{"id":55294,"date":"2025-03-10T21:12:04","date_gmt":"2025-03-10T13:12:04","guid":{"rendered":"\/\/www.gsbet888.com\/?p=55294"},"modified":"2025-03-10T21:26:25","modified_gmt":"2025-03-10T13:26:25","slug":"nature%ef%bc%9a%e8%8a%b3%e9%a6%99%e7%8e%af%e7%9a%84%e5%bc%80%e7%8e%af%e5%a4%8d%e5%88%86%e8%a7%a3%e5%8f%8d%e5%ba%94","status":"publish","type":"post","link":"\/\/www.gsbet888.com\/%e5%8c%96%e5%ad%a6%e6%9d%82%e8%ae%b0\/recentpaper\/2025\/03\/nature%ef%bc%9a%e8%8a%b3%e9%a6%99%e7%8e%af%e7%9a%84%e5%bc%80%e7%8e%af%e5%a4%8d%e5%88%86%e8%a7%a3%e5%8f%8d%e5%ba%94.html","title":{"rendered":"Nature\uff1a\u82b3\u9999\u73af\u7684\u5f00\u73af\u590d\u5206\u89e3\u53cd\u5e94"},"content":{"rendered":"

\u4f5c\u8005\uff1a\u6749\u6749<\/p>\n

\u5bfc\u8bfb\uff1a<\/h4>\n

\u82b3\u9999\u65cf\u5316\u5408\u7269\u56e0\u5176\u7a33\u5b9a\u6027\u3001\u7279\u5f81\u6027\u76f8\u4e92\u4f5c\u7528\u3001\u786e\u5b9a\u7684\u5206\u5b50\u5f62\u72b6\u4ee5\u53ca\u53c2\u4e0e\u7684\u591a\u79cd\u5408\u6210\u53cd\u5e94\uff0c\u5728\u5316\u5b66\u548c\u6750\u6599\u79d1\u5b66\u4e2d\u5f97\u5230\u5e7f\u6cdb\u5e94\u7528\u3002\u76f8\u6bd4\u4e4b\u4e0b\uff0c\u7531\u4e8e\u5f00\u73af\u65f6\u4e0d\u53ef\u907f\u514d\u5730\u4f1a\u7834\u574f\u82b3\u9999\u6027\uff0c\u60f0\u6027\u82b3\u9999\u65cf\u78b3-\u78b3\u952e\u7684\u65ad\u88c2\u5728\u5f88\u5927\u7a0b\u5ea6\u4e0a\u4ecd\u7136\u4e0d\u53ef\u884c\u3002\u5bf9\u4e8e\u975e\u82b3\u9999\u65cf\u9aa8\u67b6\uff0c\u8fc7\u6e21\u91d1\u5c5ealkylidenes\u50ac\u5316\u7684\u70ef\u70c3\u590d\u5206\u89e3\u4f5c\u4e3a\u6700\u901a\u7528\u7684\u78b3-\u78b3\u952e\u6784\u5efa\u548c\u65ad\u88c2\u53cd\u5e94\u4e4b\u4e00\u3002\u7136\u800c\uff0c\u901a\u8fc7\u590d\u5206\u89e3\u5b9e\u73b0\u82b3\u9999\u5316\u5408\u7269\u5f00\u73af\u7b56\u7565\u4ecd\u7136\u96be\u4ee5\u6349\u6478\u3002\u8fd1\u65e5\uff0c\u745e\u58ebBasel\u5927\u5b66\u7684Christof Sparr\u8bfe\u9898\u7ec4\u5728Nature<\/em>\u4e2d\u53d1\u8868\u8bba\u6587\uff0c\u62a5\u9053\u4e00\u79cd\u5168\u65b0\u7684\u82b3\u9999\u73af\u5f00\u73af\u590d\u5206\u89e3(ArROM)\uff0c\u53ef\u7528\u4e8e\u82b3\u9999\u73af\u7684\u65ad\u88c2\uff0c\u5305\u62ectetraphene\u3001\u8418\u3001\u5432\u54da\u3001\u82ef\u5e76\u544b\u5583\u4e0e\u83f2\uff0c\u6d89\u53ca\u4f7f\u7528Schrock-Hoveyda\u94bc\u50ac\u5316\u5242\u3002\u540c\u65f6\uff0c\u8be5\u53cd\u5e94\u6d89\u53ca\u4e00\u79cd\u72ec\u7279alkylidene\u4e2d\u95f4\u4f53\u7684\u5f62\u6210\u3002\u5176\u6b21\uff0c\u8be5\u7b56\u7565\u8fd8\u5b9e\u73b0\u4e86\u7acb\u4f53\u9009\u62e9\u6027\u82b3\u9999\u73af\u7684\u5f00\u73af\u590d\u5206\u89e3\u53cd\u5e94\u3002\u6b64\u5916\uff0c\u82b3\u9999\u73af\u5f00\u73af\u590d\u5206\u89e3\u662f\u4e00\u79cd\u53ef\u884c\u4e14\u6709\u6548\u7684\u65b9\u6cd5\uff0c\u65e0\u9700\u4efb\u4f55\u8bd5\u5242\u6216\u5149\u6fc0\u53d1\uff0c\u5373\u53ef\u5b9e\u73b0\u5404\u79cd\u82b3\u70c3\u7684\u76f8\u4e92\u8f6c\u5316\u3002<\/p>\n

\n

Aromatic ring-opening metathesis<\/p>\n

V. Hutskalova, C. Sparr, Nature<\/em> 2025<\/strong>, 638<\/em>, 697.doi: 10.1038\/s41586-024-08472-z<\/a>.<\/u><\/p>\n<\/blockquote>\n

\"\"<\/p>\n

\u6b63\u6587\uff1a<\/h4>\n

\u53bb\u82b3\u6784\u5316\u662f\u7834\u574f\u82b3\u9999\u4f53\u7cfb\u7684\u4e00\u79cd\u6709\u6548\u7684\u7b56\u7565\uff0c\u4f46\u6781\u5177\u6311\u6218\u6027\u3002\u5176\u4e2d\uff0cBirch\u8fd8\u539f\u3001\u82b3\u70c3\u6c22\u5316\u4ee5\u53ca\u5404\u79cd\u73af\u52a0\u6210\u4e0e\u82b3\u73af\u6c27\u5316\u7b49\u662f\u91cd\u8981\u7684\u53bb\u82b3\u6784\u5316\u65b9\u6cd5\u3002\u82b3\u70c3\u5e95\u7269\u7684\u6269\u73af\u662f\u53e6\u4e00\u79cd\u7c7b\u578b\u7684\u53bb\u82b3\u6784\u5316\u65b9\u6cd5\u3002\u7136\u800c\uff0c\u7531\u4e8e\u82b3\u9999\u65cfC=C\u952e\u7684\u9ad8\u79bb\u89e3\u80fd\uff0c\u5bfc\u81f4\u5176\u5408\u6210\u7684\u7814\u7a76\u5177\u6709\u96be\u5ea6\u3002Buchner\u8bfe\u9898\u7ec4\u7387\u5148\u63d0\u51fa\u4e86\u4e00\u79cd\u5236\u5907\u4e03\u5143\u73af\u7684\u5e38\u89c1\u65b9\u6cd5\uff0c\u6d89\u53ca\u5361\u5bbe\u3001\u6c2e\u70ef(nitrenes)\u4e0ephosphinidenes\u7684(6+1)\u52a0\u6210\u4ee5\u53ca\u968f\u540e\u76846\u03c0<\/em>\u5bf9\u65cb\u7535\u73af\u5f00\u73af\u53cd\u5e94[1]<\/sup>(Fig. 1a)\u3002\u6700\u8fd1\uff0c\u5316\u5b66\u5bb6\u4eec\u5f00\u53d1\u4e86\u4e00\u79cd\u76f8\u5173\u7684\u65b9\u6cd5\uff0c\u7528\u4e8e\u4e0earenophile\u8fdb\u884c\u73af\u52a0\u6210\u53cd\u5e94\uff0c\u7136\u540e\u8fdb\u884c\u73af\u6c27\u5316\u4e0e\u6269\u73af\u53cd\u5e94[2]<\/sup> (Fig. 1b)\u3002\u5728\u81ea\u7136\u754c\uff0c\u5229\u7528\u9176\u4fc3\u6c27\u5316\u7b56\u7565\u6765\u5b9e\u73b0(\u6742)\u82b3\u70c3\u7684\u53bb\u82b3\u6784\u5316\uff0c\u5982\u5728\u539f\u6838\u751f\u7269\u4e2d\u7684\u82b3\u70c3\u6c27\u5316\u9014\u5f84[3]<\/sup>(Fig. 1c)\u3002\u6700\u8fd1\uff0c\u5316\u5b66\u5bb6\u4eec\u8fd8\u62a5\u9053\u4e86\u4e00\u79cd\u975e\u9176\u4fc3\u65ad\u88c2\u82b3\u9999\u73af\u7684\u65b9\u6cd5\uff0c\u5728\u6c27\u6c14\u6c1b\u56f4\u4e0b\u4f7f\u7528NaN3<\/sub>\u4f5c\u4e3a\u8bd5\u5242\uff0c\u901a\u8fc7\u78b3-\u78b3\u952e\u65ad\u88c2\uff0c\u53ef\u5c06\u5404\u79cd\u5b98\u80fd\u56e2\u5316\u7684\u82b3\u70c3\u8f6c\u5316\u4e3a\u70ef\u8148[4]<\/sup>(Fig. 1d)\u3002\u8003\u8651\u5230\u82b3\u9999\u73af\u5f00\u73af\u53cd\u5e94\u7684\u6709\u9650\u6027\uff0c\u56e0\u6b64\u975e\u5e38\u9700\u8981\u5f00\u53d1\u4e00\u79cd\u65b0\u578b\u7684\u5408\u6210\u65b9\u6cd5\u7528\u4e8e\u7834\u574f\u82b3\u9999\u9aa8\u67b6\u3002\u6b64\u5916\uff0c\u8fc7\u6e21\u91d1\u5c5ealkylidene\u50ac\u5316\u7684\u70ef\u70c3\u590d\u5206\u89e3\u5728\u6709\u673a\u5408\u6210\u4e2d\u5177\u6709\u91cd\u8981\u610f\u4e49[5]<\/sup>\uff0c\u4f46\u5bf9\u4e8e\u82b3\u70c3\u590d\u5206\u89e3\u5c1a\u672a\u6709\u76f8\u5173\u7684\u7814\u7a76\u62a5\u9053(Fig. 1e)\u3002\u8fd9\u91cc\uff0c\u745e\u58ebBasel\u5927\u5b66\u7684Christof Sparr\u8bfe\u9898\u7ec4\u62a5\u9053\u4e00\u79cd\u5168\u65b0\u7684\u82b3\u9999\u73af\u5f00\u73af\u590d\u5206\u89e3(aromatic ring-opening metathesis\uff0cArROM)(Fig. 1f)\u3002\"\"<\/p>\n

Fig. 1. Background and concept.a<\/strong>, Buchner aromatic ring expansion. b<\/strong>, Dearomatization by ring expansion to form oxepines. c<\/strong>, Enzymatic cleavage of aromatic rings:\u00a0arene oxidation pathway in prokaryotes. d<\/strong>, Arene ring opening with NaN3<\/sub> and O2<\/sub> for the synthesis of alkenylnitriles. e<\/strong>, General scheme and mechanism of alkene\u2013alkene metathesis. f<\/strong>, Aromatic ring-opening metathesis (ArROM, this work). The red bonds are breaking and the blue bonds are forming. [M], metal; FG, functional group.<\/p>\n

\u9996\u5148\uff0c\u4e3a\u4e86\u7814\u7a76\u82b3\u9999\u73af\u5f00\u73af\u590d\u5206\u89e3(ArROM)\u7684\u53ef\u884c\u6027\uff0c\u4f5c\u8005\u5c06[2+2]-\u73af\u52a0\u6210\u53cd\u5e94\u4e0eRCM(ring-closing metathesis)\u76f8\u7ed3\u5408\uff0c\u901a\u8fc7\u5e38\u89c1\u7684\u91d1\u5c5e\u73af\u4e2d\u95f4\u4f53\u4fc3\u8fdb\u82b3\u9999\u73af\u7684\u65ad\u88c2\u3002\u91c7\u7528tetraphene\u884d\u751f\u72691<\/strong>\u4e3a\u5e95\u7269\uff0c\u94bc\u50ac\u5316\u5242C1<\/strong>\u4e3a\u50ac\u5316\u5242\uff0c\u53ef\u4ee582%\u7684\u6536\u7387\u83b7\u5f97\u4e86\u6240\u9700\u7684\u4ea7\u72692<\/strong>\uff0c\u5b9e\u73b0\u4e86\u82b3\u57fa-tetraphene\u81f3\u8418\u57fa-tetraphene\u7684\u8f6c\u5316(Fig. 2a)\u3002\u91c7\u7528\u8418\u884d\u751f\u72693<\/strong>\u4e3a\u5e95\u7269\uff0c\u94bc\u50ac\u5316\u5242C2<\/strong>\u4e3a\u50ac\u5316\u5242\uff0c\u53ef\u4ee574%\u7684\u6536\u7387\u83b7\u5f97\u4e86\u6240\u9700\u7684\u4ea7\u72694<\/strong>\uff0c\u5b9e\u73b0\u4e86\u8418\u81f3chrysene\u7684\u8f6c\u5316(Fig. 2b)\u3002\u901a\u8fc7ArROM\u4e0e\u53cc\u91cdRCM\u7b56\u7565\uff0c\u53ef\u5b9e\u73b0\u82ef\u5e76\u7a20\u5408\u4e94\u5143\u6742\u73af\u5316\u5408\u7269\u5411naphtho-\u5432\u54da\u4e0ephenanthro-\u5432\u54da\u7684\u8f6c\u5316\uff0c\u59826a<\/strong>\u4e0e6b<\/strong>(Fig. 2c)\u3002\u540c\u65f6\uff0c\u901a\u8fc7\u53cc\u91cdArROM\u4e0e\u53cc\u91cdRCM\u7b56\u7565\uff0c\u8fd8\u53ef\u76f4\u63a5\u5408\u6210\u591a\u73af\u82b3\u70c3(PAHs)\uff0c\u59828a<\/strong>–8d<\/strong>(Fig. 2d)\u3002<\/p>\n

\u5176\u6b21\uff0c\u91c7\u7528ArROM\u4e0eRCM\u7b56\u7565\uff0c\u4e5f\u53ef\u5b9e\u73b0\u5432\u54da\u884d\u751f\u7269\u5f97\u53e6\u4e00\u79cd\u5f00\u73af\u6a21\u5f0f(Fig. 2e)\u3002\u901a\u8fc7\u5bf9\u53cd\u5e94\u7684\u7814\u7a76\u53d1\u73b0\uff0c\u53cd\u5e94\u5f62\u6210\u4e86\u53e6\u4e00\u79cdN<\/em>–o<\/em>-\u82ef\u4e59\u70ef\u57fa\u5432\u54da\uff0c\u5e76\u4e14\u590d\u5206\u89e3\u53cd\u5e94\u662f\u53ef\u9006\u7684\u3002\u56e0\u6b64\uff0c\u53cd\u5e94\u751f\u6210\u4e86\u53d6\u4ee3\u5432\u54da9a<\/strong>–9i<\/strong>\u4e0e\u76f8\u5e94\u7684\u5f02\u6784\u4f5310a<\/strong>–10i<\/strong>\u7684\u5e73\u8861\u6df7\u5408\u7269\u3002\u5176\u4e2d\uff0c\u5bf9\u4e8e\u542b\u6709\u7532\u6c27\u57fa\u4e0e\u7532\u57fa\u7684\u5e95\u7269\uff0c\u53cd\u5e94\u5f62\u6210\u5176\u76f8\u5e94\u7684\u5f02\u6784\u4f53\u7684\u6bd4\u4f8b\u589e\u52a0(\u598210a<\/strong>\u4e0e10b<\/strong>)\u3002\u7136\u800c\uff0c\u542b\u6709\u5f3a\u5438\u7535\u5b50\u57fa\u7684\u5e95\u7269\uff0c\u53cd\u5e94\u672a\u80fd\u6709\u6548\u7684\u8fdb\u884c\uff0c\u59829h<\/strong>\u4e0e9i<\/strong>\u3002\u6b64\u5916\uff0c\u901a\u8fc7\u53cc\u91cdArROM\u4e0e\u4e09\u91cdRCM\u7684\u4e32\u8054\u7b56\u7565\uff0c\u6210\u529f\u5b9e\u73b0\u4e86\u53cc(\u90bb\u82ef\u4e59\u70ef\u57fa)-\u53cc\u5432\u54da\u81f3\u53cc\u5432\u54da-\u83f2\u7684\u8f6c\u5316\uff0c\u598212<\/strong>(Fig. 2f & Extended Data Fig. 1a)\u3002\u540c\u65f6\uff0c\u901a\u8fc7N<\/em>-\u82b3\u57fa\u5432\u54da\u8fdb\u884cArROM\u4e0e\u53cc\u91cdRCM\u53cd\u5e94\u7684\u6761\u4ef6\u4f18\u5316\u53d1\u73b0(Fig. 2g & Extended Data Fig. 1b\/Table 1)\uff0c\u4f7f\u7528\u94bc\u50ac\u5316\u5242C2<\/strong>\u65f6\uff0c\u53cd\u5e94\u53ef\u4ee595%\u7684\u6536\u7387\u83b7\u5f97phenanthrenyl-\u5432\u54da\u4ea7\u726914a<\/strong>\u3002\u5728\u653e\u5927\u89c4\u6a21\u65f6\uff0c\u6536\u7387\u540c\u6837\u53ef\u8fbe96%\u3002\u8ba1\u7b97\u7814\u7a76\u8868\u660e\uff0cRu-\u4e0eMo-catalyst\u4e4b\u95f4\u89c2\u5bdf\u5230\u7684\u53cd\u5e94\u6027\u5dee\u5f02\u4e00\u81f4\uff0c\u5e76\u9884\u6d4b\u82b3\u9999\u73af\u5f00\u73af\u5411\u94bc\u91d1\u5c5e\u73af\u7684\u6d3b\u5316\u80fd\u663e\u8457\u964d\u4f4e(Extended Data Fig. 2 & 3)\u3002\u503c\u5f97\u6ce8\u610f\u7684\u662f\uff0c\u8be5\u65b9\u6cd5\u5bf9\u4e8e\u540c\u65f6\u5177\u6709\u4f9b\u7535\u5b50\u57fa\u56e2(14c<\/strong>)\u4e0e\u5438\u7535\u5b50\u57fa\u56e2(14b<\/strong>\u4e0e14d<\/strong>–14f<\/strong>)\u7684\u5e95\u7269\u975e\u5e38\u6709\u6548\u3002<\/p>\n

\"\"<\/h3>\n

\"\"<\/p>\n

\"\"<\/p>\n

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

\u4e4b\u540e\uff0c\u8be5\u5c0f\u7ec4\u5bf9\u963b\u8f6c\u9009\u62e9\u6027\u82b3\u9999\u73af\u5f00\u73af\u590d\u5206\u89e3(atroposelective aromatic ring-opening metathesis\uff0cAArROM)\u4e0e\u95ed\u73af\u590d\u5206\u89e3(RCM)\u7684\u4e32\u8054\u53cd\u5e94\u8fdb\u884c\u4e86\u7814\u7a76(Fig. 3)\u3002\u7814\u7a76\u7ed3\u679c\u8868\u660e\uff0c\u5229\u7528\u4e0a\u8ff0\u7684\u7b56\u7565\uff0c\u53ef\u5b9e\u73b0\u83f2\u884d\u751f\u7269\u7684\u5f00\u73af\uff0c\u4ece\u800c\u751f\u6210\u56db\u90bb\u4f4d\u53d6\u4ee3\u7684\u963b\u8f6c\u5f02\u6784\u4f53\u4ea7\u726916<\/strong>\u3002\u5176\u4e2d\uff0c\u901a\u8fc7\u624b\u6027\u50ac\u5316\u5242\u7684\u9009\u62e9\uff0c\u80fd\u591f\u901a\u8fc7\u963b\u8f6c\u9009\u62e9\u6027ArROM\u63a7\u5236\u8f74\u624b\u6027\u4e2d\u5fc3\u7684\u6784\u578b\u3002\u901a\u8fc7\u5bf9\u914d\u4f53\u4ee5\u53ca\u53cd\u5e94\u6761\u4ef6\u7684\u4f18\u5316\u540e\u53d1\u73b0(Extended Data Fig. 4\/Table 2)\uff0c\u5728Mo-\u9884\u50ac\u5316\u5242\u4e0e(R<\/em>a<\/sub>)-L1<\/strong>\u50ac\u5316\u4f53\u7cfb\u4e0b\uff0c\u5e95\u726915a<\/strong>\u80fd\u591f\u987a\u5229\u8fdb\u884c\u53cd\u5e94\uff0c\u53ef\u4ee583%\u7684\u6536\u7387\u5f97\u5230\u4ea7\u7269(R<\/em>a<\/sub>)-16a<\/strong>\uff0cer\u4e3a98:2\u3002\u901a\u8fc7\u5bf9\u5e95\u7269\u7684\u8303\u56f4\u6269\u5c55\u65f6\u53d1\u73b0\uff0c\u5404\u79cd\u83f2\u884d\u751f\u7269\u5747\u53ef\u987a\u5229\u8fdb\u884c\u53cd\u5e94\uff0c\u53ef\u4ee5\u9ad8\u5ea6\u7684\u963b\u8f6c\u9009\u62e9\u6027\u4e0e\u6536\u7387\u5f97\u5230\u6240\u9700\u7684\u4ea7\u7269(R<\/em>a<\/sub>)-16<\/strong>\u3002\"\"<\/p>\n

Fig. 3. Atroposelective ArROM. a<\/sup>Conditions: phenanthrene substrate 15a<\/strong>\u201315k<\/strong> (70.0\u2009\u00b5mol), Mo precatalyst (3.50\u2009\u00b5mol, 5.0\u2009mol%), (R<\/em>a<\/sub>)–<\/strong>L1<\/strong> (10.5\u2009\u00b5mol, 15\u2009mol%), toluene (2.3\u2009ml), 65\u2009\u00b0C, 18\u2009h. Yields are given for isolated products; e.r. values were determined\u00a0of the isolated products using high-performance liquid chromatography on a chiral stationary phase. b<\/sup>Reaction performed using an (S<\/em>a<\/sub>)-configured ligand with R\u2009=\u2009mesityl. c<\/sup>With Hoveyda\u2013Grubbs II (HG-II) catalyst to (\u00b1)–<\/strong>16b<\/strong>. NMR yield. d<\/sup>Mo precatalyst (7.00\u2009\u00b5mol, 10\u2009mol%), (R<\/em>a<\/sub>)–<\/strong>L1<\/strong> (21.0\u2009\u00b5mol, 30\u2009mol%). L,\u00a0ligand.<\/p>\n

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

\u968f\u540e\uff0c\u4f5c\u8005\u5bf9\u963b\u8f6c\u9009\u62e9\u6027\u82b3\u9999\u73af\u5f00\u73af\u590d\u5206\u89e3(atroposelective aromatic ring-opening metathesis\uff0cAArROM)\u4e0e\u53cc\u91cd\u95ed\u73af\u590d\u5206\u89e3(RCM)\u7684\u4e32\u8054\u53cd\u5e94\u8fdb\u884c\u4e86\u7814\u7a76(Fig. 4a)\u3002\u7814\u7a76\u7ed3\u679c\u8868\u660e\uff0c\u4e00\u7cfb\u5217\u83f2\u884d\u751f\u7269\uff0c\u5747\u53ef\u987a\u5229\u8fdb\u884c\u53cd\u5e94\uff0c\u53ef\u4ee5\u4f18\u5f02\u7684\u963b\u8f6c\u9009\u62e9\u6027(er>99:1)\u83b7\u5f97\u76f8\u5e94\u7684\u4ea7\u7269(S<\/em>a<\/sub>)-18<\/strong>\u3002\u5176\u4e2d\uff0c\u53cd\u5e94\u7684\u9009\u62e9\u6027\u4e0d\u53d7\u53d6\u4ee3\u6a21\u5f0f\u7684\u5f71\u54cd\u3002\u540c\u65f6\uff0c\u901a\u8fc7X<\/em>-\u5c04\u7ebf\u6676\u4f53\u5b66\uff0c\u8fdb\u4e00\u6b65\u786e\u8ba4\u4e86(S<\/em>a<\/sub>)-18f<\/strong>\u7684\u7edd\u5bf9\u6784\u578b\u3002\u5176\u6b21\uff0c\u4f5c\u8005\u5bf9\u6742\u82b3\u9999\u4f53\u7cfb\u7684\u963b\u8f6c\u9009\u62e9\u6027ArROM\u8fdb\u884c\u4e86\u7814\u7a76(Fig. 4b)\u3002\u7814\u7a76\u7ed3\u679c\u8868\u660e\uff0c\u5728Mo-\u9884\u50ac\u5316\u5242\u4e0e(S<\/em>a<\/sub>)-L2<\/strong>\u50ac\u5316\u4f53\u7cfb\u4e0b\uff0cN<\/em>-\u82b3\u57fa\u5432\u54da\u5e95\u726919a<\/strong>\u80fd\u591f\u987a\u5229\u8fdb\u884c\u53cd\u5e94\uff0c\u53ef41%\u7684\u6536\u7387\u5f97\u5230\u4ea7\u7269(R<\/em>a<\/sub>)-20a<\/strong>\uff0cer\u4e3a87:13\uff0c\u800c\u56de\u6536\u672a\u53cd\u5e94\u5e95\u726919a<\/strong>\u7684er \u4e3a18:82 \uff0c\u8be5\u8fc7\u7a0b\u62c6\u5206\u7684\u6548\u679c\u8f83\u597d\uff0c\u9009\u62e9\u6027\u56e0\u5b50\u4e3a15\u3002\u76f8\u6bd4\u4e4b\u4e0b\uff0c\u901a\u8fc7\u52a8\u6001\u52a8\u529b\u5b66\u62c6\u5206(DKR)\uff0c\u4e5f\u53ef\u56de\u6536\u5177\u6709\u9ad8\u5ea6\u5bf9\u6620\u9009\u62e9\u6027\u7684\u7acb\u4f53\u52a8\u529b\u5b66\u5e95\u726919c<\/strong>\u4e0e19d<\/strong>\uff0c\u5176\u7edd\u5bf9\u6784\u578b\u662f\u901a\u8fc7\u5316\u5408\u7269(S<\/em>a<\/sub>)-20d<\/strong>\u7684\u5fae\u6676\u7535\u5b50\u884d\u5c04(microED)\u5206\u6790\u5efa\u7acb\u7684\u3002\"\"<\/p>\n

Fig. 4. Atroposelective\u00a0ArROM.a<\/strong>, AArROM of phenanthrene derivatives with twofold RCM. a<\/sup>Conditions: phenanthrene substrate 17a<\/strong>\u201317<\/strong>i<\/strong> (70.0\u2009\u00b5mol), Mo precatalyst (7.00\u2009\u00b5mol, 10\u2009mol%), (R<\/em>a<\/sub>)–<\/strong>L1<\/strong> (21.0\u2009\u00b5mol, 30\u2009mol%), toluene (2.3\u2009ml), 85\u2009\u00b0C, 18\u2009h. b<\/sup>Performed using 250\u2009\u00b5mol substrate 17a<\/strong>, Mo precatalyst (12.5\u2009\u00b5mol, 5.0\u2009mol%) and (R<\/em>a<\/sub>)–<\/strong>L1<\/strong> (25.0\u2009\u00b5mol, 10\u2009mol%). c<\/sup>Performed on a 55.0-\u00b5mol scale. b<\/strong>, AArROM of indoles. d<\/sup>Conditions: indole substrate 19a<\/strong>\u201319e<\/strong> (70.0\u2009\u00b5mol), Mo precatalyst (7.00\u2009\u00b5mol, 10\u2009mol%), (S<\/em>a<\/sub>)–<\/strong>L2<\/strong> (21.0\u2009\u00b5mol, 30\u2009mol%), toluene (2.3\u2009ml), 65\u2009\u00b0C, 18\u2009h. Yields are given for isolated products; e.r. values were determined of the isolated products\u00a0using high-performance liquid chromatography on a chiral stationary phase. e<\/sup>Absolute configuration determined by microED.<\/p>\n

\u603b\u7ed3\uff1a<\/h4>\n

\u745e\u58ebBasel\u5927\u5b66\u7684Christof Sparr\u8bfe\u9898\u7ec4\u62a5\u9053\u4e00\u79cd\u5168\u65b0\u7684\u82b3\u9999\u73af\u5f00\u73af\u590d\u5206\u89e3(ArROM)\uff0c\u6d89\u53ca\u4e00\u7cfb\u5217\u72ec\u7279\u7684\u4e32\u8054\u53cd\u5e94\u3001\u6742\u73af\u5316\u5408\u7269\u7684\u5e73\u8861\u3001\u52a8\u529b\u5b66\u62c6\u5206\u3001\u591a\u73af\u82b3\u70c3(PAHs)\u7684\u53cc\u5411\u5408\u6210\u3001\u52a8\u6001\u52a8\u529b\u5b66\u62c6\u5206\u4e0e\u7531\u624b\u6027Schrock-Hoveyda\u94bcalkylidene\u50ac\u5316\u5242\u63a7\u5236\u7684\u9ad8\u5ea6\u963b\u8f6c\u9009\u62e9\u6027\u8f6c\u5316\u7b49\u8fc7\u7a0b\u3002\u8fd9\u4e9b\u7b56\u7565\u5df2\u6210\u529f\u5e94\u7528\u4e8e\u5404\u79cd\u82b3\u9999\u4f53\u7cfb\u7684\u5f00\u73af\uff0c\u5305\u62ectetraphene\u3001\u8418\u3001\u83f2\u4e0e\u5432\u54da\/\u82ef\u5e76\u544b\u5583\u5e95\u7269\u7684\u4e94\u5143\u6742\u73af\u5316\u5408\u7269\u3002<\/p>\n

\u53c2\u8003\u6587\u732e\uff1a<\/strong><\/h4>\n

Fig. 2. Aromatic ring-opening metathesis.a<\/strong>, Tetraphene. b<\/strong>, Naphthalene. c<\/strong>, Five-membered heterocycles. d<\/strong>, Synthesis of polycyclic aromatic hydrocarbons. e<\/strong>, Equilibration of indoles. f<\/strong>, Twofold ArROM of indoles (for the intermediates, see Extended Data Fig. 1a<\/a>). g<\/strong>, ArROM for N<\/em>-aryl indoles (for the scope, see Extended Data Fig. 1b<\/a>). The red text indicates ring opening and the blue text indicates ring closing. Mes, mesityl; TBS, SiMe2<\/sub>t<\/em>Bu.<\/p>\n