{"id":15231,"date":"2017-08-12T10:45:41","date_gmt":"2017-08-12T02:45:41","guid":{"rendered":"\/\/www.gsbet888.com\/?p=15231"},"modified":"2019-08-02T18:52:53","modified_gmt":"2019-08-02T10:52:53","slug":"%e5%85%89%e5%82%ac%e5%8c%96%e5%89%82%e5%82%ac%e5%8c%96%e7%9a%84%e8%87%aa%e7%94%b1%e5%9f%ba%e6%9c%ba%e7%90%86%e7%9a%84%e6%b0%a7%e5%8c%9612-brook%e9%87%8d%e6%8e%92%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\/2017\/08\/%e5%85%89%e5%82%ac%e5%8c%96%e5%89%82%e5%82%ac%e5%8c%96%e7%9a%84%e8%87%aa%e7%94%b1%e5%9f%ba%e6%9c%ba%e7%90%86%e7%9a%84%e6%b0%a7%e5%8c%9612-brook%e9%87%8d%e6%8e%92%e5%8f%8d%e5%ba%94.html","title":{"rendered":"\u5149\u50ac\u5316\u5242\u50ac\u5316\u7684\u81ea\u7531\u57fa\u673a\u7406\u7684\u6c27\u5316[1,2]-Brook\u91cd\u6392\u53cd\u5e94"},"content":{"rendered":"

\u672c\u6587\u6295\u7a3f\u4f5c\u8005\u5b59\u82cf\u8d5f<\/strong><\/p>\n

\u5728\u4e0a\u4e16\u7eaa50\u5e74\u4ee3\uff0cBrook\u53d1\u73b0\u4e86\u5206\u5b50\u5185\u7684\u9633\u79bb\u5b50\u548c\u7845\u57fa\u53c2\u4e0e\u8fc1\u79fb\u751f\u6210\u7845\u919a\u7684\u53cd\u5e94\uff0c\u547d\u540d\u4e3aBrook\u91cd\u6392\u53cd\u5e94\uff0c\u5982Figure 1[1,2]<\/sup>\uff0c\u53cd\u5e94\u4e2d\u662f\u53d1\u751f\u4e86\u7845\u88ab\u4eb2\u6838\u7684\u6c27\u8fdb\u653b\u751f\u6210\u4e86Si-O\u952e\uff0c\u4e00\u822c\u6765\u8bb2\uff0cBrook\u91cd\u6392\u662f\u901a\u8fc7\u79bb\u5b50\u673a\u7406\u8fdb\u884c\u7684\u3002<\/p>\n

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

Figure 1 \u79bb\u5b50\u673a\u7406\u7684Brook\u91cd\u6392\u548c\u4e00\u4e2a\u5b9e\u4f8b<\/p>\n

\u6765\u81ea\u7f8e\u56fd\u5bbe\u5dde\u5927\u5b66\u7684Amos B. Smith\u56e2\u961f\u6700\u8fd1\u5728JACS\u00a0<\/em><\/strong>\u4e0a\u62a5\u9053\u4e00\u79cd\u81ea\u7531\u57fa\u673a\u7406\/SET(single electron transfer)\u901a\u8fc7\u751f\u6210\u8d85\u4ef7\u7845\u7c7b\u5316\u5408\u7269\u7684Brook\u91cd\u6392\u53cd\u5e94\uff0c\u4f46\u662f\u8fd9\u4e2a\u53cd\u5e94\u5e76\u5e76\u6ca1\u6709\u5728\u5408\u6210\u4e2d\u5e38\u7528[3]<\/sup>\u3002<\/p>\n

Oxidative [1,2]-Brook Rearrangements Exploiting Single-Electron Transfer: Photoredox-Catalyzed Alkylations and Arylations<\/p>\n

Yifan Deng, Qi Liu, and Amos B. SmithIII<\/p>\n

J. Am. Chem. Soc.<\/em>, 2017<\/strong>, 139 (28), pp 9487\u20139490, DOI:10.1021\/jacs.7b05165<\/a>)<\/p><\/blockquote>\n

 <\/p>\n

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

SCHEME 1<\/u><\/em><\/strong><\/p>\n

\u901a\u5e38\u6765\u8bb2\uff0c\u6709\u673a\u7845\u7684\u5316\u5408\u7269\u56e0\u5177\u6709\u5f88\u9ad8\u7684\u6c27\u5316\u7535\u4f4d\u800c\u96be\u5728\u53cd\u5e94\u4e2d\u88ab\u6c27\u5316\uff0c\u4f46\u662f\u5f53\u5f15\u5165\u4e00\u79cd\u6027\u8d28\u6e29\u548c\u5149\u50ac\u5316\u6c27\u5316\u8fd8\u539f\u53cd\u5e94\u7684\u50ac\u5316\u5242\u65f6\uff0c\u5c31\u53ef\u4ee5\u751f\u6210\u8d85\u4ef7\u7684\u7845\u5316\u5408\u7269\uff0c\u800c\u8fd9\u4e2a\u5316\u5408\u7269\u662f\u53ef\u4ee5\u6f5c\u5728\u5730\u8f6c\u5316\u751f\u6210\u81ea\u7531\u57fa\u7684\uff08\u5982Scheme 2\u6240\u793a\uff09\u3002\"\"<\/a><\/p>\n

SCHEME 2<\/u><\/em><\/strong><\/p>\n

 <\/p>\n

\u672c\u6587\u62a5\u9053\u7684\u662f\u5408\u6210\u4e00\u79cd\u65b0\u578b\u7684\u4e94\u914d\u4f4d\u7684\u7845\u5316\u5408\u7269\u3002\u5e76\u4e14Amos B. Smith\u56e2\u961f\u9884\u6d4b\u5230\uff0c\u901a\u8fc7\u539f\u4f4d\u7684Brook\u91cd\u6392\u548c\u540e\u7eed\u7684\u5728\u5149\u6c27\u5316\u8fd8\u539f\u50ac\u5316\u5242\u50ac\u5316\u4e0b\u8fdb\u884cC-Si\u952e\u7684SET\u89e3\u751f\u6210\u751f\u4e94\u914d\u4f4d\u7684\u7845\u5316\u5408\uff0c\u8fd9\u4e2a\u8fc7\u7a0b\u4e2d\u53ef\u4ee5\u8bf4\u751f\u6210\u03b1-\u7f9f\u57fa\u81ea\u7531\u57fa\u3002\u5982\u679c\u8981\u4f7f\u5f97\u6c27\u5316\u7684[1,2]-Brook\u91cd\u6392\u53ef\u4ee5\u53d1\u751f\uff0c\u90a3\u4e48\u9700\u8981\u6ee1\u8db3\uff1aA.\u5149\u50ac\u5316\u5242\u6fc0\u53d1\u6001\u7684\u8fd8\u539f\u7535\u52bf\u9700\u8981\u8db3\u591f\u5927\uff0c\u4ee5\u81f3\u4e8e\u53ef\u4ee5\u7834\u574fC-Si\u952e\uff1bB. \u5f53\u7845\u539f\u5b50\u4e0a\u8fde\u6709\u56db\u4e2a\u53d6\u4ee3\u57fa\u7684\u65f6\u5019\uff0cC-Si\u952e\u5fc5\u987b\u9009\u62e9\u6027\u65ad\u88c2\u751f\u6210\u70f7\u57fa\u81ea\u7531\u57fa\u3002<\/p>\n

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

SCHEME 3<\/u><\/em><\/strong><\/p>\n

 <\/p>\n

\u4ece\u673a\u7406\u4e0a\u505a\u51fa\u7684\u5047\u8bbe\uff1a\u9187\u5931\u53bb\u8d28\u5b50\u5f62\u6210\u4e09\u5143\u73afA<\/strong>\u5e76\u8fbe\u5230\u5e73\u8861\uff0c\u800cA<\/strong>\u53ef\u4ee5\u8fdb\u4e00\u6b65\u5728Ir\u50ac\u5316\u5242\u7684\u4f5c\u7528\u4e0b\u88ab\u6c27\u5316\u4e3a\u81ea\u7531\u57faB<\/strong>\uff0c\u4e4b\u540eB<\/strong>\u53d1\u751f\u5171\u8f6d\u52a0\u6210\u751f\u6210C<\/strong>\uff08Scheme 3a\uff09\uff0cC<\/strong>\u518d\u901a\u8fc7\u7535\u5b50\u8f6c\u79fb\u548c\u8d28\u5b50\u5316\u751f\u6210D<\/strong>\uff0c\u540c\u65f6\u5149\u50ac\u5316\u5242\u53d8\u6210\u57fa\u6001\u3002\u6b64\u5916\uff0cIr(III)\u8bd5\u5242\u88ab\u8fd8\u539f\u6210Ir(IV)\uff0c\u800c\u82b3\u70c3\u7c7b\u5316\u5408\u7269\u88ab\u6c27\u5316\u5316\u4e3a\u81ea\u7531\u57fa\u8d1f\u79bb\u5b50E<\/strong>\uff0c\u8fd9\u91cc\u5047\u8bbeIr(IV)\u53ef\u4ee5\u5c06A<\/strong>\u6c27\u5316\u751f\u6210\u9ad8\u4ef7\u7684\u4e2d\u95f4\u4f53B \uff0cE<\/strong>\u548cB<\/strong>\u7ed3\u5408\u8131\u53bb\u4e00\u4e2a\u6c30\u79bb\u5b50\u751f\u6210\u82b3\u57fa\u5316\u7684F<\/strong>\u3002<\/p>\n

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

TABLE 3<\/u><\/em><\/strong><\/p>\n

 <\/p>\n

\u4e3a\u4e86\u9a8c\u8bc1\u53cd\u5e94\u673a\u7406\uff0c\u5148\u9009\u7528\u7532\u57fa\u4e59\u70ef\u57fa\u916e2a<\/strong>\u548cTBS\u4f5c\u4e3a\u7845\u57fa\u7684\u5e95\u72691b<\/strong>\uff0c\u5176\u4e2d\u916e\u662f\u81ea\u7531\u57fa\u7684\u53d7\u4f53\uff0c\u5b9e\u9a8c\u53d1\u73b0\u4ee5PivOK\u548cDCE\u4e3a\u6700\u4f73\u6761\u4ef6\uff0c\u4ea7\u738738%\uff0c\u53cd\u5e94\u4e2d\u5149\u50ac\u5316\u5242Ir[dF(CF3<\/sub>)ppy]2<\/sub>(dtbpy)PF6<\/sub>\u7684\u6d53\u5ea6\u662f3 mol%\uff0c\u800c\u5176\u4ed6\u7684\u50ac\u5316\u5242\u6548\u679c\u90fd\u4e0d\u597d\u3002\u53cd\u5e94\u7684\u6eb6\u5242\u5bf9\u53cd\u5e94\u7684\u5f71\u54cd\u975e\u5e38\u5927\uff0c\u4f8b\u5982\u4e19\u916e\u548c\u4e59\u8148\u4e2d\u4e0d\u53d1\u751f\u53cd\u5e94\uff0c\u5f3a\u78b1\u5219\u4f1a\u5bfc\u81f4\u53d1\u751f\u78b1\u50ac\u5316\u7684Brook\u91cd\u6392\u53cd\u5e94\uff0c\u800c\u78b1\u6027\u8f83\u5f31\u7684\u78b1\u5219\u4f1a\u4f7f\u5f97\u8f6c\u5316\u7387\u964d\u4f4e\u3002\u6700\u4f73\u914d\u6bd4\u662fPivOK\/AcOSc=1:1\u548c1b\/2a<\/strong>=1:2 equiv. \u800c\u5f53\u53cd\u5e94\u5728\u8f83\u9ad8\u6d53\u5ea6(2.5 M)\u548c0.5 mmol\u89c4\u6a21\u4e0b\u53cd\u5e94\u65f6\uff0c2a<\/strong>\u53ef\u4ee5\u51cf\u5c11\u52301 equiv. \u4f7f\u5f97\u4ea7\u7387\u523072%\u3002<\/p>\n

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

SCHEME 4<\/u><\/em><\/strong><\/p>\n

 <\/p>\n

\u4e0b\u9762\u662f\u6d4b\u8bd5\u4e0d\u540c\u70f7\u57fa\u7845\u7684\u4e0d\u540c\u7ed3\u679c\uff0c\u6700\u521d\u662f\u4f7f\u7528\u82b3\u57fa\uff08\u4e09\u70f7\u57fa\uff09-\u7532\u9187(1a-1e<\/strong>)\u4f5c\u4e3a\u53cd\u5e94\u5e95\u7269\uff0c\u7845\u57fa\u4f7f\u7528\u7684\u662fTMS\uff0cTES\uff0cTBS\u548cTIPS\uff0c\u4ed6\u4eec\u7684\u4ea7\u7387\u90fd\u5927\u4e8e70%\uff0c\u8fd9\u8868\u660e\u7845\u4e0a\u7684\u4f4d\u963b\u4e0d\u4f1a\u5f71\u54cd\u53cd\u5e94\u7684\u53d1\u751f\u3002\u5927\u4f53\u4e0a\u6765\u770b\uff0c\u542b\u6709TES\u548cTBS\u7684\u5e95\u7269\u4f1a\u6bd4\u5bf9\u5e94\u7684TMS\u7684\u5e95\u7269\u7684\u4ea7\u7387\u8981\u9ad8\uff0c\u8fd9\u53ef\u80fd\u662f\u56e0\u4e3aTES\u548cTBS\u7684\u5e95\u7269\u4e2dC-Si\u952e\u6bd4\u8f83\u7a33\u5b9a\u3002\u5f53\u5e95\u7269\u6362\u6210\u542b\u6709DMPS(3d<\/strong>)\u65f6\uff0c\u4ea7\u7387\u5c31\u8f83\u4f4e\u4e86(56%)\uff0c\u6b64\u800c\u4e14\u82ef\u57fa\u7684\u5438\u7535\u6548\u5e94\u4e5f\u4e0d\u5229\u4e8e\u53cd\u5e94\u7684\u8fdb\u884c\u3002\u6b64\u5916\u82b3\u73af\u4e0a\u4e0d\u540c\u7684\u53d6\u4ee3\u57fa\u4e5f\u4f1a\u5f71\u54cd\u53cd\u5e94\uff0c\u4f9b\u7535\u57fa\u56e2(EDG)\u4f1a\u5bfc\u81f4\u8f83\u9ad8\u7684\u4ea7\u7387(3f-3k<\/strong>)\uff0c\u5364\u539f\u5b50\u7684\u6548\u679c\u4e5f\u4e0d\u9519(3l-3n<\/strong>)\uff0c\u7136\u800c\u5f3a\u70c8\u5438\u7535\u7684\u4e09\u6c1f\u7532\u57fa\u5c31\u4f1a\u4e0d\u5229\u4e8e\u53cd\u5e94\u7684\u4ea7\u7387(3o<\/strong>)\uff1b\u4f4d\u963b\u8f83\u5927\u7684o<\/em>-\u53d6\u4ee3\u82ef\u7684\u4ea7\u7387\u4e5f\u4e0d\u9519(3j<\/strong>, 67%)\uff1b\u4e94\u5143\u82b3\u73af\u4f5c\u4e3a\u53d6\u4ee3\u57fa\u4e5f\u53ef\u4ee5\u5f97\u5230\u8f83\u9ad8\u7684\u4ea7\u7387(3p-3q<\/strong>)\u3002\u6211\u4eec\u603b\u7ed3\u8ba4\u4e3a3q<\/strong>\u7684\u4ea7\u7387\u964d\u4f4e\u7684\u539f\u56e0\u662f\u53ef\u80fd\u662f\u751f\u62101q<\/strong>\u65f6\u53d1\u751f\u4e86\u5206\u89e3\u4f5c\u7528\u3002\u6700\u540e\uff0c\u53ef\u4ee5\u8fdb\u884c\u8f83\u89c4\u6a21\u5408\u6210\u7684\u662f1f<\/strong>\uff0cIr\u50ac\u5316\u5242\u7684\u6d53\u5ea6\u4e3a2 mol%\uff0c\u53cd\u5e94\u6d53\u5ea61.0 M\u3002<\/p>\n

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

SCHEME 5<\/u><\/em><\/strong><\/p>\n

 <\/p>\n

\u63a5\u4e0b\u6765\u662f\u5bf9\u4e8e\u81ea\u7531\u57fa\u53d7\u4f53\u70f7\u57fa\u916e\u548c\u82b3\u57fa\u916e\u7684\u6d4b\u8bd5(2b-2k<\/strong>)\u3002\u4f53\u79ef\u8f83\u5927\u7684\u57fa\u56e2\u4e0d\u4f1a\u5f71\u54cd\u53cd\u5e94\u7684\u6d3b\u6027\uff0c\u53ef\u4ee5\u5f97\u5230\u8f83\u9ad8\u4ea7\u7387\u7684\u4ea7\u7269(4b-4c<\/strong>)\uff1b\u5177\u6709\u8fdc\u7a0b\u7684OTBS\u57fa\u56e2\u7684\u916e2d<\/strong>\u4e5f\u53ef\u4ee5\u8f83\u597d\u7684\u53c2\u4e0e\u53cd\u5e94\uff0c\u56e0\u6b64\u53ef\u4ee5\u5229\u7528\u5230\u5408\u6210\u7684\u53cd\u5e94\u4e2d\u53bb\u3002\u82b3\u57fa\u916e\u901a\u5e38\u4f1a\u6bd4\u70f7\u57fa\u916e\u7684\u6548\u679c\u597d\uff0c\u82b3\u73af\u4e0a\u4e0d\u540c\u7684\u5b98\u80fd\u56e2(2e-2i<\/strong>)\u7684\u6548\u679c\u4e0d\u540c\uff0c\u7535\u5b50\u6548\u5e94\u548c\u4f4d\u963b\u6548\u5e94\u90fd\u4e0d\u4f1a\u5f71\u54cd\u53cd\u5e94\u7684\u6d3b\u6027\u3002\u4f46\u662f\uff0c1-\/2-\u53d6\u4ee3\u916e(2k<\/strong>,2j<\/strong>)\u8868\u660e\u916e\u7684\u7535\u5b50\u6548\u5e94\u548c\u4f4d\u963b\u6548\u5e94\u4f1a\u663e\u8457\u7684\u5f71\u54cd\u53cd\u5e94\u7684\u8fdb\u884c\uff0c\u4ea7\u7387\u4f1a\u5927\u5927\u964d\u4f4e\uff0c\u4f46\u662f\u8b6c\u5982\u5177\u6709\u5438\u70b9\u57fa\u56e2\u76842k<\/strong>\u5c31\u4f1a\u5f97\u5230\u5f88\u9ad8\u7684\u4ea7\u7387\u3002\u4f46\u662f\u4e19\u70ef\u9178\u76d0\u53ea\u80fd\u5f97\u5230\u75d5\u91cf\u7684\u4ea7\u7269\uff0c\u8fd9\u53ef\u80fd\u662f\u56e0\u4e3a\u5176\u4ea7\u7269\u548c\u03b1-\u7fb0\u57fa\u81ea\u7531\u57fa\u7684\u7ed3\u5408\u975e\u5e38\u56f0\u96be\u3002\u5f53\u6709\u82ef\u57fa\u5f15\u5165\u5230\u03b1-\u4f4d\u65f6\uff0c\u70f7\u57fa\u5316\u7684\u4ea7\u72694l<\/strong>\u7684\u4ea7\u7387\u4f1a\u8fbe\u523086%\u3002<\/p>\n

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

TABLE 2<\/u><\/em><\/strong><\/p>\n

 <\/p>\n

\u4ee5\u4e0a\u786e\u5b9a\u4e86\u6700\u6709\u5229\u7684\u53cd\u5e94\u5e95\u7269\u4e4b\u540e\uff0c\u63a5\u4e0b\u6765\u662f\u63a2\u7d22\u53cd\u5e94\u7684\u5386\u7a0b\u662f\u5426\u662fSET\u8fc7\u7a0b(Scheme 3b)\uff0c\u5176\u4e2d\u8ba4\u4e3aB\u53ef\u4ee5\u53c2\u4e0e\u50ac\u5316\u5faa\u73af\uff0c\u56e0\u6b64\u82b3\u57fa\u5316\u53cd\u5e94\u53ef\u4ee5\u53d1\u751f\u3002Amos B. Smith\u56e2\u961f\u9009\u62e9\u4e861b<\/strong>\u4f5c\u4e3a\u53cd\u5e94\u5e95\u7269\uff0c5a<\/strong>\u4f5c\u4e3a\u81ea\u7531\u57fa\u53d7\u4f53\uff0c\u53cd\u5e94\u4e2d\u8fd8\u4f7f\u7528\u4e86\u8f9b\u9178\uff0c\u8fd9\u6709\u5229\u4e8e\u6c30\u6839\u79bb\u5b50\u7684\u4ea7\u751f\u3002\u8d77\u521d\u662fDCE\u4f5c\u4e3a\u53cd\u5e94\u4ecb\u8d28\uff0c\u540c\u65f6\u52a0\u51651 equiv. AcOCs\u4f5c\u4e3a\u78b1\uff0c\u6b64\u65f6\u4ea7\u7269\u975e\u5e38\u5c11\u3002\u6eb6\u5242\u4f1a\u663e\u8457\u5730\u5f71\u54cd\u53cd\u5e94\u7684\u8fdb\u884c\uff0c\u6781\u6027\u6eb6\u5242\u4f8b\u5982DMF\uff0cDMA\u53ef\u4ee5\u5f97\u5230\u5f88\u597d\u7684\u6548\u679c(Entry 2-3)\uff1b\u7531\u4e8e\u6301\u4e45\u81ea\u7531\u57fa\u6548\u5e94\uff0c\u81ea\u7531\u57fa\u524d\u9a71\u4f531b<\/strong>\u53ef\u4ee5\u52a0\u901f\u53cd\u5e94\u7684\u8fdb\u884c\uff1b\u56e0\u6b64\uff0c\u52a0\u901f\u4ea7\u751f1b<\/strong>\u662f\u589e\u5927\u8f6c\u5316\u7387\u7684\u6709\u6548\u65b9\u6cd5\u3002\u5f53\u8c03\u6574\u78b1\u7684\u7528\u91cf\u65f6\u53d1\u73b0\uff0c\u4f7f\u7528\u5316\u5b66\u8ba1\u91cf\u7684\u78b1\u4f9d\u65e7\u4f1a\u5f97\u5230\u76f8\u4f3c\u7684\u4ea7\u7387(Entry 5)\uff0c\u6700\u7ec8\uff0c3equiv. \u76841b<\/strong>\u53ef\u4ee5\u5f97\u52306a<\/strong>\uff0c\u5206\u79bb\u4ea7\u7387\u4e3a83%(Entry 6)\u3002<\/p>\n

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

SCHEME 6<\/u><\/em><\/strong><\/p>\n

 <\/p>\n

\u57fa\u4e8e\u4e0a\u8ff0\u7684\u53cd\u5e94\u6761\u4ef6\uff0c\u63a5\u4e0b\u6765\u662f\u7ed3\u6784\u5bf9\u4e8e\u53cd\u5e94\u7684\u5f71\u54cd\uff0cScheme 6\u4e2d\uff0c\u542b\u6709EDG\u548cEWG\u7684\u5e95\u7269\u7684\u4ea7\u7387\u90fd\u4e0d\u9519(6a-6e<\/strong>, 66-85%)\uff0c\u544b\u5583\u548c\u567b\u5429\u4f5c\u4e3a\u53d6\u4ee3\u57fa\u65f6\u4ea7\u7387\u8f83\u9ad8(6f-6g<\/strong>)\uff1b\u5c06TMS\u6362\u6210TES\u53d1\u751f\u7684\u53cd\u5e94\u7c7b\u4f3c\uff0c\u800c6h<\/strong>\u7684\u4ea7\u7387\u5219\u8f83\u4f4e\uff0c\u56e0\u4e3a\u53d1\u751f\u4e86\u8131\u7845\u53cd\u5e94\u3002\u53d6\u4ee3\u7684\u82b3\u9999\u53d6\u4ee3\u57fa\u4f1a\u5f97\u5230\u7c7b\u4f3c\u7684\u4ea7\u7387(7a-7c<\/strong>)\uff0c\u800c\u82ef\u4e59\u8148\u548c\u781c\u3001\u916f\u53ef\u4ee5\u53d1\u751f\u8fd9\u4e2a\u53cd\u5e94\uff0c\u4f46\u662f\u4ea7\u7387\u8f83\u4f4e(7d-7e<\/strong>)\u3002<\/p>\n

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

SCHEME 7<\/u><\/em><\/strong><\/p>\n

 <\/p>\n

\u4e3a\u4e86\u8fdb\u884c\u53cd\u5e94\u673a\u7406\u7684\u7814\u7a76\uff0c\u63a2\u7a76\u53cd\u5e94\u662f\u5426\u662f\u5149\u5316\u5b66\u7684\u6c27\u5316\u8fd8\u539f\u7684Brook\u91cd\u6392\u53cd\u5e94\uff0c\u5148\u4f7f\u7528TEMPO\u4f5c\u4e3a\u81ea\u7531\u57fa\u6dec\u706d\u5242\uff0c\u548c\u5e95\u72691b<\/strong>\u53cd\u5e94\uff0c\u52a0\u5408\u4ea7\u72699<\/strong>\u5206\u79bb\u4ea7\u7387\u4e3a42%\uff0c\u540c\u65f63b<\/strong>\u7684\u4ea7\u7387\u964d\u4f4e\u5230\u4e8616%\u3002\u6b64\u5916\u53cd\u5e94\u8fd8\u9700\u8981\u78b1\u3001\u5149\u548c\u5149\u50ac\u5316\u5242\u53c2\u4e0e\uff0c\u6ca1\u6709\u5149\u6216\u8005\u5149\u50ac\u5316\u5242\uff0c\u53cd\u5e94\u7684\u539f\u6599\u57fa\u672c\u4e0d\u53d8\uff0c\u540c\u65f6\u5982\u679c\u78b1\u4e0d\u52a0\u5165\u5230\u53cd\u5e94\u4f53\u7cfb\u4e2d\uff0c\u90a3\u4e48\u53ea\u6709\u75d5\u91cf\u76843b<\/strong>\u751f\u6210\uff0c\u800c\u7531\u4e8e\u8fc7\u5ea6\u6c27\u5316\u800c\u751f\u6210\u82ef\u7532\u9178\u916f\u7c7b\u5316\u5408\u7269\uff0c1b<\/strong>\u7684\u800c\u8f6c\u5316\u7387\u4f1a\u8fbe\u523055%\u3002<\/p>\n

 <\/p>\n

\u57fa\u4e8e\u4ee5\u4e0a\u7684\u7ed3\u8bba\uff0c\u53cd\u5e94\u4e2d\u53ef\u80fd\u53d1\u751f\u4e86\u8d28\u5b50\u4f34\u968f\u7684\u7535\u5b50\u8f6c\u79fb\u8fc7\u7a0b(PCET, proton-coupled electron transfer)\u5f15\u8d77\u7684O-H\u6d3b\u5316\u8fc7\u7a0b4<\/sup>\uff0c\u4e4b\u540e\u662f\u81ea\u7531\u57fa\u673a\u7406\u7684Brook\u91cd\u6392\u53cd\u5e94\u5f97\u5230\u82c4\u81ea\u7531\u57fa\u3002\u53cd\u5e94\u52a8\u529b\u5b66\u7814\u7a76\u8868\u660e\uff0c\u867d\u7136\u968f\u7740\u53cd\u5e94\u7684\u8fdb\u884c\u9634\u79bb\u5b50\u7684\u78b1\u6027\u4f1a\u51cf\u5f31\uff0c\u4f46\u662f\u4f7f\u7528\u9ad8\u6d3b\u6027\u7684\u5149\u50ac\u5316\u5242\u5e76\u4e0d\u53ef\u4ee5\u8fdb\u884c\u8865\u507f\u3002\u6b64\u5916\uff0c\u5faa\u73af\u4f0f\u5b89\u66f2\u7ebf\u8868\u660e\u5728\u6d4b\u8bd5\u8303\u56f4\uff080-2.00 V vs SCE in MeCN\uff09\u5185\uff0c1b<\/strong>\u4e0d\u5177\u6709\u6c27\u5316\u7535\u52bf\uff1b\u5e76\u4e14\uff0c\u5f53\u65f6AcOCs\u5b58\u5728\u65f6\uff0c\u4f1a\u5b58\u5728\u6709\u6c27\u5316\u7535\u52bf\uff08E<\/em>1\/2<\/sub>o<\/sup><\/em>=0.78V vs SCE in MeCN\uff09\uff0c\u8fd9\u8868\u660e\u78b1\u7684\u5fc5\u8981\u6027\u3002\u6700\u540e\uff0c\u5f53\u4f7f\u7528\u8f83\u5f31\u7684\u78b1\u6bd4\u5982BzOCs\u65f6\uff0c\u6c27\u5316\u7535\u52bf\u4e5f\u662f\u76f8\u4f3c\u7684\uff0c\u8fd9\u4e9b\u8868\u660ePCET\u6a21\u578b\u662f\u4e0d\u592a\u53ef\u80fd\u7684\u3002<\/p>\n

 <\/p>\n

\u53c2\u8003\u6587\u732e<\/strong><\/h4>\n
    \n
  1. Strategic Applications of Named Reactions in Organic Synthesis<\/em>, L\u00e1szl\u00f3K\u00fcrti\u00a0and\u00a0Barbara\u00a0Czak\u00f3, \u00a0pp 64-65<\/li>\n
  2. Org. Lett<\/em>., 2002<\/strong>, 4, 1981-1984, doi: 10.1021\/ol025729m<\/li>\n
  3. J. Org. Chem.<\/em>, 2000<\/strong>, 65, 2292, doi: 10.1021\/jo9912855<\/li>\n
  4. J. Am. Chem. Soc. <\/em>2016<\/strong>, 138, 10794, doi: 10.1021\/jacs.6b06517<\/li>\n<\/ol>\n

    \u672c\u6587\u7248\u6743\u5c5e\u4e8e\u00a0Chem-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<\/strong> <\/p>\n","protected":false},"excerpt":{"rendered":"\u672c\u6587\u6295\u7a3f\u4f5c\u8005\u5b59\u82cf\u8d5f \u5728\u4e0a\u4e16\u7eaa50\u5e74\u4ee3\uff0cBrook\u53d1\u73b0\u4e86\u5206\u5b50\u5185\u7684\u9633\u79bb\u5b50\u548c\u7845\u57fa\u53c2\u4e0e\u8fc1\u79fb\u751f\u6210\u7845\u919a\u7684\u53cd\u5e94\uff0c\u547d\u540d\u4e3aBrook\u91cd\u6392\u53cd\u5e94\uff0c\u5982Figure 1[1,2]\uff0c\u53cd\u5e94\u4e2d\u662f\u53d1\u751f\u4e86\u7845\u88ab\u4eb2\u6838\u7684\u6c27\u8fdb\u653b\u751f\u6210\u4e86Si-O\u952e\uff0c\u4e00\u822c\u6765\u8bb2\uff0cBrook\u91cd\u6392\u662f\u901a\u8fc7\u79bb\u5b50\u673a\u7406\u8fdb\u884c\u7684\u3002 Figure 1 \u79bb\u5b50\u673a\u7406\u7684Brook\u91cd\u6392\u548c\u4e00\u4e2a\u5b9e\u4f8b \u6765\u81ea\u7f8e\u56fd\u5bbe\u5dde\u5927\u5b66\u7684Amos B. Smith\u56e2\u961f\u6700\u8fd1\u5728JACS\u00a0\u4e0a\u62a5\u9053\u4e00\u79cd\u81ea\u7531\u57fa\u673a\u7406\/SET(single electron transfer)\u901a\u8fc7\u751f\u6210\u8d85\u4ef7\u7845\u7c7b\u5316\u5408\u7269\u7684Brook\u91cd\u6392\u53cd\u5e94\uff0c\u4f46\u662f\u8fd9\u4e2a\u53cd\u5e94\u5e76\u5e76\u6ca1\u6709\u5728\u5408\u6210\u4e2d\u5e38\u7528[3]\u3002 Oxidative [1,2]-Brook Rearrangements Exploiting Single-Electron Transfer: Photoredox-Catalyzed Alkylations and Arylations Yifan Deng, Qi Liu, and Amos B. SmithIII J. Am. Chem. Soc., 2017, 139 (28), pp 9487\u20139490, DOI:10.1021\/jacs.7b05165)   SCHEME 1 \u901a\u5e38\u6765\u8bb2\uff0c\u6709\u673a\u7845\u7684\u5316\u5408\u7269\u56e0\u5177\u6709\u5f88\u9ad8\u7684\u6c27\u5316\u7535\u4f4d\u800c\u96be\u5728\u53cd\u5e94\u4e2d\u88ab\u6c27\u5316\uff0c\u4f46\u662f\u5f53\u5f15\u5165\u4e00\u79cd\u6027\u8d28\u6e29\u548c\u5149\u50ac\u5316\u6c27\u5316\u8fd8\u539f\u53cd\u5e94\u7684\u50ac\u5316\u5242\u65f6\uff0c\u5c31\u53ef\u4ee5\u751f\u6210\u8d85\u4ef7\u7684\u7845\u5316\u5408\u7269\uff0c\u800c\u8fd9\u4e2a\u5316\u5408\u7269\u662f\u53ef\u4ee5\u6f5c\u5728\u5730\u8f6c\u5316\u751f\u6210\u81ea\u7531\u57fa\u7684\uff08\u5982Scheme 2\u6240\u793a\uff09\u3002 SCHEME 2   \u672c\u6587\u62a5\u9053\u7684\u662f\u5408\u6210\u4e00\u79cd\u65b0\u578b\u7684\u4e94\u914d\u4f4d\u7684\u7845\u5316\u5408\u7269\u3002\u5e76\u4e14Amos B. Smith\u56e2\u961f\u9884\u6d4b\u5230\uff0c\u901a\u8fc7\u539f\u4f4d\u7684Brook\u91cd\u6392\u548c\u540e\u7eed\u7684\u5728\u5149\u6c27\u5316\u8fd8\u539f\u50ac\u5316\u5242\u50ac\u5316\u4e0b\u8fdb\u884cC-Si\u952e\u7684SET\u89e3\u751f\u6210\u751f\u4e94\u914d\u4f4d\u7684\u7845\u5316\u5408\uff0c\u8fd9\u4e2a\u8fc7\u7a0b\u4e2d\u53ef\u4ee5\u8bf4\u751f\u6210\u03b1-\u7f9f\u57fa\u81ea\u7531\u57fa\u3002\u5982\u679c\u8981\u4f7f\u5f97\u6c27\u5316\u7684[1,2]-Brook\u91cd\u6392\u53ef\u4ee5\u53d1\u751f\uff0c\u90a3\u4e48\u9700\u8981\u6ee1\u8db3\uff1aA.\u5149\u50ac\u5316\u5242\u6fc0\u53d1\u6001\u7684\u8fd8\u539f\u7535\u52bf\u9700\u8981\u8db3\u591f\u5927\uff0c\u4ee5\u81f3\u4e8e\u53ef\u4ee5\u7834\u574fC-Si\u952e\uff1bB. \u5f53\u7845\u539f\u5b50\u4e0a\u8fde\u6709\u56db\u4e2a\u53d6\u4ee3\u57fa\u7684\u65f6\u5019\uff0cC-Si\u952e\u5fc5\u987b\u9009\u62e9\u6027\u65ad\u88c2\u751f\u6210\u70f7\u57fa\u81ea\u7531\u57fa\u3002 SCHEME 3   \u4ece\u673a\u7406\u4e0a\u505a\u51fa\u7684\u5047\u8bbe\uff1a\u9187\u5931\u53bb\u8d28\u5b50\u5f62\u6210\u4e09\u5143\u73afA\u5e76\u8fbe\u5230\u5e73\u8861\uff0c\u800cA\u53ef\u4ee5\u8fdb\u4e00\u6b65\u5728Ir\u50ac\u5316\u5242\u7684\u4f5c\u7528\u4e0b\u88ab\u6c27\u5316\u4e3a\u81ea\u7531\u57faB\uff0c\u4e4b\u540eB\u53d1\u751f\u5171\u8f6d\u52a0\u6210\u751f\u6210C\uff08Scheme 3a\uff09\uff0cC\u518d\u901a\u8fc7\u7535\u5b50\u8f6c\u79fb\u548c\u8d28\u5b50\u5316\u751f\u6210D\uff0c\u540c\u65f6\u5149\u50ac\u5316\u5242\u53d8\u6210\u57fa\u6001\u3002\u6b64\u5916\uff0cIr(III)\u8bd5\u5242\u88ab\u8fd8\u539f\u6210Ir(IV)\uff0c\u800c\u82b3\u70c3\u7c7b\u5316\u5408\u7269\u88ab\u6c27\u5316\u5316\u4e3a\u81ea\u7531\u57fa\u8d1f\u79bb\u5b50E\uff0c\u8fd9\u91cc\u5047\u8bbeIr(IV)\u53ef\u4ee5\u5c06A\u6c27\u5316\u751f\u6210\u9ad8\u4ef7\u7684\u4e2d\u95f4\u4f53B \uff0cE\u548cB\u7ed3\u5408\u8131\u53bb\u4e00\u4e2a\u6c30\u79bb\u5b50\u751f\u6210\u82b3\u57fa\u5316\u7684F\u3002 TABLE 3   \u4e3a\u4e86\u9a8c\u8bc1\u53cd\u5e94\u673a\u7406\uff0c\u5148\u9009\u7528\u7532\u57fa\u4e59\u70ef\u57fa\u916e2a\u548cTBS\u4f5c\u4e3a\u7845\u57fa\u7684\u5e95\u72691b\uff0c\u5176\u4e2d\u916e\u662f\u81ea\u7531\u57fa\u7684\u53d7\u4f53\uff0c\u5b9e\u9a8c\u53d1\u73b0\u4ee5PivOK\u548cDCE\u4e3a\u6700\u4f73\u6761\u4ef6\uff0c\u4ea7\u738738%\uff0c\u53cd\u5e94\u4e2d\u5149\u50ac\u5316\u5242Ir[dF(CF3)ppy]2(dtbpy)PF6\u7684\u6d53\u5ea6\u662f3 mol%\uff0c\u800c\u5176\u4ed6\u7684\u50ac\u5316\u5242\u6548\u679c\u90fd\u4e0d\u597d\u3002\u53cd\u5e94\u7684\u6eb6\u5242\u5bf9\u53cd\u5e94\u7684\u5f71\u54cd\u975e\u5e38\u5927\uff0c\u4f8b\u5982\u4e19\u916e\u548c\u4e59\u8148\u4e2d\u4e0d\u53d1\u751f\u53cd\u5e94\uff0c\u5f3a\u78b1\u5219\u4f1a\u5bfc\u81f4\u53d1\u751f\u78b1\u50ac\u5316\u7684Brook\u91cd\u6392\u53cd\u5e94\uff0c\u800c\u78b1\u6027\u8f83\u5f31\u7684\u78b1\u5219\u4f1a\u4f7f\u5f97\u8f6c\u5316\u7387\u964d\u4f4e\u3002\u6700\u4f73\u914d\u6bd4\u662fPivOK\/AcOSc=1:1\u548c1b\/2a=1:2 equiv. \u800c\u5f53\u53cd\u5e94\u5728\u8f83\u9ad8\u6d53\u5ea6(2.5 M)\u548c0.5 mmol\u89c4\u6a21\u4e0b\u53cd\u5e94\u65f6\uff0c2a\u53ef\u4ee5\u51cf\u5c11\u52301 equiv. \u4f7f\u5f97\u4ea7\u7387\u523072%\u3002 SCHEME 4   \u4e0b\u9762\u662f\u6d4b\u8bd5\u4e0d\u540c\u70f7\u57fa\u7845\u7684\u4e0d\u540c\u7ed3\u679c\uff0c\u6700\u521d\u662f\u4f7f\u7528\u82b3\u57fa\uff08\u4e09\u70f7\u57fa\uff09-\u7532\u9187(1a-1e)\u4f5c\u4e3a\u53cd\u5e94\u5e95\u7269\uff0c\u7845\u57fa\u4f7f\u7528\u7684\u662fTMS\uff0cTES\uff0cTBS\u548cTIPS\uff0c\u4ed6\u4eec\u7684\u4ea7\u7387\u90fd\u5927\u4e8e70%\uff0c\u8fd9\u8868\u660e\u7845\u4e0a\u7684\u4f4d\u963b\u4e0d\u4f1a\u5f71\u54cd\u53cd\u5e94\u7684\u53d1\u751f\u3002\u5927\u4f53\u4e0a\u6765\u770b\uff0c\u542b\u6709TES\u548cTBS\u7684\u5e95\u7269\u4f1a\u6bd4\u5bf9\u5e94\u7684TMS\u7684\u5e95\u7269\u7684\u4ea7\u7387\u8981\u9ad8\uff0c\u8fd9\u53ef\u80fd\u662f\u56e0\u4e3aTES\u548cTBS\u7684\u5e95\u7269\u4e2dC-Si\u952e\u6bd4\u8f83\u7a33\u5b9a\u3002\u5f53\u5e95\u7269\u6362\u6210\u542b\u6709DMPS(3d)\u65f6\uff0c\u4ea7\u7387\u5c31\u8f83\u4f4e\u4e86(56%)\uff0c\u6b64\u800c\u4e14\u82ef\u57fa\u7684\u5438\u7535\u6548\u5e94\u4e5f\u4e0d\u5229\u4e8e\u53cd\u5e94\u7684\u8fdb\u884c\u3002\u6b64\u5916\u82b3\u73af\u4e0a\u4e0d\u540c\u7684\u53d6\u4ee3\u57fa\u4e5f\u4f1a\u5f71\u54cd\u53cd\u5e94\uff0c\u4f9b\u7535\u57fa\u56e2(EDG)\u4f1a\u5bfc\u81f4\u8f83\u9ad8\u7684\u4ea7\u7387(3f-3k)\uff0c\u5364\u539f\u5b50\u7684\u6548\u679c\u4e5f\u4e0d\u9519(3l-3n)\uff0c\u7136\u800c\u5f3a\u70c8\u5438\u7535\u7684\u4e09\u6c1f\u7532\u57fa\u5c31\u4f1a\u4e0d\u5229\u4e8e\u53cd\u5e94\u7684\u4ea7\u7387(3o)\uff1b\u4f4d\u963b\u8f83\u5927\u7684o-\u53d6\u4ee3\u82ef\u7684\u4ea7\u7387\u4e5f\u4e0d\u9519(3j, 67%)\uff1b\u4e94\u5143\u82b3\u73af\u4f5c\u4e3a\u53d6\u4ee3\u57fa\u4e5f\u53ef\u4ee5\u5f97\u5230\u8f83\u9ad8\u7684\u4ea7\u7387(3p-3q)\u3002\u6211\u4eec\u603b\u7ed3\u8ba4\u4e3a3q\u7684\u4ea7\u7387\u964d\u4f4e\u7684\u539f\u56e0\u662f\u53ef\u80fd\u662f\u751f\u62101q\u65f6\u53d1\u751f\u4e86\u5206\u89e3\u4f5c\u7528\u3002\u6700\u540e\uff0c\u53ef\u4ee5\u8fdb\u884c\u8f83\u89c4\u6a21\u5408\u6210\u7684\u662f1f\uff0cIr\u50ac\u5316\u5242\u7684\u6d53\u5ea6\u4e3a2 mol%\uff0c\u53cd\u5e94\u6d53\u5ea61.0 M\u3002 SCHEME 5   \u63a5\u4e0b\u6765\u662f\u5bf9\u4e8e\u81ea\u7531\u57fa\u53d7\u4f53\u70f7\u57fa\u916e\u548c\u82b3\u57fa\u916e\u7684\u6d4b\u8bd5(2b-2k)\u3002\u4f53\u79ef\u8f83\u5927\u7684\u57fa\u56e2\u4e0d\u4f1a\u5f71\u54cd\u53cd\u5e94\u7684\u6d3b\u6027\uff0c\u53ef\u4ee5\u5f97\u5230\u8f83\u9ad8\u4ea7\u7387\u7684\u4ea7\u7269(4b-4c)\uff1b\u5177\u6709\u8fdc\u7a0b\u7684OTBS\u57fa\u56e2\u7684\u916e2d\u4e5f\u53ef\u4ee5\u8f83\u597d\u7684\u53c2\u4e0e\u53cd\u5e94\uff0c\u56e0\u6b64\u53ef\u4ee5\u5229\u7528\u5230\u5408\u6210\u7684\u53cd\u5e94\u4e2d\u53bb\u3002\u82b3\u57fa\u916e\u901a\u5e38\u4f1a\u6bd4\u70f7\u57fa\u916e\u7684\u6548\u679c\u597d\uff0c\u82b3\u73af\u4e0a\u4e0d\u540c\u7684\u5b98\u80fd\u56e2(2e-2i)\u7684\u6548\u679c\u4e0d\u540c\uff0c\u7535\u5b50\u6548\u5e94\u548c\u4f4d\u963b\u6548\u5e94\u90fd\u4e0d\u4f1a\u5f71\u54cd\u53cd\u5e94\u7684\u6d3b\u6027\u3002\u4f46\u662f\uff0c1-\/2-\u53d6\u4ee3\u916e(2k,2j)\u8868\u660e\u916e\u7684\u7535\u5b50\u6548\u5e94\u548c\u4f4d\u963b\u6548\u5e94\u4f1a\u663e\u8457\u7684\u5f71\u54cd\u53cd\u5e94\u7684\u8fdb\u884c\uff0c\u4ea7\u7387\u4f1a\u5927\u5927\u964d\u4f4e\uff0c\u4f46\u662f\u8b6c\u5982\u5177\u6709\u5438\u70b9\u57fa\u56e2\u76842k\u5c31\u4f1a\u5f97\u5230\u5f88\u9ad8\u7684\u4ea7\u7387\u3002\u4f46\u662f\u4e19\u70ef\u9178\u76d0\u53ea\u80fd\u5f97\u5230\u75d5\u91cf\u7684\u4ea7\u7269\uff0c\u8fd9\u53ef\u80fd\u662f\u56e0\u4e3a\u5176\u4ea7\u7269\u548c\u03b1-\u7fb0\u57fa\u81ea\u7531\u57fa\u7684\u7ed3\u5408\u975e\u5e38\u56f0\u96be\u3002\u5f53\u6709\u82ef\u57fa\u5f15\u5165\u5230\u03b1-\u4f4d\u65f6\uff0c\u70f7\u57fa\u5316\u7684\u4ea7\u72694l\u7684\u4ea7\u7387\u4f1a\u8fbe\u523086%\u3002 TABLE 2   \u4ee5\u4e0a\u786e\u5b9a\u4e86\u6700\u6709\u5229\u7684\u53cd\u5e94\u5e95\u7269\u4e4b\u540e\uff0c\u63a5\u4e0b\u6765\u662f\u63a2\u7d22\u53cd\u5e94\u7684\u5386\u7a0b\u662f\u5426\u662fSET\u8fc7\u7a0b(Scheme 3b)\uff0c\u5176\u4e2d\u8ba4\u4e3aB\u53ef\u4ee5\u53c2\u4e0e\u50ac\u5316\u5faa\u73af\uff0c\u56e0\u6b64\u82b3\u57fa\u5316\u53cd\u5e94\u53ef\u4ee5\u53d1\u751f\u3002Amos B. Smith\u56e2\u961f\u9009\u62e9\u4e861b\u4f5c\u4e3a\u53cd\u5e94\u5e95\u7269\uff0c5a\u4f5c\u4e3a\u81ea\u7531\u57fa\u53d7\u4f53\uff0c\u53cd\u5e94\u4e2d\u8fd8\u4f7f\u7528\u4e86\u8f9b\u9178\uff0c\u8fd9\u6709\u5229\u4e8e\u6c30\u6839\u79bb\u5b50\u7684\u4ea7\u751f\u3002\u8d77\u521d\u662fDCE\u4f5c\u4e3a\u53cd\u5e94\u4ecb\u8d28\uff0c\u540c\u65f6\u52a0\u51651 equiv. AcOCs\u4f5c\u4e3a\u78b1\uff0c\u6b64\u65f6\u4ea7\u7269\u975e\u5e38\u5c11\u3002\u6eb6\u5242\u4f1a\u663e\u8457\u5730\u5f71\u54cd\u53cd\u5e94\u7684\u8fdb\u884c\uff0c\u6781\u6027\u6eb6\u5242\u4f8b\u5982DMF\uff0cDMA\u53ef\u4ee5\u5f97\u5230\u5f88\u597d\u7684\u6548\u679c(Entry 2-3)\uff1b\u7531\u4e8e\u6301\u4e45\u81ea\u7531\u57fa\u6548\u5e94\uff0c\u81ea\u7531\u57fa\u524d\u9a71\u4f531b\u53ef\u4ee5\u52a0\u901f\u53cd\u5e94\u7684\u8fdb\u884c\uff1b\u56e0\u6b64\uff0c\u52a0\u901f\u4ea7\u751f1b\u662f\u589e\u5927\u8f6c\u5316\u7387\u7684\u6709\u6548\u65b9\u6cd5\u3002\u5f53\u8c03\u6574\u78b1\u7684\u7528\u91cf\u65f6\u53d1\u73b0\uff0c\u4f7f\u7528\u5316\u5b66\u8ba1\u91cf\u7684\u78b1\u4f9d\u65e7\u4f1a\u5f97\u5230\u76f8\u4f3c\u7684\u4ea7\u7387(Entry 5)\uff0c\u6700\u7ec8\uff0c3equiv. \u76841b\u53ef\u4ee5\u5f97\u52306a\uff0c\u5206\u79bb\u4ea7\u7387\u4e3a83%(Entry 6)\u3002 SCHEME 6   \u57fa\u4e8e\u4e0a\u8ff0\u7684\u53cd\u5e94\u6761\u4ef6\uff0c\u63a5\u4e0b\u6765\u662f\u7ed3\u6784\u5bf9\u4e8e\u53cd\u5e94\u7684\u5f71\u54cd\uff0cScheme 6\u4e2d\uff0c\u542b\u6709EDG\u548cEWG\u7684\u5e95\u7269\u7684\u4ea7\u7387\u90fd\u4e0d\u9519(6a-6e, 66-85%)\uff0c\u544b\u5583\u548c\u567b\u5429\u4f5c\u4e3a\u53d6\u4ee3\u57fa\u65f6\u4ea7\u7387\u8f83\u9ad8(6f-6g)\uff1b\u5c06TMS\u6362\u6210TES\u53d1\u751f\u7684\u53cd\u5e94\u7c7b\u4f3c\uff0c\u800c6h\u7684\u4ea7\u7387\u5219\u8f83\u4f4e\uff0c\u56e0\u4e3a\u53d1\u751f\u4e86\u8131\u7845\u53cd\u5e94\u3002\u53d6\u4ee3\u7684\u82b3\u9999\u53d6\u4ee3\u57fa\u4f1a\u5f97\u5230\u7c7b\u4f3c\u7684\u4ea7\u7387(7a-7c)\uff0c\u800c\u82ef\u4e59\u8148\u548c\u781c\u3001\u916f\u53ef\u4ee5\u53d1\u751f\u8fd9\u4e2a\u53cd\u5e94\uff0c\u4f46\u662f\u4ea7\u7387\u8f83\u4f4e(7d-7e)\u3002 SCHEME 7   \u4e3a\u4e86\u8fdb\u884c\u53cd\u5e94\u673a\u7406\u7684\u7814\u7a76\uff0c\u63a2\u7a76\u53cd\u5e94\u662f\u5426\u662f\u5149\u5316\u5b66\u7684\u6c27\u5316\u8fd8\u539f\u7684Brook\u91cd\u6392\u53cd\u5e94\uff0c\u5148\u4f7f\u7528TEMPO\u4f5c\u4e3a\u81ea\u7531\u57fa\u6dec\u706d\u5242\uff0c\u548c\u5e95\u72691b\u53cd\u5e94\uff0c\u52a0\u5408\u4ea7\u72699\u5206\u79bb\u4ea7\u7387\u4e3a42%\uff0c\u540c\u65f63b\u7684\u4ea7\u7387\u964d\u4f4e\u5230\u4e8616%\u3002\u6b64\u5916\u53cd\u5e94\u8fd8\u9700\u8981\u78b1\u3001\u5149\u548c\u5149\u50ac\u5316\u5242\u53c2\u4e0e\uff0c\u6ca1\u6709\u5149\u6216\u8005\u5149\u50ac\u5316\u5242\uff0c\u53cd\u5e94\u7684\u539f\u6599\u57fa\u672c\u4e0d\u53d8\uff0c\u540c\u65f6\u5982\u679c\u78b1\u4e0d\u52a0\u5165\u5230\u53cd\u5e94\u4f53\u7cfb\u4e2d\uff0c\u90a3\u4e48\u53ea\u6709\u75d5\u91cf\u76843b\u751f\u6210\uff0c\u800c\u7531\u4e8e\u8fc7\u5ea6\u6c27\u5316\u800c\u751f\u6210\u82ef\u7532\u9178\u916f\u7c7b\u5316\u5408\u7269\uff0c1b\u7684\u800c\u8f6c\u5316\u7387\u4f1a\u8fbe\u523055%\u3002   \u57fa\u4e8e\u4ee5\u4e0a\u7684\u7ed3\u8bba\uff0c\u53cd\u5e94\u4e2d\u53ef\u80fd\u53d1\u751f\u4e86\u8d28\u5b50\u4f34\u968f\u7684\u7535\u5b50\u8f6c\u79fb\u8fc7\u7a0b(PCET, proton-coupled electron transfer)\u5f15\u8d77\u7684O-H\u6d3b\u5316\u8fc7\u7a0b4\uff0c\u4e4b\u540e\u662f\u81ea\u7531\u57fa\u673a\u7406\u7684Brook\u91cd\u6392\u53cd\u5e94\u5f97\u5230\u82c4\u81ea\u7531\u57fa\u3002\u53cd\u5e94\u52a8\u529b\u5b66\u7814\u7a76\u8868\u660e\uff0c\u867d\u7136\u968f\u7740\u53cd\u5e94\u7684\u8fdb\u884c\u9634\u79bb\u5b50\u7684\u78b1\u6027\u4f1a\u51cf\u5f31\uff0c\u4f46\u662f\u4f7f\u7528\u9ad8\u6d3b\u6027\u7684\u5149\u50ac\u5316\u5242\u5e76\u4e0d\u53ef\u4ee5\u8fdb\u884c\u8865\u507f\u3002\u6b64\u5916\uff0c\u5faa\u73af\u4f0f\u5b89\u66f2\u7ebf\u8868\u660e\u5728\u6d4b\u8bd5\u8303\u56f4\uff080-2.00 V vs SCE […]","protected":false},"author":8,"featured_media":15297,"comment_status":"open","ping_status":"open","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":[1271],"tags":[1960,1961],"jetpack_publicize_connections":[],"jetpack_featured_media_url":"https:\/\/assets.www.gsbet888.com\/uploads\/2017\/08\/Brook-rearrangement.jpg","jetpack_shortlink":"https:\/\/wp.me\/p96op1-3XF","jetpack_sharing_enabled":true,"_links":{"self":[{"href":"\/\/www.gsbet888.com\/wp-json\/wp\/v2\/posts\/15231"}],"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\/8"}],"replies":[{"embeddable":true,"href":"\/\/www.gsbet888.com\/wp-json\/wp\/v2\/comments?post=15231"}],"version-history":[{"count":2,"href":"\/\/www.gsbet888.com\/wp-json\/wp\/v2\/posts\/15231\/revisions"}],"predecessor-version":[{"id":27356,"href":"\/\/www.gsbet888.com\/wp-json\/wp\/v2\/posts\/15231\/revisions\/27356"}],"wp:featuredmedia":[{"embeddable":true,"href":"\/\/www.gsbet888.com\/wp-json\/wp\/v2\/media\/15297"}],"wp:attachment":[{"href":"\/\/www.gsbet888.com\/wp-json\/wp\/v2\/media?parent=15231"}],"wp:term":[{"taxonomy":"category","embeddable":true,"href":"\/\/www.gsbet888.com\/wp-json\/wp\/v2\/categories?post=15231"},{"taxonomy":"post_tag","embeddable":true,"href":"\/\/www.gsbet888.com\/wp-json\/wp\/v2\/tags?post=15231"}],"curies":[{"name":"wp","href":"https:\/\/api.w.org\/{rel}","templated":true}]}}