{"id":49125,"date":"2024-03-06T09:36:29","date_gmt":"2024-03-06T01:36:29","guid":{"rendered":"\/\/www.gsbet888.com\/?p=49125"},"modified":"2024-03-06T09:37:41","modified_gmt":"2024-03-06T01:37:41","slug":"jacs-%e9%95%8d%e5%82%ac%e5%8c%96%e8%bf%9c%e7%a8%8b%e6%b0%a7%e5%8c%96%e5%8a%a0%e6%88%90%e5%ae%9e%e7%8e%b0%e7%a2%b3%e6%b0%a7%e9%94%ae%e9%80%89%e6%8b%a9%e6%80%a7%e6%96%ad%e8%a3%82","status":"publish","type":"post","link":"\/\/www.gsbet888.com\/%e5%8c%96%e5%ad%a6%e6%9d%82%e8%ae%b0\/recentpaper\/2024\/03\/jacs-%e9%95%8d%e5%82%ac%e5%8c%96%e8%bf%9c%e7%a8%8b%e6%b0%a7%e5%8c%96%e5%8a%a0%e6%88%90%e5%ae%9e%e7%8e%b0%e7%a2%b3%e6%b0%a7%e9%94%ae%e9%80%89%e6%8b%a9%e6%80%a7%e6%96%ad%e8%a3%82.html","title":{"rendered":"JACS: \u954d\u50ac\u5316\u201c\u8fdc\u7a0b\u6c27\u5316\u52a0\u6210\u201d\u5b9e\u73b0\u78b3\u6c27\u952e\u9009\u62e9\u6027\u65ad\u88c2\u548c\u73af\u6c27\u6811\u8102\u964d\u89e3"},"content":{"rendered":"<p style=\"text-align: justify;\">\u4f5c\u8005\uff1aYumeng<\/p>\n<h4 style=\"text-align: justify;\">\u5bfc\u8bfb\uff1a<\/h4>\n<p style=\"text-align: justify;\">\u00a0\u00a0\u00a0\u00a0\u00a0 \u4e1c\u4eac\u5927\u5b66\u7684Kyoko Nozaki\u8bfe\u9898\u7ec4\u5728<em>J. Am. Chem. Soc.<\/em>\u4e2d\u53d1\u8868\u8bba\u6587\uff0c\u62a5\u9053\u4e86\u4e00\u79cd\u954d\u50ac\u5316\u201c\u8fdc\u7a0b\u6c27\u5316\u52a0\u6210\u201d\u5b9e\u73b0\u7684\u78b3\u2212\u6c27\u952e\u6c22\u89e3\u53cd\u5e94\uff0c\u6210\u529f\u5c06\u6b64\u65b9\u6cd5\u5e94\u7528\u5230\u53cc\u915aA\u578b\u73af\u6c27\u6811\u8102\u7684\u964d\u89e3\u5e76\u4ece\u4e2d\u56de\u6536\u53cc\u915aA\u3002<\/p>\n<blockquote><p>Nickel-Catalyzed C(sp<sup>3<\/sup>)\u2212O Hydrogenolysis via a Remote Concerted Oxidative Addition and its Application to Degradation of a Bisphenol A-Based Epoxy Resin<\/p>\n<p>Yumeng Liao, Kohei Takahashi,* and Kyoko Nozaki*<\/p>\n<p><em>J. Am. Chem. Soc. <\/em><strong>2024<\/strong>, <em>146<\/em>, 2419\u20132425.<\/p>\n<p>DOI: <a href=\"https:\/\/doi.org\/10.1021\/jacs.3c09061\">10.1021\/jacs.3c09061<\/a><\/p><\/blockquote>\n<p style=\"text-align: justify;\">\u78b3\u2212\u6c27\u919a\u952e\uff08C\u2212O\u2212C\uff09\u5e38\u89c1\u4e8e\u5404\u7c7b\u5851\u6599\u5206\u5b50\u4e2d\uff0c\u5176\u4e2d\u4ee5\u53cc\u915aA\u578b\u73af\u6c27\u6811\u8102\u5c24\u4e3a\u91cd\u8981\u3002\u8fd9\u7c7b\u6811\u8102\u901a\u5e38\u7531\u53cc\u915a A \u4e8c\u7f29\u6c34\u7518\u6cb9\u919a\uff08BADGE\u00a0\uff09\u548c\u80fa\u3001\u7fa7\u9178\u9150\u548c\u82ef\u915a\u4f4e\u805a\u7269\u7b49\u5404\u7c7b\u56fa\u5316\u5242\u6765\u5408\u6210\uff08Scheme 1a\uff09\u3002\u663e\u800c\u6613\u89c1\uff0c\u901a\u8fc7\u9009\u62e9\u6027\u7684<em>sp<\/em><sup>3<\/sup>\u78b3\u6c27\u00a0\u952e\u65ad\u88c2\u53ef\u4ee5\u5b9e\u73b0\u4ece\u53cc\u915aA\u578b\u73af\u6c27\u6811\u8102\u4e2d\u56de\u6536\u91cd\u8981\u5316\u5de5\u539f\u6599\u53cc\u915aA\u3002\u7136\u800c\uff0c\u8fc7\u53bb\u7684\u5927\u91cf\u62a5\u9053\u90fd\u96c6\u4e2d\u5728<em>sp<\/em><sup>2<\/sup>\u78b3\u2212\u6c27\u952e\u7684\u65ad\u88c2\uff0c\u5e76\u4f7f\u7528\u954d\u3001\u94c1\u548c\u94d1\u7b49\u8fc7\u6e21\u91d1\u5c5e\uff1b\u76f8\u6bd4\u4e4b\u4e0b\uff0c<em>sp<\/em><sup>3<\/sup>\u78b3\u2212\u6c27\u952e\u7684\u65ad\u88c2\u5219\u4ec5\u6709\u51e0\u4f8b\uff0c\u5e76\u4e14\u9700\u4f7f\u7528\u8d35\u91d1\u5c5e\u50ac\u5316\u5242 (\u94f1\uff0c\u94d1)\uff08Scheme 1b\uff09\uff0c\u4f8b\u5982Skrydstrup\u7b49\u4eba\u57282023\u5e74\u62a5\u9053\u7684\u9996\u4f8b\u4f7f\u7528\u5747\u76f8\u948c\u50ac\u5316\u5242\u7684\u73af\u6c27\u6811\u8102\u53ca\u5176\u590d\u5408\u6750\u6599\u7684\u964d\u89e3\uff08<em>Nature <\/em><strong>2023<\/strong>, <em>617<\/em>, 730\u2212737\uff09\u3002<\/p>\n<p style=\"text-align: justify;\">\u57fa\u4e8e\u954d\u5728\u78b3\u2212\u6c27\u952e\u7684\u50ac\u5316\u65ad\u88c2\u4e2d\u7684\u72ec\u7279\u50ac\u5316\u6d3b\u6027\uff0c\u4ee5\u53ca\u5176\u5ec9\u4ef7\u548c\u50a8\u91cf\u4e30\u5bcc\u7684\u4f18\u52bf\uff0c\u4f5c\u8005\u901a\u8fc7\u4f7f\u7528\u954d\u50ac\u5316\u5242\u7684\u201c\u8fdc\u7a0b\u534f\u540c\u6c27\u5316\u52a0\u6210\u201d\u7b56\u7565\u5b9e\u73b0\u4e86<em>sp<\/em><sup>3<\/sup>\u78b3\u2212\u6c27\u952e\u7684\u9009\u62e9\u6027\u65ad\u88c2\uff0c\u5e76\u6210\u529f\u5c06\u5176\u5e94\u7528\u4e8e\u53cc\u915aA\u578b\u73af\u6c27\u6811\u8102\u7684\u964d\u89e3\uff0c\u6700\u7ec8\u5b8c\u6210\u53cc\u915aA\u7684\u9009\u62e9\u6027\u56de\u6536\uff08Scheme 1c\uff09\u3002<\/p>\n<p style=\"text-align: justify;\"><img loading=\"lazy\" decoding=\"async\" class=\"aligncenter wp-image-49127 size-full\" src=\"https:\/\/assets.www.gsbet888.com\/uploads\/2024\/03\/image002.gif\" alt=\"\" width=\"1247\" height=\"723\" \/><\/p>\n<p style=\"text-align: justify;\">\u4f5c\u8005\u9996\u5148\u5408\u6210\u80fa\u56fa\u5316\u73af\u6c27\u6811\u8102\u7684\u6a21\u578b\u5e95\u7269<strong>1<\/strong>\u6765\u4f18\u5316\u53cd\u5e94\u6761\u4ef6\u3002\u5728\u8003\u5bdf\u4e86\u4e0d\u540c\u7684\u954d\u524d\u4f53\u3001\u914d\u4f53\u4ee5\u53ca\u6c14\u4f53\u6c1b\u56f4\u540e\uff0c\u53d1\u73b0\u8be5\u53cd\u5e94\u5e76\u4e0d\u9700\u8981\u989d\u5916\u6c22\u6e90\uff0c\u6700\u4f73\u53cd\u5e94\u6761\u4ef6\u4e3a\uff1a\u5728\u6c2e\u6c14\u6c1b\u56f4\u4e2d\uff0c\u4f7f\u752810 mol% Ni(cod)(dcype)\u50ac\u5316\u5242\u5728200 \u00b0C\u6761\u4ef6\u4e0b\u53cd\u5e9424\u5c0f\u65f6\uff0c\u6700\u7ec8\u4ee590%\u4ea7\u7387\u83b7\u5f97\u4e86\u76ee\u6807\u4ea7\u72692\uff08Table 1, entry 13\uff09\u3002<\/p>\n<p style=\"text-align: justify;\"><img loading=\"lazy\" decoding=\"async\" class=\"aligncenter wp-image-49128 size-full\" src=\"https:\/\/assets.www.gsbet888.com\/uploads\/2024\/03\/image003.gif\" alt=\"\" width=\"797\" height=\"1072\" \/><\/p>\n<p style=\"text-align: justify;\">\u63a5\u7740\u4f5c\u8005\u8fdb\u884c\u4e86\u4e00\u7cfb\u5217\u7684\u5bf9\u7167\u8bd5\u9a8c\u6765\u63a2\u7a76\u673a\u7406\uff1a\u5728\u6807\u51c6\u6761\u4ef6\u4e0b\uff0c\u82b3\u57fa\u7532\u57fa\u919a<strong>3<\/strong>\u65e0\u6cd5\u53d1\u751f\u78b3\u2212\u6c27\u952e\u7684\u65ad\u88c2\uff0c\u663e\u793a\u8be5\u4f53\u7cfb\u9700\u8981\u5bfc\u5411\u57fa\u56e2\uff08Scheme 2a\uff09\uff1b\u5316\u5408\u7269<strong>6<\/strong>\u5728\u6c2e\u6c14\u6c1b\u56f4\u4e2d\u80fd\u4ee5\u9ad8\u4ea7\u7387\u751f\u6210\u5bf9\u53d4\u4e01\u57fa\u82ef\u915a\uff08<strong>2<\/strong>\uff09\u548c2-\u7678\u916e(<strong>7<\/strong>)\uff0c\u8868\u660e\u8fd9\u662f\u4e00\u4e2a\u8f6c\u79fb\u6c22\u89e3\u53cd\u5e94\uff0c\u5e76\u4e14\u5e95\u7269\u4e2d\u7684\u7f9f\u57fa\u548c\u5176<em>\u03b1-<\/em>\u6c22\u539f\u5b50\u4e3a\u53cd\u5e94\u7684\u6c22\u6e90\uff08Scheme 2b\uff09\u3002\u800c\u5c06\u5316\u5408\u7269<strong>6<\/strong>\u7684\u7f9f\u57fa\u7532\u57fa\u5316\uff08<strong>8<\/strong>\uff0cScheme 2c\uff09\u6216\u5728\u5176<em>\u03b1-<\/em>\u4f4d\u5f15\u5165\u7532\u57fa\uff08<strong>9<\/strong>\uff0cScheme 2d\uff09\u90fd\u4f7f\u5f97\u53cd\u5e94\u65e0\u6cd5\u8fdb\u884c\uff0c\u8fd9\u4e9b\u7ed3\u679c\u66f4\u8fdb\u4e00\u6b65\u9a8c\u8bc1\u4e86\u4e0a\u8ff0\u7ed3\u8bba\u3002<\/p>\n<p style=\"text-align: justify;\"><img loading=\"lazy\" decoding=\"async\" class=\"aligncenter wp-image-49129 size-full\" src=\"https:\/\/assets.www.gsbet888.com\/uploads\/2024\/03\/image004.jpg\" alt=\"\" width=\"879\" height=\"898\" srcset=\"https:\/\/assets.www.gsbet888.com\/uploads\/2024\/03\/image004.jpg 879w, https:\/\/assets.www.gsbet888.com\/uploads\/2024\/03\/image004-294x300.jpg 294w, https:\/\/assets.www.gsbet888.com\/uploads\/2024\/03\/image004-680x695.jpg 680w, https:\/\/assets.www.gsbet888.com\/uploads\/2024\/03\/image004-768x785.jpg 768w\" sizes=\"(max-width: 879px) 100vw, 879px\" \/><\/p>\n<p style=\"text-align: justify;\">\u901a\u8fc7DFT\u8ba1\u7b97\uff0c\u4f5c\u8005\u63d0\u51fa\u4e86\u4e00\u7cfb\u5217\u53cd\u5e94\u673a\u7406\uff1a\u96f6\u4ef7\u954d\u9996\u5148\u4e0e\u5e95\u7269\u7684O\u2212H\u952e\u53d1\u751f\u6c27\u5316\u52a0\u6210\uff08<strong>Int-1<\/strong>\uff09\uff0c\u63a5\u7740\u7ecf\u8fc7<em>\u03b2<\/em>-\u6c22\u6d88\u9664\u4e0e\u82ef\u73af\u914d\u4f4d\u5f97\u5230\u4e2d\u95f4\u4f53<strong>Int-4<\/strong>\uff0c\u518d\u901a\u8fc7\u534f\u540c\u7684\u8fdc\u7a0b\u6c27\u5316\u52a0\u6210\uff08<em>remote-concerted oxidative addition<\/em>\uff09\u53d1\u751fC\u2212O\u952e\u65ad\u88c2\u751f\u6210\u70ef\u9187\u82ef\u57fa\u954d\u4e2d\u95f4\u4f53<strong>Int-5a<\/strong>\uff0c\u5e76\u4e14\u8fdb\u4e00\u6b65\u5f02\u6784\u5316\u5f97\u5230\u66f4\u52a0\u7a33\u5b9a\u7684\u4e2d\u95f4\u4f53<strong>Int-5c<\/strong>\uff08Figure 1a\uff09\u3002\u968f\u540e\uff0c\u53e6\u4e00\u5206\u5b50\u5e95\u7269\u53c2\u4e0e\u914d\u4f4d\u5e76\u8d28\u5b50\u5316\u70ef\u9187\u8d1f\u79bb\u5b50\u5f97\u5230\u916e\u954d\u4e2d\u95f4\u4f53<strong>Int-7<\/strong>\u3002\u5728\u916e\u4ea7\u7269\u89e3\u79bb\u540e\uff0c\u901a\u8fc7\u6c22\u6c14\u7684\u534f\u52a9\u5f97\u5230\u6700\u7ec8\u4ea7\u7269\u915a\uff08Figure 2b\uff09\u3002<\/p>\n<p style=\"text-align: justify;\"><img loading=\"lazy\" decoding=\"async\" class=\"aligncenter wp-image-49130 size-full\" src=\"https:\/\/assets.www.gsbet888.com\/uploads\/2024\/03\/image005.gif\" alt=\"\" width=\"1249\" height=\"1151\" \/><\/p>\n<p style=\"text-align: justify;\">\u63a5\u7740\uff0c\u4f5c\u8005\u4f7f\u7528Ni(SIPr)(C<sub>6<\/sub>H<sub>6<\/sub>)\u914d\u5408\u7269\u548c\u5316\u5408\u7269<strong>11<\/strong>\u8fdb\u884c\u5f53\u91cf\u6df7\u5408\uff0c\u53d1\u73b0\u53cd\u5e94\u5feb\u901f\u4ea7\u751f\u4e86\u5316\u5408\u7269<strong>12<\/strong>\uff0c\u5e76\u901a\u8fc7X\u5c04\u7ebf\u5355\u6676\u884d\u5c04\u786e\u5b9a\u5176\u4e3a<em>\u03b7<\/em><sup>3<\/sup>-\u70ef\u9187\u82ef\u6c27\u57fa\u954d\u7edc\u5408\u7269\uff08Scheme 3\uff09\u3002\u503c\u5f97\u6ce8\u610f\u7684\u662f\uff0c\u914d\u5408\u7269<strong>12<\/strong>\u4e0eDFT\u8ba1\u7b97\u4e2d\u78b3\u2212\u6c27\u952e\u65ad\u88c2\u540e\u7684\u7a33\u5b9a\u4e2d\u95f4\u4f53<strong>Int-5c<\/strong>\u6709\u7740\u76f8\u540c\u6784\u9020\uff0c\u4e14\u751f\u6210<strong>12<\/strong>\u7684\u53cd\u5e94\u5728\u5ba4\u6e29\u6761\u4ef6\u4e0b\u4ec5\u97005\u5206\u949f\u4fbf\u80fd\u5b8c\u6210\uff0c\u8fd9\u4e5f\u7b26\u5408DFT\u8ba1\u7b97\u7ed3\u679c\u4e2d<strong>Int-4<\/strong>\u5230<strong>TS-2<\/strong>\u4ec5\u670913.2 kcal\/mol\u80fd\u5792\u7684\u7ed3\u8bba\uff0c\u8fdb\u4e00\u6b65\u9a8c\u8bc1\u4e86\u673a\u7406\u7684\u5408\u7406\u6027\u3002<\/p>\n<p style=\"text-align: justify;\"><img loading=\"lazy\" decoding=\"async\" class=\"aligncenter wp-image-49131 size-full\" src=\"https:\/\/assets.www.gsbet888.com\/uploads\/2024\/03\/image006.gif\" alt=\"\" width=\"764\" height=\"302\" \/><\/p>\n<p style=\"text-align: justify;\">\u56e0\u6b64\uff0c\u4f5c\u8005\u63d0\u51fa\u4e86\u8be5\u53cd\u5e94\u4e2d\u954d\u50ac\u5316\u7684\u201c\u8fdc\u7a0b\u6c27\u5316\u52a0\u6210\u201d\u7684\u78b3\u2212\u6c27\u952e\u65ad\u88c2\u673a\u7406\uff0c\u5373\u954d\u5728\u53c2\u4e0e\u6c27\u5316\u52a0\u6210\u7684\u8fc7\u7a0b\u4e2d\u5e76\u4e0d\u4e0e\u53d1\u751f\u65ad\u88c2\u7684\u78b3\u2212\u6c27\u952e\u539f\u5b50\u76f4\u63a5\u76f8\u8fde\u3002\u4f5c\u8005\u4e5f\u5bf9\u201c\u76f4\u63a5\u6c27\u5316\u52a0\u6210\u201d\u8fc7\u7a0b\u8fdb\u884c\u4e86DFT\u8ba1\u7b97\uff08Scheme 4\uff09\uff0c\u7ed3\u679c\u663e\u793a\uff0c\u76f8\u6bd4\u4e8e\u201c\u8fdc\u7a0b\u6c27\u5316\u52a0\u6210\u201d\u4e2d13.2 kcal\/mol\u7684\u80fd\u5792\uff0c\u201c\u76f4\u63a5\u6c27\u5316\u52a0\u6210\u201d\u5219\u9700\u8981\u66f4\u9ad8\u7684\u80fd\u91cf\uff0826.0 kcal\/mol\uff09\u3002<\/p>\n<p style=\"text-align: justify;\"><img loading=\"lazy\" decoding=\"async\" class=\"aligncenter wp-image-49132 size-full\" src=\"https:\/\/assets.www.gsbet888.com\/uploads\/2024\/03\/image007.gif\" alt=\"\" width=\"799\" height=\"480\" \/><\/p>\n<p style=\"text-align: justify;\">\u5728\u638c\u63e1\u6700\u4f73\u53cd\u5e94\u6761\u4ef6\u4ee5\u53ca\u53ef\u80fd\u7684\u53cd\u5e94\u673a\u7406\u540e\uff0c\u6700\u540e\uff0c\u4f5c\u8005\u4f7f\u75284,4\u2032-\u53cc\u4e8c\u82ef\u57fa\u81a6\u7532\u70f7(\u73af\u5df1\u80fa)\u548c\u53cc\u915a A \u4e8c\u7f29\u6c34\u7518\u6cb9\u919a\uff08BADGE\uff09\u5408\u6210\u4e86\u4e00\u79cd\u80fa\u56fa\u5316\u7684\u53cc\u915aA\u578b\u73af\u6c27\u6811\u8102\uff08Scheme 6a\uff09\uff0c\u5e76\u5c06\u5176\u7f6e\u4e8e\u6807\u51c6\u6761\u4ef6\u4e0b\u8fdb\u884c\u5206\u89e3\u3002\u7ed3\u679c\u663e\u793a\uff0c\u5728\u6c22\u6c14\u6c1b\u56f4\u4e2d\uff0c\u4f7f\u752810 mol% Ni(cod)(dcype)\u50ac\u5316\u5242\u5728<em>N-<\/em>\u7532\u57fa\u5421\u54af\u70f7\u916e\uff08NMP\uff09\u6eb6\u5242\u4e2d\u3001200 \u00b0C\u4e0b\u53cd\u5e9436\u5c0f\u65f6\uff0c\u5c31\u80fd\u4ee566%\u5206\u79bb\u4ea7\u7387\u6210\u529f\u56de\u6536\u53cc\u915aA\uff08Scheme 6b\uff09\u3002<\/p>\n<p style=\"text-align: justify;\"><img loading=\"lazy\" decoding=\"async\" class=\"aligncenter wp-image-49133 size-full\" src=\"https:\/\/assets.www.gsbet888.com\/uploads\/2024\/03\/image008.gif\" alt=\"\" width=\"1247\" height=\"635\" \/><\/p>\n<h4 style=\"text-align: justify;\">\u603b\u7ed3\uff1a<\/h4>\n<p style=\"text-align: justify;\">\u4e1c\u4eac\u5927\u5b66\u7684Kyoko Nozaki\u8bfe\u9898\u7ec4\u4f7f\u7528\u5ec9\u4ef7\u7684\u954d\u50ac\u5316\u5242\uff0c\u62a5\u9053\u4e86\u4e00\u79cd<em>sp<\/em><sup>3<\/sup>\u78b3\u2212\u6c27\u952e\u7684\u9009\u62e9\u6027\u6c22\u89e3\u53cd\u5e94\uff0c\u5c06<em>\u03b2<\/em>-\u7f9f\u57fa\u70f7\u57fa\u82b3\u57fa\u919a\u9009\u62e9\u6027\u5730\u8f6c\u5316\u4e3a\u76f8\u5e94\u7684\u915a\u548c\u916e\u3002\u673a\u7406\u5b9e\u9a8c\u548cDFT\u8ba1\u7b97\u7ed3\u679c\u8868\u660e\u8be5\u53cd\u5e94\u662f\u8f6c\u79fb\u6c22\u89e3\u53cd\u5e94\uff0c\u5176\u4e2d\u5173\u952e\u7684\u78b3\u2212\u6c27\u952e\u65ad\u88c2\u6b65\u9aa4\u662f\u901a\u8fc7\u954d\u50ac\u5316\u7684\u201c\u8fdc\u7a0b\u6c27\u5316\u52a0\u6210\u201d\u8fc7\u7a0b\u5b9e\u73b0\u7684\u3002\u6700\u540e\uff0c\u4f5c\u8005\u5408\u6210\u4e86\u4e00\u79cd\u80fa\u56fa\u5316\u53cc\u915aA\u578b\u73af\u6c27\u6811\u8102\uff0c\u5728\u6807\u51c6\u6761\u4ef6\u4e0b\u6210\u529f\u8fdb\u884c\u964d\u89e3\u5e76\u56de\u6536\u4e86\u53ef\u89c2\u6536\u7387\u7684\u53cc\u915aA\u3002\u8be5\u62a5\u9053\u4e0d\u4ec5\u4e3a\u954d\u50ac\u5316\u78b3\u2212\u6c27\u952e\u65ad\u88c2\u8d21\u732e\u4e86\u65b0\u7684\u673a\u7406\uff0c\u4e5f\u4e3a\u5851\u6599\u964d\u89e3\u548c\u5316\u5b66\u56de\u6536\u63d0\u4f9b\u4e86\u65b0\u7684\u601d\u8def\u3002<\/p>\n<h4 style=\"text-align: justify;\">\u8bfe\u9898\u7ec4\u4e3b\u9875\uff1a<\/h4>\n<p style=\"text-align: justify;\"><a href=\"http:\/\/park.itc.u-tokyo.ac.jp\/nozakilab\/indexE.html\">http:\/\/park.itc.u-tokyo.ac.jp\/nozakilab\/indexE.html<\/a><\/p>\n<p style=\"text-align: justify;\">\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.<\/p>\n","protected":false},"excerpt":{"rendered":"\u4f5c\u8005\uff1aYumeng \u5bfc\u8bfb\uff1a \u00a0\u00a0\u00a0\u00a0\u00a0 \u4e1c\u4eac\u5927\u5b66\u7684Kyoko Nozaki\u8bfe\u9898\u7ec4\u5728J. Am. Chem. Soc.\u4e2d\u53d1\u8868\u8bba\u6587\uff0c\u62a5\u9053\u4e86\u4e00\u79cd\u954d\u50ac\u5316\u201c\u8fdc\u7a0b\u6c27\u5316\u52a0\u6210\u201d\u5b9e\u73b0\u7684\u78b3\u2212\u6c27\u952e\u6c22\u89e3\u53cd\u5e94\uff0c\u6210\u529f\u5c06\u6b64\u65b9\u6cd5\u5e94\u7528\u5230\u53cc\u915aA\u578b\u73af\u6c27\u6811\u8102\u7684\u964d\u89e3\u5e76\u4ece\u4e2d\u56de\u6536\u53cc\u915aA\u3002 Nickel-Catalyzed C(sp3)\u2212O Hydrogenolysis via a Remote Concerted Oxidative Addition and its Application to Degradation of a Bisphenol A-Based Epoxy Resin Yumeng Liao, Kohei Takahashi,* and Kyoko Nozaki* J. Am. Chem. Soc. 2024, 146, 2419\u20132425. DOI: 10.1021\/jacs.3c09061 \u78b3\u2212\u6c27\u919a\u952e\uff08C\u2212O\u2212C\uff09\u5e38\u89c1\u4e8e\u5404\u7c7b\u5851\u6599\u5206\u5b50\u4e2d\uff0c\u5176\u4e2d\u4ee5\u53cc\u915aA\u578b\u73af\u6c27\u6811\u8102\u5c24\u4e3a\u91cd\u8981\u3002\u8fd9\u7c7b\u6811\u8102\u901a\u5e38\u7531\u53cc\u915a A \u4e8c\u7f29\u6c34\u7518\u6cb9\u919a\uff08BADGE\u00a0\uff09\u548c\u80fa\u3001\u7fa7\u9178\u9150\u548c\u82ef\u915a\u4f4e\u805a\u7269\u7b49\u5404\u7c7b\u56fa\u5316\u5242\u6765\u5408\u6210\uff08Scheme 1a\uff09\u3002\u663e\u800c\u6613\u89c1\uff0c\u901a\u8fc7\u9009\u62e9\u6027\u7684sp3\u78b3\u6c27\u00a0\u952e\u65ad\u88c2\u53ef\u4ee5\u5b9e\u73b0\u4ece\u53cc\u915aA\u578b\u73af\u6c27\u6811\u8102\u4e2d\u56de\u6536\u91cd\u8981\u5316\u5de5\u539f\u6599\u53cc\u915aA\u3002\u7136\u800c\uff0c\u8fc7\u53bb\u7684\u5927\u91cf\u62a5\u9053\u90fd\u96c6\u4e2d\u5728sp2\u78b3\u2212\u6c27\u952e\u7684\u65ad\u88c2\uff0c\u5e76\u4f7f\u7528\u954d\u3001\u94c1\u548c\u94d1\u7b49\u8fc7\u6e21\u91d1\u5c5e\uff1b\u76f8\u6bd4\u4e4b\u4e0b\uff0csp3\u78b3\u2212\u6c27\u952e\u7684\u65ad\u88c2\u5219\u4ec5\u6709\u51e0\u4f8b\uff0c\u5e76\u4e14\u9700\u4f7f\u7528\u8d35\u91d1\u5c5e\u50ac\u5316\u5242 (\u94f1\uff0c\u94d1)\uff08Scheme 1b\uff09\uff0c\u4f8b\u5982Skrydstrup\u7b49\u4eba\u57282023\u5e74\u62a5\u9053\u7684\u9996\u4f8b\u4f7f\u7528\u5747\u76f8\u948c\u50ac\u5316\u5242\u7684\u73af\u6c27\u6811\u8102\u53ca\u5176\u590d\u5408\u6750\u6599\u7684\u964d\u89e3\uff08Nature 2023, 617, 730\u2212737\uff09\u3002 \u57fa\u4e8e\u954d\u5728\u78b3\u2212\u6c27\u952e\u7684\u50ac\u5316\u65ad\u88c2\u4e2d\u7684\u72ec\u7279\u50ac\u5316\u6d3b\u6027\uff0c\u4ee5\u53ca\u5176\u5ec9\u4ef7\u548c\u50a8\u91cf\u4e30\u5bcc\u7684\u4f18\u52bf\uff0c\u4f5c\u8005\u901a\u8fc7\u4f7f\u7528\u954d\u50ac\u5316\u5242\u7684\u201c\u8fdc\u7a0b\u534f\u540c\u6c27\u5316\u52a0\u6210\u201d\u7b56\u7565\u5b9e\u73b0\u4e86sp3\u78b3\u2212\u6c27\u952e\u7684\u9009\u62e9\u6027\u65ad\u88c2\uff0c\u5e76\u6210\u529f\u5c06\u5176\u5e94\u7528\u4e8e\u53cc\u915aA\u578b\u73af\u6c27\u6811\u8102\u7684\u964d\u89e3\uff0c\u6700\u7ec8\u5b8c\u6210\u53cc\u915aA\u7684\u9009\u62e9\u6027\u56de\u6536\uff08Scheme 1c\uff09\u3002 \u4f5c\u8005\u9996\u5148\u5408\u6210\u80fa\u56fa\u5316\u73af\u6c27\u6811\u8102\u7684\u6a21\u578b\u5e95\u72691\u6765\u4f18\u5316\u53cd\u5e94\u6761\u4ef6\u3002\u5728\u8003\u5bdf\u4e86\u4e0d\u540c\u7684\u954d\u524d\u4f53\u3001\u914d\u4f53\u4ee5\u53ca\u6c14\u4f53\u6c1b\u56f4\u540e\uff0c\u53d1\u73b0\u8be5\u53cd\u5e94\u5e76\u4e0d\u9700\u8981\u989d\u5916\u6c22\u6e90\uff0c\u6700\u4f73\u53cd\u5e94\u6761\u4ef6\u4e3a\uff1a\u5728\u6c2e\u6c14\u6c1b\u56f4\u4e2d\uff0c\u4f7f\u752810 mol% Ni(cod)(dcype)\u50ac\u5316\u5242\u5728200 \u00b0C\u6761\u4ef6\u4e0b\u53cd\u5e9424\u5c0f\u65f6\uff0c\u6700\u7ec8\u4ee590%\u4ea7\u7387\u83b7\u5f97\u4e86\u76ee\u6807\u4ea7\u72692\uff08Table 1, entry 13\uff09\u3002 \u63a5\u7740\u4f5c\u8005\u8fdb\u884c\u4e86\u4e00\u7cfb\u5217\u7684\u5bf9\u7167\u8bd5\u9a8c\u6765\u63a2\u7a76\u673a\u7406\uff1a\u5728\u6807\u51c6\u6761\u4ef6\u4e0b\uff0c\u82b3\u57fa\u7532\u57fa\u919a3\u65e0\u6cd5\u53d1\u751f\u78b3\u2212\u6c27\u952e\u7684\u65ad\u88c2\uff0c\u663e\u793a\u8be5\u4f53\u7cfb\u9700\u8981\u5bfc\u5411\u57fa\u56e2\uff08Scheme 2a\uff09\uff1b\u5316\u5408\u72696\u5728\u6c2e\u6c14\u6c1b\u56f4\u4e2d\u80fd\u4ee5\u9ad8\u4ea7\u7387\u751f\u6210\u5bf9\u53d4\u4e01\u57fa\u82ef\u915a\uff082\uff09\u548c2-\u7678\u916e(7)\uff0c\u8868\u660e\u8fd9\u662f\u4e00\u4e2a\u8f6c\u79fb\u6c22\u89e3\u53cd\u5e94\uff0c\u5e76\u4e14\u5e95\u7269\u4e2d\u7684\u7f9f\u57fa\u548c\u5176\u03b1-\u6c22\u539f\u5b50\u4e3a\u53cd\u5e94\u7684\u6c22\u6e90\uff08Scheme 2b\uff09\u3002\u800c\u5c06\u5316\u5408\u72696\u7684\u7f9f\u57fa\u7532\u57fa\u5316\uff088\uff0cScheme 2c\uff09\u6216\u5728\u5176\u03b1-\u4f4d\u5f15\u5165\u7532\u57fa\uff089\uff0cScheme 2d\uff09\u90fd\u4f7f\u5f97\u53cd\u5e94\u65e0\u6cd5\u8fdb\u884c\uff0c\u8fd9\u4e9b\u7ed3\u679c\u66f4\u8fdb\u4e00\u6b65\u9a8c\u8bc1\u4e86\u4e0a\u8ff0\u7ed3\u8bba\u3002 \u901a\u8fc7DFT\u8ba1\u7b97\uff0c\u4f5c\u8005\u63d0\u51fa\u4e86\u4e00\u7cfb\u5217\u53cd\u5e94\u673a\u7406\uff1a\u96f6\u4ef7\u954d\u9996\u5148\u4e0e\u5e95\u7269\u7684O\u2212H\u952e\u53d1\u751f\u6c27\u5316\u52a0\u6210\uff08Int-1\uff09\uff0c\u63a5\u7740\u7ecf\u8fc7\u03b2-\u6c22\u6d88\u9664\u4e0e\u82ef\u73af\u914d\u4f4d\u5f97\u5230\u4e2d\u95f4\u4f53Int-4\uff0c\u518d\u901a\u8fc7\u534f\u540c\u7684\u8fdc\u7a0b\u6c27\u5316\u52a0\u6210\uff08remote-concerted oxidative addition\uff09\u53d1\u751fC\u2212O\u952e\u65ad\u88c2\u751f\u6210\u70ef\u9187\u82ef\u57fa\u954d\u4e2d\u95f4\u4f53Int-5a\uff0c\u5e76\u4e14\u8fdb\u4e00\u6b65\u5f02\u6784\u5316\u5f97\u5230\u66f4\u52a0\u7a33\u5b9a\u7684\u4e2d\u95f4\u4f53Int-5c\uff08Figure 1a\uff09\u3002\u968f\u540e\uff0c\u53e6\u4e00\u5206\u5b50\u5e95\u7269\u53c2\u4e0e\u914d\u4f4d\u5e76\u8d28\u5b50\u5316\u70ef\u9187\u8d1f\u79bb\u5b50\u5f97\u5230\u916e\u954d\u4e2d\u95f4\u4f53Int-7\u3002\u5728\u916e\u4ea7\u7269\u89e3\u79bb\u540e\uff0c\u901a\u8fc7\u6c22\u6c14\u7684\u534f\u52a9\u5f97\u5230\u6700\u7ec8\u4ea7\u7269\u915a\uff08Figure 2b\uff09\u3002 \u63a5\u7740\uff0c\u4f5c\u8005\u4f7f\u7528Ni(SIPr)(C6H6)\u914d\u5408\u7269\u548c\u5316\u5408\u726911\u8fdb\u884c\u5f53\u91cf\u6df7\u5408\uff0c\u53d1\u73b0\u53cd\u5e94\u5feb\u901f\u4ea7\u751f\u4e86\u5316\u5408\u726912\uff0c\u5e76\u901a\u8fc7X\u5c04\u7ebf\u5355\u6676\u884d\u5c04\u786e\u5b9a\u5176\u4e3a\u03b73-\u70ef\u9187\u82ef\u6c27\u57fa\u954d\u7edc\u5408\u7269\uff08Scheme 3\uff09\u3002\u503c\u5f97\u6ce8\u610f\u7684\u662f\uff0c\u914d\u5408\u726912\u4e0eDFT\u8ba1\u7b97\u4e2d\u78b3\u2212\u6c27\u952e\u65ad\u88c2\u540e\u7684\u7a33\u5b9a\u4e2d\u95f4\u4f53Int-5c\u6709\u7740\u76f8\u540c\u6784\u9020\uff0c\u4e14\u751f\u621012\u7684\u53cd\u5e94\u5728\u5ba4\u6e29\u6761\u4ef6\u4e0b\u4ec5\u97005\u5206\u949f\u4fbf\u80fd\u5b8c\u6210\uff0c\u8fd9\u4e5f\u7b26\u5408DFT\u8ba1\u7b97\u7ed3\u679c\u4e2dInt-4\u5230TS-2\u4ec5\u670913.2 kcal\/mol\u80fd\u5792\u7684\u7ed3\u8bba\uff0c\u8fdb\u4e00\u6b65\u9a8c\u8bc1\u4e86\u673a\u7406\u7684\u5408\u7406\u6027\u3002 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