e2d\u95f4\u4f53IV\u7ecf\u5386\u540e\u7eed\u7684Friedel-Crafts\u8fc7\u7a0b\uff0c\u4f18\u5148\u5f62\u6210\u76f8\u5e94\u7684Wheland\u4e2d\u95f4\u4f53V\u3002\u518d\u901a\u8fc7V\u7684\u53bb\u8d28\u5b50\u5316\u8fc7\u7a0b\uff0c\u8f6c\u5316\u4e3a\u4e2d\u95f4\u4f53VI\uff0c\u5e76\u8fdb\u4e00\u6b65\u7ecf\u5386\u540e\u7eed\u7684\u8d28\u5b50\u53bb\u91d1\u5316 (protodeauration)\u4ee5\u53ca\u914d\u4f53\u4ea4\u6362\u6b65\u9aa4\uff0c\u6700\u7ec8\u83b7\u5f97\u76f8\u5e94\u7684\u73af\u4e01\u70ef\u916e\u4ea7\u72694a\u3002\u5176\u4e2d\uff0c\u533a\u5206\u4e0a\u8ff0\u4e24\u79cd\u4e0d\u540c\u673a\u7406\u8def\u5f84\u7684\u5173\u952e\u5219\u5728\u4e8e\u70ef\u952eC1\u4f4d\u7f6e\u4e2d\u76f8\u5173\u53d6\u4ee3\u57fa\u7684\u7a33\u5b9a\u5316\u4f5c\u7528\u3002 \u603b\u7ed3 \u897f\u73ed\u7259ICIQ\u7684A. M. Echavarren\u8bfe\u9898\u7ec4\u6210\u529f\u8bbe\u8ba1\u51fa\u4e00\u79cd\u91c7\u7528\u91d1\u50ac\u5316\u5242\u4fc3\u8fdb\u7684\u82b3\u57fa\u7094\u9187\u919a\u4e0e\u70ef\u57fa\u5316\u5408\u7269\u4e4b\u95f4\u7684\u533a\u57df\u9009\u62e9\u6027[2+2]\u73af\u52a0\u6210\u53cd\u5e94\u65b9\u6cd5\u5b66\uff0c\u8fdb\u800c\u6210\u529f\u5b8c\u6210\u4e00\u7cfb\u5217\u73af\u4e01\u916e\u5206\u5b50\u7684\u6784\u5efa\u3002\u540c\u65f6\uff0c\u4f5c\u8005\u8fdb\u4e00\u6b65\u53d1\u73b0\uff0c\u5185\u7094\u9187\u919a\u4e0e\u5404\u7c7b\u5bcc\u7535\u5b50\u7684\u82ef\u4e59\u70ef\u5e95\u7269\u4e4b\u95f4\uff0c\u5219\u4f18\u5148\u8fdb\u884c\u76f8\u5e94\u7684\u5f62\u5f0f[4+2]\u73af\u52a0\u6210\u8fc7\u7a0b\u3002 \u53c2\u8003\u6587\u732e [1]\u00a0B. B.\u00a0Snider, Chem. Rev.\u00a01988, 88,\u00a0793.\u00a0doi:\u00a010.1021\/cr00087a005. [2]\u00a0Y.\u00a0Wang, Z. Zheng, L. Zhang, Angew.\u00a0Chem.\u00a0Int. Ed.\u00a02014, 53, 9572.\u00a0doi:\u00a010.1002\/anie.201403796. [3]\u00a0B. M.\u00a0Trost, J. Xie, N. \u00a0Maulide, J. Am. Chem. Soc. 2008, 130, 17258.\u00a0doi:\u00a010.1021\/ja807894t. [4]\u00a0Y.\u00a0Deng, L. A.\u00a0Massey, P. Y. Zavalij, M. P. Doyle,\u00a0Angew.\u00a0Chem. Int. 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