{"id":41251,"date":"2022-02-24T08:00:57","date_gmt":"2022-02-24T00:00:57","guid":{"rendered":"\/\/www.gsbet888.com\/?p=41251"},"modified":"2022-02-28T19:18:09","modified_gmt":"2022-02-28T11:18:09","slug":"%e6%89%8b%e6%80%a7bronsted%e9%85%b8%e6%8e%a7%e5%88%b6%e7%9a%84%e4%b8%8d%e5%af%b9%e7%a7%b0%e5%85%8922%e7%8e%af%e5%8a%a0%e6%88%90%e5%8f%8d%e5%ba%94%e7%a0%94%e7%a9%b6","status":"publish","type":"post","link":"\/\/www.gsbet888.com\/%e5%8c%96%e5%ad%a6%e6%9d%82%e8%ae%b0\/recentpaper\/2022\/02\/%e6%89%8b%e6%80%a7bronsted%e9%85%b8%e6%8e%a7%e5%88%b6%e7%9a%84%e4%b8%8d%e5%af%b9%e7%a7%b0%e5%85%8922%e7%8e%af%e5%8a%a0%e6%88%90%e5%8f%8d%e5%ba%94%e7%a0%94%e7%a9%b6.html","title":{"rendered":"\u624b\u6027Br\u00f8nsted\u9178\u63a7\u5236\u7684\u4e0d\u5bf9\u79f0\u5149[2+2]\u73af\u52a0\u6210\u53cd\u5e94\u7814\u7a76"},"content":{"rendered":"<p>\u672c\u6587\u4f5c\u8005\uff1a\u6749\u6749<\/p>\n<h4>\u5bfc\u8bfb<\/h4>\n<p>\u8fd1\u65e5\uff0cWisconsin\u5927\u5b66\u7684T. P. Yoon\u4e0eKAIST (Korea Advanced Institute of Science and Technology)\u7684M.-H. Baik\u56e2\u961f\u5728<em>Nat. Commun.<\/em>\u4e2d\u53d1\u8868\u8bba\u6587\uff0c\u5171\u540c\u62a5\u9053\u4e00\u79cd\u5168\u65b0\u7684\u901a\u8fc7\u624b\u6027Br\u00f8nsted\u9178\u63a7\u5236\u7684\u9ad8\u5ea6\u5bf9\u6620\u4e0e\u975e\u5bf9\u6620\u9009\u62e9\u6027\u7684\u5149[2+2]\u73af\u52a0\u6210\u53cd\u5e94\u65b9\u6cd5\u5b66\u3002\u8fd9\u4e00\u5168\u65b0\u7684\u5bf9\u6620\u9009\u62e9\u6027\u5149[2+2]\u73af\u52a0\u6210\u7b56\u7565\u4e2d\uff0c\u5f62\u6210\u7684\u73af\u4e01\u70f7\u4ea7\u7269\u5177\u6709<em>trans<\/em>&#8211;<em>cis<\/em>\u7acb\u4f53\u5316\u5b66\uff0c\u8fdb\u800c\u4e0e\u5176\u4ed6\u5bf9\u6620\u9009\u62e9\u6027\u50ac\u5316\u7684\u5149[2+2]\u73af\u52a0\u6210\u65b9\u6cd5\u5b66\u76f8\u5173\u7684\u7814\u7a76\u62a5\u9053\u5f62\u6210\u6709\u529b\u7684\u4e92\u8865\u3002<\/p>\n<blockquote><p>Chiral Br\u00f8nsted acid-controlled intermolecular asymmetric [2+2] photocycloadditions<\/p>\n<p>E. M. Sherbrook, M. J. Genzink, B. Park, I. A. Guzei, M.-H. Baik, T. P. Yoon<\/p>\n<p><em>Nat. Commun. <\/em><strong>2021<\/strong>, ASAP. <a href=\"https:\/\/www.nature.com\/articles\/s41467-021-25878-9?utm_source=xmol&amp;utm_medium=affiliate&amp;utm_content=meta&amp;utm_campaign=DDCN_1_GL01_metadata\">Doi:10.1038\/s41467-021-25878-9.<\/a><\/p><\/blockquote>\n<p><a href=\"https:\/\/assets.www.gsbet888.com\/uploads\/2022\/02\/2-13.png\"><img loading=\"lazy\" decoding=\"async\" class=\"aligncenter wp-image-41244 size-full\" src=\"https:\/\/assets.www.gsbet888.com\/uploads\/2022\/02\/2-13.png\" alt=\"\" width=\"629\" height=\"352\" srcset=\"https:\/\/assets.www.gsbet888.com\/uploads\/2022\/02\/2-13.png 629w, https:\/\/assets.www.gsbet888.com\/uploads\/2022\/02\/2-13-300x168.png 300w\" sizes=\"(max-width: 629px) 100vw, 629px\" \/><\/a><\/p>\n<h4>\u6b63\u6587<\/h4>\n<p>\u8bbe\u8ba1\u9ad8\u5ea6\u5bf9\u6620\u9009\u62e9\u6027\u7684\u5408\u6210\u8f6c\u5316\u7b56\u7565\uff0c\u5728\u73b0\u4ee3\u5408\u6210\u5316\u5b66\u7684\u7814\u7a76\u4e2d\u5907\u53d7\u5e7f\u6cdb\u5173\u6ce8\u3002\u7136\u800c\uff0c\u901a\u8fc7\u5149\u5316\u5b66\u7b56\u7565\u8fdb\u884c\u7684\u5bf9\u6620\u9009\u62e9\u6027\u5408\u6210\u8bbe\u8ba1\uff0c\u5219\u9762\u4e34\u8bf8\u591a\u6311\u6218<sup>[1]-[2]<\/sup>(Fig. 1)\u3002\u53d7\u5230\u524d\u671f\u5bf9\u4e8eBr\u00f8nsted\u9178\u5728\u4e0d\u5bf9\u79f0\u5408\u6210\u8f6c\u5316\u7b56\u7565\u4e2d\u7684\u5e94\u7528<sup>[4]-[6]<\/sup>\u4ee5\u53ca\u8fd1\u671f\u5bf9\u4e8e\u5bf9\u6620\u9009\u62e9\u6027[2+2]\u5149\u73af\u52a0\u6210\u53cd\u5e94<sup>[7]<\/sup>\u76f8\u5173\u7814\u7a76\u7684\u542f\u53d1\uff0c\u8fd9\u91cc\uff0cT. P. Yoon\u4e0eM.-H. Baik\u56e2\u961f\u5171\u540c\u62a5\u9053\u4e00\u79cd\u5168\u65b0\u7684\u901a\u8fc7 BINOL\u884d\u751f\u7684\u624b\u6027\u78f7\u9170\u80faBr\u00f8nsted\u9178\u4fc3\u8fdb\u7684\u5bf9\u6620\u4e0e\u975e\u5bf9\u6620\u9009\u62e9\u6027\u5149[2+2]\u73af\u52a0\u6210\u53cd\u5e94\u65b9\u6cd5\u5b66 (Fig. 1)\u3002\u540c\u65f6\uff0c\u901a\u8fc7\u5149\u8c31\u4e0e\u8ba1\u7b97\u5316\u5b66\u7684\u76f8\u5173\u7814\u7a76\u8868\u660e\uff0c\u8fd9\u4e00\u5168\u65b0\u7684\u50ac\u5316\u73af\u52a0\u6210\u8fc7\u7a0b\u6d89\u53ca\u53d1\u8272\u56e2\u6d3b\u5316\u539f\u7406 (principle of chromophore activation )\u3002<\/p>\n<p><a href=\"https:\/\/assets.www.gsbet888.com\/uploads\/2022\/02\/3-14.png\"><img loading=\"lazy\" decoding=\"async\" class=\"aligncenter wp-image-41245 size-large\" src=\"https:\/\/assets.www.gsbet888.com\/uploads\/2022\/02\/3-14-680x219.png\" alt=\"\" width=\"680\" height=\"219\" srcset=\"https:\/\/assets.www.gsbet888.com\/uploads\/2022\/02\/3-14-680x219.png 680w, https:\/\/assets.www.gsbet888.com\/uploads\/2022\/02\/3-14-300x97.png 300w, https:\/\/assets.www.gsbet888.com\/uploads\/2022\/02\/3-14.png 718w\" sizes=\"(max-width: 680px) 100vw, 680px\" \/><\/a><\/p>\n<p>\u9996\u5148\uff0c\u4f5c\u8005\u91c7\u7528\u82ef\u4e59\u70ef\u4e0e\u70ef\u916e\u884d\u751f\u7269<strong>1<\/strong>\u4f5c\u4e3a\u6a21\u578b\u5e95\u7269\uff0c\u8fdb\u884c\u76f8\u5173\u53cd\u5e94\u6761\u4ef6\u7684\u4f18\u5316\u7b5b\u9009 (Fig. 2)\u3002\u786e\u5b9a\u6700\u4f73\u7684\u53cd\u5e94\u6761\u4ef6\u4e3a\uff1a\u91c7\u7528[Ir(Fppy)<sub>2<\/sub>(dtbbpy)]PF<sub>6<\/sub>\u4f5c\u4e3a\u5149\u50ac\u5316\u5242\uff0c<strong>AC-3<\/strong>\u4f5c\u4e3a\u624b\u6027Br\u00f8nsted\u9178\u50ac\u5316\u5242\uff0c\u901a\u8fc7Kessil H150 Blue LED\u8f90\u5c04\uff0c\u7532\u82ef\u4f5c\u4e3a\u53cd\u5e94\u6eb6\u5242\uff0c\u53cd\u5e94\u6e29\u5ea6\u4e3a-78<sup>o<\/sup>C\uff0c\u6700\u7ec8\u83b7\u5f9774%\u6536\u7387\u7684\u73af\u52a0\u6210\u4ea7\u7269 (7:1d.r.\uff0c95% ee)\u3002<\/p>\n<p><a href=\"https:\/\/assets.www.gsbet888.com\/uploads\/2022\/02\/4-14.png\"><img loading=\"lazy\" decoding=\"async\" class=\"aligncenter wp-image-41246 size-full\" src=\"https:\/\/assets.www.gsbet888.com\/uploads\/2022\/02\/4-14.png\" alt=\"\" width=\"616\" height=\"785\" srcset=\"https:\/\/assets.www.gsbet888.com\/uploads\/2022\/02\/4-14.png 616w, https:\/\/assets.www.gsbet888.com\/uploads\/2022\/02\/4-14-235x300.png 235w\" sizes=\"(max-width: 616px) 100vw, 616px\" \/><\/a><\/p>\n<p>\u5728\u4e0a\u8ff0\u7684\u6700\u4f73\u53cd\u5e94\u6761\u4ef6\u4e0b\uff0c\u4f5c\u8005\u9996\u5148\u5bf9\u5404\u7c7b<em>\u03b1,\u03b2-<\/em>\u4e0d\u9971\u548c\u7fb0\u57fa\u5e95\u7269\u7684\u5e94\u7528\u8303\u56f4\u8fdb\u884c\u8003\u5bdf (Fig. 3)\u3002\u7814\u7a76\u8868\u660e\uff0c\u4e00\u7cfb\u5217\u5177\u6709\u4f9b\u7535\u5b50\u4e0e\u5438\u7535\u5b50\u57fa\u56e2\u53d6\u4ee3\u7684<em>\u03b2<\/em>-\u82b3\u57fa<em>\u03b1,\u03b2-<\/em>\u4e0d\u9971\u548c\u7fb0\u57fa\u5e95\u7269\uff0c\u5747\u80fd\u591f\u8f83\u597d\u5730\u4e0e\u4e0a\u8ff0\u7684\u6807\u51c6\u53cd\u5e94\u6761\u4ef6\u517c\u5bb9\uff0c\u5e76\u4ee5\u826f\u597d\u7684\u53cd\u5e94\u6536\u7387\u4e0e\u5bf9\u6620\u4ee5\u53ca\u975e\u5bf9\u6620\u9009\u62e9\u6027\uff0c\u83b7\u5f97\u76f8\u5e94\u7684\u624b\u6027\u4ea7\u7269<strong>2-9<\/strong>\u3002\u5e76\u4e14\uff0c\u4f5c\u8005\u53d1\u73b0\uff0c\u5bf9\u4e8e\u8418\u57fa\u3001\u567b\u5429\u57fa\u53d6\u4ee3\u7684\u5e95\u7269\uff0c\u540c\u6837\u80fd\u591f\u987a\u5229\u5730\u5b8c\u6210\u4e0a\u8ff0\u7684\u73af\u52a0\u6210\u8fc7\u7a0b\uff0c\u5e76\u83b7\u5f97\u76f8\u5e94\u7684\u624b\u6027\u4ea7\u7269<strong>10<\/strong>\u4e0e<strong>11<\/strong>\u3002\u540c\u65f6\uff0c\u8fd9\u4e00\u5168\u65b0\u7684\u5bf9\u6620\u9009\u62e9\u6027\u73af\u52a0\u6210\u7b56\u7565\u5bf9\u4e8e\u785d\u57fa\u82b3\u70c3 (<strong>12<\/strong>)\u4ee5\u53ca\u82b3\u57fa\u7898 (<strong>13<\/strong>)\u5e95\u7269\uff0c\u540c\u6837\u80fd\u591f\u6709\u6548\u5730\u517c\u5bb9\u3002<\/p>\n<p>\u4e4b\u540e\uff0c\u8be5\u5c0f\u7ec4\u8fdb\u4e00\u6b65\u5bf9\u5404\u7c7b\u70ef\u57fa\u5e95\u7269\u7684\u5e94\u7528\u8303\u56f4\u8fdb\u884c\u6df1\u5165\u7814\u7a76\u3002\u4f5c\u8005\u53d1\u73b0\uff0c\u82ef\u73af\u4e2d\u6709\u4e0d\u540c\u4f9b\u7535\u5b50\u4e0e\u5438\u7535\u5b50\u57fa\u56e2\u53d6\u4ee3\u7684\u82ef\u4e59\u70ef\u5e95\u7269\uff0c\u5747\u80fd\u591f\u987a\u5229\u5730\u5b8c\u6210\u4e0a\u8ff0\u7684\u4e0d\u5bf9\u79f0\u73af\u52a0\u6210\u8fc7\u7a0b\uff0c\u5e76\u83b7\u5f97\u76f8\u5e94\u7684\u624b\u6027\u4ea7\u7269<strong>14<\/strong>&#8211;<strong>25<\/strong>\u3002\u540c\u65f6\uff0c\u4e0a\u8ff0\u7684\u6807\u51c6\u53cd\u5e94\u6761\u4ef6\u5bf9\u4e8e\u6742\u82b3\u57fa\u53d6\u4ee3\u7684\u82b3\u4e59\u70ef\u3001\u53d6\u4ee3\u4ee5\u53ca\u672a\u53d6\u4ee3\u7684\u4e8c\u70ef\u5e95\u7269\uff0c\u540c\u6837\u80fd\u591f\u6709\u6548\u5730\u517c\u5bb9 (<strong>28<\/strong>&#8211;<strong>31<\/strong>)\u3002 \u7136\u800c\uff0c\u7814\u7a76\u53d1\u73b0\uff0c\u80fd\u591f\u4e0e\u624b\u6027\u50ac\u5316\u5242\u8fdb\u884c\u914d\u4f4d\u7684\u82b3\u4e59\u70ef\u5e95\u7269\uff0c\u901a\u5e38\u8868\u73b0\u51fa\u8f83\u4f4e\u7684\u53cd\u5e94\u6d3b\u6027 (<strong>32<\/strong>)\u3002\u540c\u65f6\uff0c\u4e0a\u8ff0\u7684\u6807\u51c6\u53cd\u5e94\u4f53\u7cfb\uff0c\u5bf9\u4e8e\u8102\u80aa\u65cf\u73af\u5916\u70ef\u57fa\u5e95\u7269 (<strong>34<\/strong>&#8211;<strong>35<\/strong>)\uff0c\u540c\u6837\u80fd\u591f\u83b7\u5f97\u4e2d\u7b49\u6536\u7387\u4e0e\u826f\u597d\u5bf9\u6620\u9009\u62e9\u6027\u7684\u73af\u52a0\u6210\u4ea7\u7269\u3002\u4e4b\u540e\uff0c\u4f5c\u8005\u8fdb\u4e00\u6b65\u53d1\u73b0\uff0c\u4e0a\u8ff0\u7684\u6807\u51c6\u53cd\u5e94\u6761\u4ef6\u5bf9\u4e8e\u9ad8\u5ea6\u5b98\u80fd\u56e2\u5316\u7684\u82b3\u57fa\u4e59\u70ef\u4e0e<em>\u03b1,\u03b2-<\/em>\u4e0d\u9971\u548c\u7fb0\u57fa\u5e95\u7269\uff0c\u540c\u6837\u80fd\u591f\u9ad8\u5ea6\u7684\u5bf9\u6620\u9009\u62e9\u6027\u5730\u83b7\u5f97\u76f8\u5e94\u7684\u76ee\u6807\u4ea7\u7269<strong>36<\/strong>\uff0c\u5e76\u80fd\u591f\u901a\u8fc7\u54aa\u5511\u57fa\u56e2\u7684\u53bb\u9664\uff0c\u8fdb\u4e00\u6b65\u8f6c\u5316\u4e3a\u5176\u4ed6\u7c7b\u578b\u7684\u624b\u6027\u780c\u5757 (Fig. 4)\u3002<\/p>\n<p><a href=\"https:\/\/assets.www.gsbet888.com\/uploads\/2022\/02\/5-14.png\"><img loading=\"lazy\" decoding=\"async\" class=\"aligncenter wp-image-41247 size-large\" src=\"https:\/\/assets.www.gsbet888.com\/uploads\/2022\/02\/5-14-680x777.png\" alt=\"\" width=\"680\" height=\"777\" srcset=\"https:\/\/assets.www.gsbet888.com\/uploads\/2022\/02\/5-14-680x777.png 680w, https:\/\/assets.www.gsbet888.com\/uploads\/2022\/02\/5-14-262x300.png 262w, https:\/\/assets.www.gsbet888.com\/uploads\/2022\/02\/5-14-768x878.png 768w, https:\/\/assets.www.gsbet888.com\/uploads\/2022\/02\/5-14.png 783w\" sizes=\"(max-width: 680px) 100vw, 680px\" \/><\/a><\/p>\n<p><a href=\"https:\/\/assets.www.gsbet888.com\/uploads\/2022\/02\/6-11.png\"><img loading=\"lazy\" decoding=\"async\" class=\"aligncenter wp-image-41248 size-full\" src=\"https:\/\/assets.www.gsbet888.com\/uploads\/2022\/02\/6-11.png\" alt=\"\" width=\"606\" height=\"358\" srcset=\"https:\/\/assets.www.gsbet888.com\/uploads\/2022\/02\/6-11.png 606w, https:\/\/assets.www.gsbet888.com\/uploads\/2022\/02\/6-11-300x177.png 300w\" sizes=\"(max-width: 606px) 100vw, 606px\" \/><\/a><\/p>\n<p>\u63a5\u4e0b\u6765\uff0c\u4f5c\u8005\u901a\u8fc7UV-Vis\u5149\u8c31 (Fig. 5a)\u8bc1\u5b9e\uff0cBr\u00f8nsted\u9178\u5728\u73af\u52a0\u6210\u53cd\u5e94\u8fc7\u7a0b\u4e2d\uff0c\u5e76\u975e\u4f5c\u4e3a\u5e38\u89c4\u7684\u4e09\u7ebf\u6001\u5149\u654f\u5316\u5242\u3002\u540c\u65f6\uff0c\u4f5c\u8005\u8fdb\u4e00\u6b65\u901a\u8fc7NMR\u6ef4\u5b9a\u5b9e\u9a8c (NMR titration experiment)\uff0c\u8ba1\u7b97\u51fa\u76f8\u5e94\u7684\u7ed3\u5408\u5e38\u6570<em>K<\/em><sub>a<\/sub> = 7.5\u00d710<sup>6 <\/sup>(<a href=\"https:\/\/static-content.springer.com\/esm\/art%3A10.1038%2Fs41467-021-25878-9\/MediaObjects\/41467_2021_25878_MOESM1_ESM.pdf\">Supplementary <\/a>Fig. 5)\u3002\u4e4b\u540e\uff0c\u4f5c\u8005\u8fdb\u4e00\u6b65\u5206\u79bb\u51fa\u76f8\u5e94\u7684\u5e95\u7269-\u9178\u914d\u5408\u7269 (substrate-acid complex)\uff0c\u5e76\u901a\u8fc7<em>X<\/em>-\u5c04\u7ebf\u6676\u4f53\u5b66\u5206\u6790\uff0c\u786e\u5b9a\u5176\u7ed3\u6784 (Fig. 5b-c)\uff0c\u8fdb\u800c\u8fdb\u4e00\u6b65\u9610\u660e\u4e0a\u8ff0\u73af\u52a0\u6210\u8fc7\u7a0b\u4e2d\uff0c\u76f8\u5173\u5bf9\u6620\u9009\u62e9\u6027\u7684\u63a7\u5236\u56e0\u7d20\u3002<\/p>\n<p>\u57fa\u4e8e\u4e0a\u8ff0\u7684\u5b9e\u9a8c\u7814\u7a76\uff0c\u4f5c\u8005\u63d0\u51fa\u901a\u8fc7\u5e95\u7269-\u9178\u914d\u5408\u7269\u4e2d\u5bf9\u4e8e\u76f8\u5173\u5e95\u7269\u7684\u6d3b\u5316\uff0c\u5b58\u5728\u4e24\u79cd\u53ef\u80fd\u7684\u6d3b\u5316\u6a21\u5f0f\uff0c\u5373\u751f\u8272\u56e2\u6d3b\u5316\u673a\u7406 (chromophore activation mechanism)\u4e0e\u7535\u5b50\u4f9b\u4f53-\u53d7\u4f53\u673a\u7406\u3002\u6700\u7ec8\uff0c\u4f5c\u8005\u901a\u8fc7\u5bf9\u5404\u7c7b\u9178\u50ac\u5316\u5242\u4fc3\u8fdb\u7684\u5149\u73af\u52a0\u6210\u8fc7\u7a0b\u4e2d\u53cd\u5e94\u6536\u7387\u7684\u76f8\u5173\u7814\u7a76 (Fig. 6)\u8fdb\u4e00\u6b65\u8bc1\u5b9e\uff0c\u53cd\u5e94\u8fc7\u7a0b\u4e2d\u6d89\u53ca\u751f\u8272\u56e2\u6d3b\u5316\u673a\u7406\u3002\u4e4b\u540e\uff0c\u4f5c\u8005\u901a\u8fc7DFT\u4e0eTDDFT (time-dependent DFT)\u8ba1\u7b97\uff0c\u5bf9\u8fd9\u4e00\u673a\u7406\u7684\u8d77\u6e90\u8fdb\u884c\u6df1\u5165\u7814\u7a76 (Fig. 5d)\u3002<\/p>\n<p><a href=\"https:\/\/assets.www.gsbet888.com\/uploads\/2022\/02\/7-8.png\"><img loading=\"lazy\" decoding=\"async\" class=\"aligncenter wp-image-41249 size-large\" src=\"https:\/\/assets.www.gsbet888.com\/uploads\/2022\/02\/7-8-680x270.png\" alt=\"\" width=\"680\" height=\"270\" srcset=\"https:\/\/assets.www.gsbet888.com\/uploads\/2022\/02\/7-8-680x270.png 680w, https:\/\/assets.www.gsbet888.com\/uploads\/2022\/02\/7-8-300x119.png 300w, https:\/\/assets.www.gsbet888.com\/uploads\/2022\/02\/7-8.png 762w\" sizes=\"(max-width: 680px) 100vw, 680px\" \/><\/a><\/p>\n<p><a href=\"https:\/\/assets.www.gsbet888.com\/uploads\/2022\/02\/8-5.png\"><img loading=\"lazy\" decoding=\"async\" class=\"aligncenter wp-image-41250 size-full\" src=\"https:\/\/assets.www.gsbet888.com\/uploads\/2022\/02\/8-5.png\" alt=\"\" width=\"662\" height=\"422\" srcset=\"https:\/\/assets.www.gsbet888.com\/uploads\/2022\/02\/8-5.png 662w, https:\/\/assets.www.gsbet888.com\/uploads\/2022\/02\/8-5-300x191.png 300w\" sizes=\"(max-width: 662px) 100vw, 662px\" \/><\/a><\/p>\n<h4>\u603b\u7ed3<\/h4>\n<p>T. P. Yoon\u4e0eM.-H. Baik\u7814\u7a76\u56e2\u961f\u5171\u540c\u8bbe\u8ba1\u51fa\u4e00\u79cd\u5168\u65b0\u7684\u901a\u8fc7\u624b\u6027Br\u00f8nsted\u9178\u63a7\u5236\u7684\u5177\u6709\u9ad8\u5ea6\u5bf9\u6620\u4e0e\u975e\u5bf9\u6620\u9009\u62e9\u6027\u7684\u5149[2+2]\u73af\u52a0\u6210\u53cd\u5e94\u65b9\u6cd5\u5b66\u3002\u8fd9\u4e00\u5168\u65b0\u7684\u73af\u52a0\u6210\u7b56\u7565\u5177\u6709\u9ad8\u5ea6\u7684\u5bf9\u6620\u9009\u62e9\u6027\u63a7\u5236\u3001\u5e7f\u6cdb\u7684\u5e95\u7269\u5e94\u7528\u8303\u56f4\u4ee5\u53ca\u826f\u597d\u7684\u5b98\u80fd\u56e2\u517c\u5bb9\u6027\u7b49\u4f18\u52bf\u3002<\/p>\n<h4><strong>\u53c2\u8003\u6587\u732e<\/strong><\/h4>\n<ul>\n<li>[1] (a) H. A. Rau, <em>Chem. Rev.<\/em> <strong>1983<\/strong>, <em>83<\/em>, 535. doi: <a href=\"https:\/\/doi.org\/10.1021\/cr00057a003\">10.1021\/cr00057a003<\/a>.\u00a0(b) Y. Inoue, <em>Chem. Rev.<\/em> <strong>1992<\/strong>, <em>92<\/em>,741. doi: <a href=\"https:\/\/doi.org\/10.1021\/cr00013a001\">10.1021\/cr00013a001<\/a>.<\/li>\n<li>[2] (a) R. Brimioulle, T. Bach, <em>Science<\/em> <strong>2013<\/strong>, <em>342<\/em>, 840. doi: <a href=\"https:\/\/doi.org\/10.1126\/science.1244809\">10.1126\/science.1244809<\/a>.\u00a0(b) C. Brenninger, J. D. Jolliffe, T. Bach, <em>Angew. Chem. Int. Ed.<\/em> <strong>2018<\/strong>, <em>57<\/em>, 14338. doi: <a href=\"https:\/\/doi.org\/10.1002\/anie.201804006\">10.1002\/anie.201804006<\/a>.<\/li>\n<li>[3] (a) T. R. Blum, Z. D. Miller, D. M. Bates, I. A. Guzei, T. P. Yoon, <em>Science<\/em> <strong>2016<\/strong>, <em>354<\/em>, 1391. doi:<a href=\"https:\/\/doi.org\/10.1126\/science.aai8228\">10.1126\/science.aai8228<\/a>.\u00a0(b) Z. D. Miller, B. J. Lee, T. P. E. Yoon, <em>Angew. Chem. Int. Ed.<\/em> <strong>2017<\/strong>, <em>56<\/em>, 11891. doi: <a href=\"https:\/\/doi.org\/10.1002\/anie.201706975\">10.1002\/anie.201706975<\/a>.<\/li>\n<li>[4] (a) A. Erkkil\u00e4, , I. Majander, &amp; P. M. Pihko, <em>Chem. Rev.<\/em> <strong>2007<\/strong>, <em>107<\/em>, 5416. doi: <a href=\"https:\/\/doi.org\/10.1021\/cr068388p\">10.1021\/cr068388p<\/a>.\u00a0(b) S. Mukherjee, J. W. Yang, S. Hoffmann, B. List, <em>Chem. Rev.<\/em> <strong>2007<\/strong>, <em>107<\/em>, 5471. doi: <a href=\"https:\/\/doi.org\/10.1021\/cr0684016\">10.1021\/cr0684016<\/a><\/li>\n<li>[5] R. Takagi, C. Tabuchi, <em>Org. Biomol. Chem.<\/em> <strong>2020<\/strong>, <em>18<\/em>, 9261. doi: <a href=\"https:\/\/doi.org\/10.1039\/D0OB02054K\">10.1039\/D0OB02054K<\/a>.<\/li>\n<li>[6] N. Vallavoju, S. Selvakumar, S. Jockusch, M. P. Sibi, J. Sivaguru, <em>Angew. Chem. Int. Ed.<\/em> <strong>2014<\/strong>, <em>53<\/em>, 5604. doi:<a href=\"https:\/\/doi.org\/10.1002\/anie.201310940\">10.1002\/anie.201310940<\/a>.<\/li>\n<li>[7] F. M. H\u00f6rmann, T. S. Chung, E. Rodriguez, M. Jakob, <em>Angew. Chem. Int. Ed. <\/em><strong>2018<\/strong>, <em>57<\/em>, 827. doi:<a href=\"https:\/\/doi.org\/10.1002\/anie.201710441\">10.1002\/anie.201710441<\/a>.<\/li>\n<\/ul>\n<p><strong>\u672c\u6587\u7248\u6743\u5c5e\u4e8e\u00a0Chem-Station\u5316\u5b66\u7a7a\u95f4\uff0c \u6b22\u8fce\u70b9\u51fb\u6309\u94ae\u5206\u4eab\uff0c\u672a\u7ecf\u8bb8\u53ef\uff0c\u8c22\u7edd\u8f6c\u8f7d<\/strong><\/p>\n","protected":false},"excerpt":{"rendered":"\u672c\u6587\u4f5c\u8005\uff1a\u6749\u6749 \u5bfc\u8bfb \u8fd1\u65e5\uff0cWisconsin\u5927\u5b66\u7684T. P. Yoon\u4e0eKAIST (Korea Advanced Institute of Science and Technology)\u7684M.-H. Baik\u56e2\u961f\u5728Nat. Commun.\u4e2d\u53d1\u8868\u8bba\u6587\uff0c\u5171\u540c\u62a5\u9053\u4e00\u79cd\u5168\u65b0\u7684\u901a\u8fc7\u624b\u6027Br\u00f8nsted\u9178\u63a7\u5236\u7684\u9ad8\u5ea6\u5bf9\u6620\u4e0e\u975e\u5bf9\u6620\u9009\u62e9\u6027\u7684\u5149[2+2]\u73af\u52a0\u6210\u53cd\u5e94\u65b9\u6cd5\u5b66\u3002\u8fd9\u4e00\u5168\u65b0\u7684\u5bf9\u6620\u9009\u62e9\u6027\u5149[2+2]\u73af\u52a0\u6210\u7b56\u7565\u4e2d\uff0c\u5f62\u6210\u7684\u73af\u4e01\u70f7\u4ea7\u7269\u5177\u6709trans&#8211;cis\u7acb\u4f53\u5316\u5b66\uff0c\u8fdb\u800c\u4e0e\u5176\u4ed6\u5bf9\u6620\u9009\u62e9\u6027\u50ac\u5316\u7684\u5149[2+2]\u73af\u52a0\u6210\u65b9\u6cd5\u5b66\u76f8\u5173\u7684\u7814\u7a76\u62a5\u9053\u5f62\u6210\u6709\u529b\u7684\u4e92\u8865\u3002 Chiral Br\u00f8nsted acid-controlled intermolecular asymmetric [2+2] photocycloadditions E. M. Sherbrook, M. J. Genzink, B. Park, I. A. Guzei, M.-H. Baik, T. P. Yoon Nat. Commun. 2021, ASAP. Doi:10.1038\/s41467-021-25878-9. \u6b63\u6587 \u8bbe\u8ba1\u9ad8\u5ea6\u5bf9\u6620\u9009\u62e9\u6027\u7684\u5408\u6210\u8f6c\u5316\u7b56\u7565\uff0c\u5728\u73b0\u4ee3\u5408\u6210\u5316\u5b66\u7684\u7814\u7a76\u4e2d\u5907\u53d7\u5e7f\u6cdb\u5173\u6ce8\u3002\u7136\u800c\uff0c\u901a\u8fc7\u5149\u5316\u5b66\u7b56\u7565\u8fdb\u884c\u7684\u5bf9\u6620\u9009\u62e9\u6027\u5408\u6210\u8bbe\u8ba1\uff0c\u5219\u9762\u4e34\u8bf8\u591a\u6311\u6218[1]-[2](Fig. 1)\u3002\u53d7\u5230\u524d\u671f\u5bf9\u4e8eBr\u00f8nsted\u9178\u5728\u4e0d\u5bf9\u79f0\u5408\u6210\u8f6c\u5316\u7b56\u7565\u4e2d\u7684\u5e94\u7528[4]-[6]\u4ee5\u53ca\u8fd1\u671f\u5bf9\u4e8e\u5bf9\u6620\u9009\u62e9\u6027[2+2]\u5149\u73af\u52a0\u6210\u53cd\u5e94[7]\u76f8\u5173\u7814\u7a76\u7684\u542f\u53d1\uff0c\u8fd9\u91cc\uff0cT. P. Yoon\u4e0eM.-H. Baik\u56e2\u961f\u5171\u540c\u62a5\u9053\u4e00\u79cd\u5168\u65b0\u7684\u901a\u8fc7 BINOL\u884d\u751f\u7684\u624b\u6027\u78f7\u9170\u80faBr\u00f8nsted\u9178\u4fc3\u8fdb\u7684\u5bf9\u6620\u4e0e\u975e\u5bf9\u6620\u9009\u62e9\u6027\u5149[2+2]\u73af\u52a0\u6210\u53cd\u5e94\u65b9\u6cd5\u5b66 (Fig. 1)\u3002\u540c\u65f6\uff0c\u901a\u8fc7\u5149\u8c31\u4e0e\u8ba1\u7b97\u5316\u5b66\u7684\u76f8\u5173\u7814\u7a76\u8868\u660e\uff0c\u8fd9\u4e00\u5168\u65b0\u7684\u50ac\u5316\u73af\u52a0\u6210\u8fc7\u7a0b\u6d89\u53ca\u53d1\u8272\u56e2\u6d3b\u5316\u539f\u7406 (principle of chromophore activation )\u3002 \u9996\u5148\uff0c\u4f5c\u8005\u91c7\u7528\u82ef\u4e59\u70ef\u4e0e\u70ef\u916e\u884d\u751f\u72691\u4f5c\u4e3a\u6a21\u578b\u5e95\u7269\uff0c\u8fdb\u884c\u76f8\u5173\u53cd\u5e94\u6761\u4ef6\u7684\u4f18\u5316\u7b5b\u9009 (Fig. 2)\u3002\u786e\u5b9a\u6700\u4f73\u7684\u53cd\u5e94\u6761\u4ef6\u4e3a\uff1a\u91c7\u7528[Ir(Fppy)2(dtbbpy)]PF6\u4f5c\u4e3a\u5149\u50ac\u5316\u5242\uff0cAC-3\u4f5c\u4e3a\u624b\u6027Br\u00f8nsted\u9178\u50ac\u5316\u5242\uff0c\u901a\u8fc7Kessil H150 Blue LED\u8f90\u5c04\uff0c\u7532\u82ef\u4f5c\u4e3a\u53cd\u5e94\u6eb6\u5242\uff0c\u53cd\u5e94\u6e29\u5ea6\u4e3a-78oC\uff0c\u6700\u7ec8\u83b7\u5f9774%\u6536\u7387\u7684\u73af\u52a0\u6210\u4ea7\u7269 (7:1d.r.\uff0c95% ee)\u3002 \u5728\u4e0a\u8ff0\u7684\u6700\u4f73\u53cd\u5e94\u6761\u4ef6\u4e0b\uff0c\u4f5c\u8005\u9996\u5148\u5bf9\u5404\u7c7b\u03b1,\u03b2-\u4e0d\u9971\u548c\u7fb0\u57fa\u5e95\u7269\u7684\u5e94\u7528\u8303\u56f4\u8fdb\u884c\u8003\u5bdf (Fig. 3)\u3002\u7814\u7a76\u8868\u660e\uff0c\u4e00\u7cfb\u5217\u5177\u6709\u4f9b\u7535\u5b50\u4e0e\u5438\u7535\u5b50\u57fa\u56e2\u53d6\u4ee3\u7684\u03b2-\u82b3\u57fa\u03b1,\u03b2-\u4e0d\u9971\u548c\u7fb0\u57fa\u5e95\u7269\uff0c\u5747\u80fd\u591f\u8f83\u597d\u5730\u4e0e\u4e0a\u8ff0\u7684\u6807\u51c6\u53cd\u5e94\u6761\u4ef6\u517c\u5bb9\uff0c\u5e76\u4ee5\u826f\u597d\u7684\u53cd\u5e94\u6536\u7387\u4e0e\u5bf9\u6620\u4ee5\u53ca\u975e\u5bf9\u6620\u9009\u62e9\u6027\uff0c\u83b7\u5f97\u76f8\u5e94\u7684\u624b\u6027\u4ea7\u72692-9\u3002\u5e76\u4e14\uff0c\u4f5c\u8005\u53d1\u73b0\uff0c\u5bf9\u4e8e\u8418\u57fa\u3001\u567b\u5429\u57fa\u53d6\u4ee3\u7684\u5e95\u7269\uff0c\u540c\u6837\u80fd\u591f\u987a\u5229\u5730\u5b8c\u6210\u4e0a\u8ff0\u7684\u73af\u52a0\u6210\u8fc7\u7a0b\uff0c\u5e76\u83b7\u5f97\u76f8\u5e94\u7684\u624b\u6027\u4ea7\u726910\u4e0e11\u3002\u540c\u65f6\uff0c\u8fd9\u4e00\u5168\u65b0\u7684\u5bf9\u6620\u9009\u62e9\u6027\u73af\u52a0\u6210\u7b56\u7565\u5bf9\u4e8e\u785d\u57fa\u82b3\u70c3 (12)\u4ee5\u53ca\u82b3\u57fa\u7898 (13)\u5e95\u7269\uff0c\u540c\u6837\u80fd\u591f\u6709\u6548\u5730\u517c\u5bb9\u3002 \u4e4b\u540e\uff0c\u8be5\u5c0f\u7ec4\u8fdb\u4e00\u6b65\u5bf9\u5404\u7c7b\u70ef\u57fa\u5e95\u7269\u7684\u5e94\u7528\u8303\u56f4\u8fdb\u884c\u6df1\u5165\u7814\u7a76\u3002\u4f5c\u8005\u53d1\u73b0\uff0c\u82ef\u73af\u4e2d\u6709\u4e0d\u540c\u4f9b\u7535\u5b50\u4e0e\u5438\u7535\u5b50\u57fa\u56e2\u53d6\u4ee3\u7684\u82ef\u4e59\u70ef\u5e95\u7269\uff0c\u5747\u80fd\u591f\u987a\u5229\u5730\u5b8c\u6210\u4e0a\u8ff0\u7684\u4e0d\u5bf9\u79f0\u73af\u52a0\u6210\u8fc7\u7a0b\uff0c\u5e76\u83b7\u5f97\u76f8\u5e94\u7684\u624b\u6027\u4ea7\u726914&#8211;25\u3002\u540c\u65f6\uff0c\u4e0a\u8ff0\u7684\u6807\u51c6\u53cd\u5e94\u6761\u4ef6\u5bf9\u4e8e\u6742\u82b3\u57fa\u53d6\u4ee3\u7684\u82b3\u4e59\u70ef\u3001\u53d6\u4ee3\u4ee5\u53ca\u672a\u53d6\u4ee3\u7684\u4e8c\u70ef\u5e95\u7269\uff0c\u540c\u6837\u80fd\u591f\u6709\u6548\u5730\u517c\u5bb9 (28&#8211;31)\u3002 \u7136\u800c\uff0c\u7814\u7a76\u53d1\u73b0\uff0c\u80fd\u591f\u4e0e\u624b\u6027\u50ac\u5316\u5242\u8fdb\u884c\u914d\u4f4d\u7684\u82b3\u4e59\u70ef\u5e95\u7269\uff0c\u901a\u5e38\u8868\u73b0\u51fa\u8f83\u4f4e\u7684\u53cd\u5e94\u6d3b\u6027 (32)\u3002\u540c\u65f6\uff0c\u4e0a\u8ff0\u7684\u6807\u51c6\u53cd\u5e94\u4f53\u7cfb\uff0c\u5bf9\u4e8e\u8102\u80aa\u65cf\u73af\u5916\u70ef\u57fa\u5e95\u7269 (34&#8211;35)\uff0c\u540c\u6837\u80fd\u591f\u83b7\u5f97\u4e2d\u7b49\u6536\u7387\u4e0e\u826f\u597d\u5bf9\u6620\u9009\u62e9\u6027\u7684\u73af\u52a0\u6210\u4ea7\u7269\u3002\u4e4b\u540e\uff0c\u4f5c\u8005\u8fdb\u4e00\u6b65\u53d1\u73b0\uff0c\u4e0a\u8ff0\u7684\u6807\u51c6\u53cd\u5e94\u6761\u4ef6\u5bf9\u4e8e\u9ad8\u5ea6\u5b98\u80fd\u56e2\u5316\u7684\u82b3\u57fa\u4e59\u70ef\u4e0e\u03b1,\u03b2-\u4e0d\u9971\u548c\u7fb0\u57fa\u5e95\u7269\uff0c\u540c\u6837\u80fd\u591f\u9ad8\u5ea6\u7684\u5bf9\u6620\u9009\u62e9\u6027\u5730\u83b7\u5f97\u76f8\u5e94\u7684\u76ee\u6807\u4ea7\u726936\uff0c\u5e76\u80fd\u591f\u901a\u8fc7\u54aa\u5511\u57fa\u56e2\u7684\u53bb\u9664\uff0c\u8fdb\u4e00\u6b65\u8f6c\u5316\u4e3a\u5176\u4ed6\u7c7b\u578b\u7684\u624b\u6027\u780c\u5757 (Fig. 4)\u3002 \u63a5\u4e0b\u6765\uff0c\u4f5c\u8005\u901a\u8fc7UV-Vis\u5149\u8c31 (Fig. 5a)\u8bc1\u5b9e\uff0cBr\u00f8nsted\u9178\u5728\u73af\u52a0\u6210\u53cd\u5e94\u8fc7\u7a0b\u4e2d\uff0c\u5e76\u975e\u4f5c\u4e3a\u5e38\u89c4\u7684\u4e09\u7ebf\u6001\u5149\u654f\u5316\u5242\u3002\u540c\u65f6\uff0c\u4f5c\u8005\u8fdb\u4e00\u6b65\u901a\u8fc7NMR\u6ef4\u5b9a\u5b9e\u9a8c (NMR titration experiment)\uff0c\u8ba1\u7b97\u51fa\u76f8\u5e94\u7684\u7ed3\u5408\u5e38\u6570Ka = 7.5\u00d7106 (Supplementary Fig. 5)\u3002\u4e4b\u540e\uff0c\u4f5c\u8005\u8fdb\u4e00\u6b65\u5206\u79bb\u51fa\u76f8\u5e94\u7684\u5e95\u7269-\u9178\u914d\u5408\u7269 (substrate-acid complex)\uff0c\u5e76\u901a\u8fc7X-\u5c04\u7ebf\u6676\u4f53\u5b66\u5206\u6790\uff0c\u786e\u5b9a\u5176\u7ed3\u6784 (Fig. 5b-c)\uff0c\u8fdb\u800c\u8fdb\u4e00\u6b65\u9610\u660e\u4e0a\u8ff0\u73af\u52a0\u6210\u8fc7\u7a0b\u4e2d\uff0c\u76f8\u5173\u5bf9\u6620\u9009\u62e9\u6027\u7684\u63a7\u5236\u56e0\u7d20\u3002 \u57fa\u4e8e\u4e0a\u8ff0\u7684\u5b9e\u9a8c\u7814\u7a76\uff0c\u4f5c\u8005\u63d0\u51fa\u901a\u8fc7\u5e95\u7269-\u9178\u914d\u5408\u7269\u4e2d\u5bf9\u4e8e\u76f8\u5173\u5e95\u7269\u7684\u6d3b\u5316\uff0c\u5b58\u5728\u4e24\u79cd\u53ef\u80fd\u7684\u6d3b\u5316\u6a21\u5f0f\uff0c\u5373\u751f\u8272\u56e2\u6d3b\u5316\u673a\u7406 (chromophore activation mechanism)\u4e0e\u7535\u5b50\u4f9b\u4f53-\u53d7\u4f53\u673a\u7406\u3002\u6700\u7ec8\uff0c\u4f5c\u8005\u901a\u8fc7\u5bf9\u5404\u7c7b\u9178\u50ac\u5316\u5242\u4fc3\u8fdb\u7684\u5149\u73af\u52a0\u6210\u8fc7\u7a0b\u4e2d\u53cd\u5e94\u6536\u7387\u7684\u76f8\u5173\u7814\u7a76 (Fig. 6)\u8fdb\u4e00\u6b65\u8bc1\u5b9e\uff0c\u53cd\u5e94\u8fc7\u7a0b\u4e2d\u6d89\u53ca\u751f\u8272\u56e2\u6d3b\u5316\u673a\u7406\u3002\u4e4b\u540e\uff0c\u4f5c\u8005\u901a\u8fc7DFT\u4e0eTDDFT (time-dependent DFT)\u8ba1\u7b97\uff0c\u5bf9\u8fd9\u4e00\u673a\u7406\u7684\u8d77\u6e90\u8fdb\u884c\u6df1\u5165\u7814\u7a76 (Fig. 5d)\u3002 \u603b\u7ed3 T. P. Yoon\u4e0eM.-H. Baik\u7814\u7a76\u56e2\u961f\u5171\u540c\u8bbe\u8ba1\u51fa\u4e00\u79cd\u5168\u65b0\u7684\u901a\u8fc7\u624b\u6027Br\u00f8nsted\u9178\u63a7\u5236\u7684\u5177\u6709\u9ad8\u5ea6\u5bf9\u6620\u4e0e\u975e\u5bf9\u6620\u9009\u62e9\u6027\u7684\u5149[2+2]\u73af\u52a0\u6210\u53cd\u5e94\u65b9\u6cd5\u5b66\u3002\u8fd9\u4e00\u5168\u65b0\u7684\u73af\u52a0\u6210\u7b56\u7565\u5177\u6709\u9ad8\u5ea6\u7684\u5bf9\u6620\u9009\u62e9\u6027\u63a7\u5236\u3001\u5e7f\u6cdb\u7684\u5e95\u7269\u5e94\u7528\u8303\u56f4\u4ee5\u53ca\u826f\u597d\u7684\u5b98\u80fd\u56e2\u517c\u5bb9\u6027\u7b49\u4f18\u52bf\u3002 \u53c2\u8003\u6587\u732e [1] (a) H. 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