{"id":51867,"date":"2024-12-10T08:22:55","date_gmt":"2024-12-10T00:22:55","guid":{"rendered":"\/\/www.gsbet888.com\/?p=51867"},"modified":"2024-12-10T08:24:07","modified_gmt":"2024-12-10T00:24:07","slug":"jacs%ef%bc%9an-%e7%94%b2%e5%9f%ba%e4%b8%89%e7%ba%a7%e8%83%ba%e4%b8%ad%e4%b8%80%e7%ba%a7csp3%e2%88%92h%e9%94%ae%e7%9a%84%e5%af%b9%e6%98%a0%e9%80%89%e6%8b%a9%e6%80%a7%e7%83%b7%e5%9f%ba%e5%8c%96","status":"publish","type":"post","link":"\/\/www.gsbet888.com\/%e5%8c%96%e5%ad%a6%e6%9d%82%e8%ae%b0\/recentpaper\/2024\/12\/jacs%ef%bc%9an-%e7%94%b2%e5%9f%ba%e4%b8%89%e7%ba%a7%e8%83%ba%e4%b8%ad%e4%b8%80%e7%ba%a7csp3%e2%88%92h%e9%94%ae%e7%9a%84%e5%af%b9%e6%98%a0%e9%80%89%e6%8b%a9%e6%80%a7%e7%83%b7%e5%9f%ba%e5%8c%96.html","title":{"rendered":"JACS\uff1aN-\u7532\u57fa\u4e09\u7ea7\u80fa\u4e2d\u4e00\u7ea7C(sp3)\u2212H\u952e\u7684\u5bf9\u6620\u9009\u62e9\u6027\u70f7\u57fa\u5316\u53cd\u5e94"},"content":{"rendered":"

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

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

\u8fd1\u65e5\uff0c\u540c\u6d4e\u5927\u5b66\u7684\u8d75\u6653\u660e\u7b49\u8bfe\u9898\u7ec4\u5728J. Am. Chem. Soc.<\/em>\u4e2d\u53d1\u8868\u8bba\u6587\uff0c\u62a5\u9053\u4e00\u79cd\u8f74\u624b\u6027\u03b2<\/em>-\u82b3\u57fa\u94f1\u535f\u5549\u914d\u5408\u7269\u50ac\u5316N<\/em>-\u7532\u57fa\u4e09\u7ea7\u80fa\u4e2d\u4e00\u7ea7C(sp<\/em>3<\/sup>)\u2212H\u952e\u4e0e\u91cd\u6c2e\u5316\u5408\u7269\u7684\u5bf9\u6620\u9009\u62e9\u6027\u70f7\u57fa\u5316\u53cd\u5e94\uff0c\u5408\u6210\u4e86\u4e00\u7cfb\u5217\u03b2<\/em>-\u624b\u6027\u4e09\u7ea7\u80fa\uff0c\u5177\u6709\u4f18\u5f02\u7684\u5bf9\u6620\u9009\u62e9\u6027\u3002\u503c\u5f97\u6ce8\u610f\u7684\u662f\uff0c\u8be5\u7b56\u7565\u6210\u529f\u5e94\u7528\u4e8e\u624b\u6027\u8377\u5305\u7261\u4e39\u78b1(bicuculline)\u7684\u540e\u671f\u4fee\u9970\uff0c\u5177\u6709\u9ad8\u5ea6\u7684\u975e\u5bf9\u6620\u9009\u62e9\u6027\u3002\u6b64\u5916\uff0c\u901a\u8fc7\u6c18\u4ee3\u5b9e\u9a8c\u4e0eHRMS\u5206\u6790\u9274\u5b9a\u7684\u9633\u79bb\u5b50\u94f1\u914d\u5408\u7269\uff0c\u5e76\u63d0\u51fa\u4e86\u4e00\u79cd\u5408\u7406\u7684\u53cd\u5e94\u673a\u7406\u3002<\/p>\n

Enantioselective Alkylation of Primary C(sp<\/em>3<\/sup>)\u2212H Bonds in N<\/em>\u2011<\/strong>Methyl Tertiary Amine Enabled by Iridium Complex of Axially Chiral \u03b2<\/em><\/strong>\u2011<\/strong>Aryl Porphyrins<\/p>\n

S. Yuan, S. Li, X. Zhao, Y. Lin, S. Zheng, J. Am. Chem. Soc.<\/em> 2024<\/strong>, ASAP. doi: 10.1021\/jacs.4c12449<\/a>.<\/u><\/p><\/blockquote>\n

\"\"<\/p>\n

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

\u4e09\u7ea7\u80fa\u5e7f\u6cdb\u5b58\u5728\u4e8e\u5404\u7c7b\u836f\u7269\u3001\u751f\u7269\u78b1\u5929\u7136\u4ea7\u7269\u3001\u529f\u80fd\u6750\u6599\u3001\u914d\u4f53\u4e0e\u50ac\u5316\u5242\u7b49\u4e2d\u3002\u5176\u4e2d\uff0c\u80fa\u7c7b\u5316\u5408\u7269\u7684\u76f4\u63a5C-H\u5b98\u80fd\u56e2\u5316\u662f\u5408\u6210\u4e09\u7ea7\u80fa\u7684\u4e00\u79cd\u6709\u6548\u7684\u65b9\u6cd5\u3002\u8fc4\u4eca\u4e3a\u6b62\uff0c\u4e09\u7ea7\u80fa\u7684\u76f4\u63a5\u03b1<\/em>-\u70f7\u57fa\u5316\u7ecf\u5386\u4e86\u5feb\u901f\u589e\u957f[1]<\/sup>\u3002\u5728\u8fd9\u4e9b\u65b9\u6cd5\u4e2d\uff0c\u91d1\u5c5e\u50ac\u5316\u4e09\u7ea7\u80fa\u4e2dC(sp<\/em>3<\/sup>)\u2212H\u952e\u4e0e\u5361\u5bbe\u524d\u4f53\u7684\u70f7\u57fa\u5316\u5907\u53d7\u5173\u6ce8[2]<\/sup>\uff0c\u7279\u522b\u662f\u5728\u4e0d\u5bf9\u79f0\u5408\u6210\u4e2d\u7684\u5e94\u7528\u3002\u7136\u800c\uff0c\u6b64\u7c7b\u53cd\u5e94\u4ecd\u7136\u5b58\u5728\u4e24\u4e2a\u4e3b\u8981\u6311\u6218(Scheme 1a)\uff1a1)\u901a\u8fc7\u80fa\u5bf9\u5361\u5bbe\u4e2d\u5fc3\u7684\u4eb2\u6838\u653b\u51fb\u5f62\u6210N<\/em>-\u53f6\u7acb\u5fb7\u7684\u7ade\u4e89\u53cd\u5e94\u53ef\u80fd\u4f1a\u8fdb\u884c\uff0c\u7279\u522b\u662f\u5bf9\u4e8e\u8102\u80aa\u65cf\u4e09\u7ea7\u80fa\uff0c\u8fd9\u4f7f\u5f97C-H\u6d3b\u5316\u96be\u4ee5\u5b9e\u73b0\uff1b2)\u4e0d\u540c\u7c7b\u578b\u7684C-H\u952e\uff0c\u5982\u4e00\u7ea7\u3001\u4e8c\u7ea7C(sp<\/em>3<\/sup>)\u2212H\u952e\u6216C(sp<\/em>2<\/sup>)\u2212H\u952e\uff0c\u53ef\u80fd\u4f1a\u9020\u6210\u9009\u62e9\u6027\u95ee\u9898\u3002\u4e3a\u4e86\u5e94\u5bf9\u8fd9\u4e9b\u6311\u6218\uff0c\u5f00\u53d1\u80fd\u591f\u5fae\u5999\u5730\u533a\u5206\u4e0d\u540c\u7c7b\u578bC-H\u952e\u4e4b\u95f4\u80fd\u969c\u7684\u65b0\u578b\u50ac\u5316\u5242\u662f\u975e\u5e38\u53ef\u53d6\u7684\u3002<\/p>\n

1999\u5e74\uff0cDavies\u4e0eWinkler\u8bfe\u9898\u7ec4\u5206\u522b\u62a5\u9053\u4e86\u5728\u4e8c\u94d1\u914d\u5408\u7269\u5b58\u5728\u4e0b\uff0c\u73af\u80fa\u4e0e\u5361\u5bbe\u7684\u4e0d\u5bf9\u79f0C-H\u5b98\u80fd\u56e2\u5316\u53cd\u5e94\u3002\u5728\u4ed6\u4eec\u7684\u5f00\u521b\u6027\u7814\u7a76\u4e2d\uff0c\u5fc5\u987b\u4f7f\u7528N<\/em>-Boc\u4fdd\u62a4\u7b56\u7565\u4f7f\u4e24\u79cd\u80fa\u5931\u6d3b\uff0c\u4ee5\u5e94\u5bf9\u53f6\u7acb\u5fb7\u5f62\u6210\u7684\u6311\u6218\u30022002\u5e74\uff0cDavies\u8bfe\u9898\u7ec4[3]<\/sup>\u53d1\u73b0\uff0c\u5373\u4f7f\u5728\u7535\u5b50\u4e0a\u66f4\u6709\u5229\u7684\u70ef\u4e19\u57fa\u4f4d\u70b9\u4e0a(R1<\/sup> = allyl, Scheme 1b)\uff0c\u7a7a\u95f4\u8981\u6c42\u9ad8\u7684\u4e8c\u94d1\u914d\u5408\u7269\u4e5f\u4f1a\u5bfc\u81f4N<\/em>-Me C-H\u63d2\u5165\u9009\u62e9\u6027\u3002\u7136\u800c\uff0cN<\/em>-Boc\u4fdd\u62a4\u7b56\u7565\u4ecd\u7136\u662f\u5fc5\u8981\u7684\uff0c\u5e76\u4e14\u4e0d\u540c\u7684\u53d6\u4ee3\u4e25\u91cd\u5f71\u54cd\u53cd\u5e94\u7684\u5bf9\u6620\u9009\u62e9\u6027\u3002\u6b64\u5916\uff0c\u80fa\u4e2d\u6c2e\u4e0a\u7684\u03b1<\/em>-\u4f4d\u82b3\u57fa\u4e5f\u53ef\u7528\u4e8eN<\/em>-\u5931\u6d3b\uff0c\u4f34\u968f\u7740\u7ade\u4e89\u6027\u7684C(sp<\/em>2<\/sup>)\u2212H\u952e\u6d3b\u5316\uff0c\u8fd9\u9700\u8981\u4f7f\u7528\u9644\u8fd1\u7684\u4fdd\u62a4\u57fa\u56e2\u6216\u5927\u4f53\u79ef\u57fa\u56e2\u6765\u907f\u514d\u4e0d\u5fc5\u8981\u7684\u53cd\u5e94(Scheme 1c)\u3002\u6700\u8fd1\uff0c\u8d75\u6653\u660e\u8bfe\u9898\u7ec4[4]<\/sup>\u62a5\u9053\u4e86\u4e00\u79cd\u65b0\u8bbe\u8ba1\u7684C<\/em>4<\/sub>-\u5bf9\u79f0\u03b2<\/em>-\u8f74\u5411\u624b\u6027\u535f\u5549(Por*)\uff0c\u5e76\u6210\u529f\u5e94\u7528\u4e8e\u94f1\u50ac\u53161,4-\u5df1\u4e8c\u70ef\u7684C-H\u70f7\u57fa\u5316\u53cd\u5e94\u4e2d\u3002\u8fd1\u65e5\uff0c\u540c\u6d4e\u5927\u5b66\u7684\u8d75\u6653\u660e\u7b49\u8bfe\u9898\u7ec4\u62a5\u9053\u4e00\u79cd\u03b2<\/em>-\u8f74\u624b\u6027\u94f1\u535f\u5549\u914d\u5408\u7269\u50ac\u5316N<\/em>-\u7532\u57fa\u4e09\u7ea7\u80fa\u4e2d\u4e00\u7ea7C(sp<\/em>3<\/sup>)\u2212H\u952e\u4e0e\u91cd\u6c2e\u5316\u5408\u7269\u7684\u9ad8\u5ea6\u4f4d\u70b9\u9009\u62e9\u6027\u4e0e\u5bf9\u6620\u9009\u62e9\u6027\u70f7\u57fa\u5316\u53cd\u5e94\uff0c\u5408\u6210\u4e86\u4e00\u7cfb\u5217\u03b2<\/em>-\u624b\u6027\u4e09\u7ea7\u80fa(Scheme 1d)\u3002\"\"<\/p>\n

\u9996\u5148\uff0c\u4f5c\u8005\u91c7\u7528\u91cd\u6c2e\u4e59\u9178\u916f\u884d\u751f\u72691a<\/strong>\u4e0eN<\/em>,N<\/em>-\u4e8c\u7532\u57fa\u82ef\u80fa2a<\/strong>\u4f5c\u4e3a\u6a21\u578b\u5e95\u7269\uff0c\u8fdb\u884c\u76f8\u5173\u53cd\u5e94\u6761\u4ef6\u7684\u4f18\u5316\u7b5b\u9009 (Table 1)\u3002\u8fdb\u800c\u786e\u5b9a\u6700\u4f73\u7684\u53cd\u5e94\u6761\u4ef6\u4e3a\uff1a\u91c7\u75281aa<\/strong>\u4f5c\u4e3a\u5e95\u7269\uff0c4e<\/strong>\u4f5c\u4e3a\u50ac\u5316\u5242\uff0c5\u00c5 MS\u4f5c\u4e3a\u6dfb\u52a0\u5242\uff0c\u5728DCM\u53cd\u5e94\u6eb6\u5242\u4e2d\uff0c\u53cd\u5e94\u6e29\u5ea6\u4e3a\u5ba4\u6e29\uff0c\u6700\u7ec8\u83b7\u5f9792%\u6536\u7387\u7684\u4ea7\u72693aaa<\/strong>(94% ee<\/em>)\u3002\u5176\u4e2d\uff0c\u4f7f\u7528\u8f74\u5411\u624b\u6027\u94f1\u535f\u5549Ir(Por*)(CO)(Cl)\u53ef\u4ee5\u6709\u6548\u5730\u63a7\u5236\u4f4d\u70b9\u9009\u62e9\u6027\u4e0e\u5bf9\u6620\u4f53\u9009\u62e9\u6027\u3002\u5f53\u4f7f\u7528\u5176\u4ed6\u91cd\u6c2e\u4e59\u9178\u916f1ab<\/strong>–1ad<\/strong>\u65f6\uff0c\u5bf9\u6620\u9009\u62e9\u6027\u6025\u5267\u4e0b\u964d\u3002\"\"<\/p>\n

\u5728\u4e0a\u8ff0\u7684\u6700\u4f73\u53cd\u5e94\u6761\u4ef6\u4e0b\uff0c\u4f5c\u8005\u5bf9\u4e00\u7cfb\u5217\u91cd\u6c2e\u5e95\u7269(1<\/strong>)\u7684\u5e94\u7528\u8303\u56f4\u8fdb\u884c\u6df1\u5165\u7814\u7a76(Scheme 2)\u3002\u7814\u7a76\u7ed3\u679c\u8868\u660e\uff0c\u5f53\u91cd\u6c2e\u5e95\u7269\u4e2d\u542b\u6709\u4e0d\u540c\u7535\u6027\u53d6\u4ee3\u7684\u82b3\u57fa\u65f6\uff0c\u5747\u53ef\u987a\u5229\u8fdb\u884c\u53cd\u5e94\uff0c\u83b7\u5f97\u76f8\u5e94\u7684\u4ea7\u72693ab<\/strong>–3at<\/strong>\uff0c\u6536\u7387\u4e3a87-99%\uff0cee\u4e3a87-95%\u3002\u503c\u5f97\u6ce8\u610f\u7684\u662f\uff0c\u4e00\u7cfb\u5217\u6d3b\u6027\u7684\u57fa\u56e2\uff0c\u5982\u5364\u7d20\u3001\u70f7\u6c27\u7fb0\u57fa\u3001\u787c\u57fa\u3001\u7094\u57fa\u7b49\uff0c\u5747\u4e0e\u4f53\u7cfb\u517c\u5bb9\u3002\u540c\u65f6\uff0c\u542b\u6709\u82b4\u57fa\u4e0e\u6742\u73af\u53d6\u4ee3\u7684\u91cd\u6c2e\u916f\uff0c\u4e5f\u662f\u5408\u9002\u7684\u5e95\u7269\uff0c\u83b7\u5f97\u76f8\u5e94\u7684\u4ea7\u72693au<\/strong>–3ay<\/strong>\uff0c\u6536\u7387\u4e3a87-96%\uff0cee\u4e3a90-95%\u3002\"\"<\/p>\n

\u968f\u540e\uff0c\u4f5c\u8005\u5bf9N<\/em>-\u7532\u57fa\u4e09\u7ea7\u80fa(2<\/strong>)\u7684\u5e94\u7528\u8303\u56f4\u8fdb\u884c\u6df1\u5165\u7814\u7a76(Scheme 3)\u3002\u9996\u5148\uff0c\u5f53\u5e95\u7269N<\/em>,N<\/em>-\u4e8c\u7532\u57fa\u82ef\u80fa\u7684\u82b3\u57fa\u4e0a\u542b\u6709\u4e0d\u540c\u7535\u6027\u53d6\u4ee3\u57fa\u65f6\uff0c\u5747\u53ef\u987a\u5229\u8fdb\u884c\u53cd\u5e94\uff0c\u83b7\u5f97\u76f8\u5e94\u7684\u4ea7\u72693ba<\/strong>–3bk<\/strong>\uff0c\u6536\u7387\u4e3a60-98%\uff0cee\u4e3a87-95%\u3002\u5176\u6b21\uff0c\u975e\u5bf9\u79f0\u7684N<\/em>-\u7532\u57fa-N<\/em>-\u70f7\u57fa\u82b3\u57fa\u80fa\uff0c\u4e5f\u662f\u5408\u9002\u7684\u5e95\u7269\uff0c\u83b7\u5f97\u76f8\u5e94\u7684\u4ea7\u72693bl<\/strong>–3bn<\/strong>\uff0c\u6536\u7387\u4e3a85-90%\uff0cee\u4e3a95-96%\uff0c\u5177\u6709\u4f18\u5f02\u7684\u5bf9\u6620\u9009\u62e9\u6027\u3002\u503c\u5f97\u6ce8\u610f\u7684\u662f\uff0c\u5bf9\u4e8e\u6d3b\u6027\u7684\u4e8c\u7ea7\u82c4\u57fa\u6216\u70ef\u4e19\u57faC(sp<\/em>3<\/sup>)\u2212H\u952e\u5728\u53cd\u5e94\u4e2d\u662f\u60f0\u6027\u7684\uff0c\u800c\u4e00\u7ea7C(sp<\/em>3<\/sup>)\u2212H\u5bf9C(sp<\/em>2<\/sup>)\u2212H\u70f7\u57fa\u5316\u4ea7\u7269\u7684\u9009\u62e9\u6027\u4e3a10\/1(3bl<\/strong>\/3bl<\/strong>\u2032\u22123bn<\/strong>\/3bn<\/strong>\u2032)\u3002\u8fd9\u79cd\u7279\u6b8a\u7684\u9009\u62e9\u6027\u8868\u73b0\u51fa\u7a7a\u95f4\u8981\u6c42\u9ad8\u7684\u8f74\u624b\u6027\u94f1\u535f\u5549\u7684\u4f18\u70b9\u3002\u6b64\u5916\uff0cN<\/em>-\u7532\u57fa\u56db\u6c22\u55b9\u5549\u3001\u5432\u54da\u5549\u884d\u751f\u7269\u4e0eN<\/em>-\u7532\u57fa\u6742\u82b3\u80fa\uff0c\u4e5f\u53ef\u987a\u5229\u8fdb\u884c\u53cd\u5e94\uff0c\u83b7\u5f97\u76f8\u5e94\u7684\u4ea7\u72693bo<\/strong>–3br<\/strong>\uff0c\u6536\u7387\u4e3a70-94%\uff0cee\u4e3a88-96%\u3002N<\/em>-\u7532\u57fa\u70f7\u57fa\u4e09\u7ea7\u80fa\u5e95\u7269\uff0c\u4e5f\u662f\u5408\u9002\u7684\u5e95\u7269\uff0c\u83b7\u5f97\u76f8\u5e94\u7684\u4ea7\u72693bs-3bu<\/strong>\uff0c\u6536\u7387\u4e3a60-94%\uff0cee\u4e3a93-98%\u3002\"\"<\/p>\n

\u6b64\u5916\uff0c\u8be5\u7b56\u7565\u8fd8\u53ef\u7528\u4e8eN<\/em>-\u7532\u57fa\u751f\u7269\u78b1\u5929\u7136\u4ea7\u7269\u7684\u540e\u4fee\u9970\uff0c\u5982\u8377\u5305\u7261\u4e39\u78b1(Scheme 4)\u3002\u5f53\u4f7f\u7528\u5916\u6d88\u65cb\u94f1\u535f\u5549\u50ac\u5316\u5242\u65f6\uff0c\u53cd\u5e94\u8fdb\u884c\u987a\u5229\uff0c\u5f97\u52303bv<\/strong>\u4e0e3bw<\/strong>\u7684\u975e\u5bf9\u6620\u4f53\u6df7\u5408\u7269\uff0c\u603b\u6536\u7387\u4e3a76%\uff0cdr\u4e3a2\/1\u3002\u5728\u624b\u6027\u50ac\u5316\u52424e<\/strong>\u7684\u5b58\u5728\u4e0b\uff0c\u53ef\u4ee577%\u7684\u6536\u7387\u5f97\u5230\u4ea7\u72693bv<\/strong>\uff0c\u5177\u6709\u9ad8\u5ea6\u7684\u975e\u5bf9\u6620\u9009\u62e9\u6027(dr > 20\/1)\u3002\u76f8\u6bd4\u4e4b\u4e0b\uff0c\u5f53\u4f7f\u7528\u50ac\u5316\u52424e<\/strong>(ent<\/em>–4e<\/strong>)\u7684\u5bf9\u6620\u5f02\u6784\u4f53\u65f6\uff0c\u53ef\u4ee576%\u7684\u6536\u7387\u5f97\u5230\u4ea7\u72693bw<\/strong>\uff0c\u5177\u6709\u540c\u6837\u9ad8\u5ea6\u7684\u975e\u5bf9\u6620\u9009\u62e9\u6027\u3002\"\"<\/p>\n

\u540c\u65f6\uff0c1aa<\/strong>\u4e0e2d<\/strong>\u7684\u514b\u7ea7\u89c4\u6a21\u5b9e\u9a8c\uff0c\u540c\u6837\u53ef\u4ee590%\u7684\u6536\u7387\u5f97\u5230\u4ea7\u72693bd<\/strong>\uff0cee\u4e3a95% (Scheme 5a)\u3002\u5e76\u4e14\uff0c3bd<\/strong>\u901a\u8fc7\u8fdb\u4e00\u6b65\u7684\u8fd8\u539f\uff0c\u53ef\u4ee595%\u7684\u6536\u7387\u5f97\u5230\u76f8\u5e94\u7684\u6c28\u57fa\u9187\u5316\u5408\u72696<\/strong>\uff0cee\u4e3a95%\u3002\u5316\u5408\u72696<\/strong>\u901a\u8fc7\u8fdb\u4e00\u6b65\u7684\u884d\u751f\u5316\uff0c\u53ef\u83b7\u5f97\u5177\u6709\u4ef7\u503c\u7684\u624b\u60271,3-oxazinanes(7<\/strong>)\uff0c\u6536\u7387\u4e3a95%\uff0cee\u4e3a94% (Scheme 5b)\u3002\"\"<\/p>\n

\u63a5\u4e0b\u6765\uff0c\u4f5c\u8005\u5bf9\u4e0a\u8ff0\u5bf9\u6620\u9009\u62e9\u6027\u70f7\u57fa\u5316\u8fc7\u7a0b\u7684\u53cd\u5e94\u673a\u7406\u8fdb\u884c\u8fdb\u4e00\u6b65\u7814\u7a76 (Scheme 6)\u3002\u6c18\u4ee3\u5b9e\u9a8c\u7ed3\u679c\u8868\u660e\uff0c\u5361\u5bbe\u63d2\u5165C(sp<\/em>3<\/sup>)\u2212H\u952e\u53ef\u80fd\u662f\u4e00\u4e2a\u534f\u540c\u8fc7\u7a0b(Scheme 6a\u4e0eScheme 6b)\u3002KIE\u5b9e\u9a8c\u7ed3\u679c\u8868\u660e\uff0cC(sp<\/em>3<\/sup>)\u2212H\u6d3b\u5316\u662f\u53cd\u5e94\u7684\u901f\u7387\u51b3\u5b9a\u6b65\u9aa4(Scheme 6c)\u3002HRMS\u5206\u6790\u8868\u660e\uff0c\u53cd\u5e94\u5f62\u6210\u4e86\u4e00\u79cd\u65b0\u578b\u7684\u94f1\u535f\u5549\u914d\u5408\u7269(4e\u2032<\/strong>)\uff0c\u5176\u662f\u4e00\u79cd\u9633\u79bb\u5b50\u94f1\u914d\u5408\u7269\uff0c\u4e5f\u662f\u5b9e\u9645\u7684\u50ac\u5316\u5242(Scheme 6d)\u3002\"\"<\/p>\n

\u57fa\u4e8e\u4e0a\u8ff0\u7684\u5b9e\u9a8c\u7814\u7a76\u4ee5\u53ca\u524d\u671f\u76f8\u5173\u7684\u6587\u732e\u62a5\u9053[1]<\/sup>\uff0c\u4f5c\u8005\u63d0\u51fa\u5982\u4e0b\u5408\u7406\u7684\u53cd\u5e94\u673a\u7406 (Scheme 7)\u3002\u9996\u5148\uff0c\u91cd\u6c2e\u4e59\u9178\u916f1<\/strong>\u4e0e\u9884\u50ac\u5316\u5242Ir(Por*)(CO)(Cl) 4<\/strong>\/5<\/strong>\u4e2d\u7684Cl\u914d\u4f53\u4e4b\u95f4\u53d1\u751f\u914d\u4f53\u4ea4\u6362\uff0c\u901a\u8fc7N2<\/sub>\u7684\u91ca\u653e\uff0c\u751f\u6210\u94f1\u5361\u5bbe\u4e2d\u95f4\u4f53Int A<\/strong>\u3002\u5176\u6b21\uff0c\u5728\u5f62\u6210\u7684\u5361\u5bbe\u4e2d\u95f4\u4f53\u7684\u60c5\u51b5\u4e0b\uff0c\u03b1<\/em>-N\u4e00\u7ea7C-H\u53d1\u751f\u6d3b\u5316\uff0c\u751f\u6210\u8fc7\u6e21\u6001Int B<\/strong>\u3002\u6700\u540e\uff0c\u4ece\u03b1<\/em>-N\u4e00\u7ea7C-H\u952e\u5230\u624b\u6027\u4e2d\u5fc3\u7684\u534f\u540c\u6c22\u8f6c\u79fb\uff0c\u4ee5\u53ca\u9633\u79bb\u5b50\u94f1\u50ac\u5316\u5242\u7684\u5206\u79bb\uff0c\u4ece\u800c\u751f\u6210\u76ee\u6807\u7684\u624b\u6027\u4e09\u7ea7\u80fa\u4ea7\u72693<\/strong>\uff0c\u5e76\u5b8c\u6210\u50ac\u5316\u5faa\u73af\u7684\u8fc7\u7a0b\u3002\"\"<\/p>\n

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

\u540c\u6d4e\u5927\u5b66\u7684\u8d75\u6653\u660e\u7b49\u8bfe\u9898\u7ec4\u62a5\u9053\u4e00\u79cd\u8f74\u624b\u6027\u94f1\u535f\u5549\u914d\u5408\u7269\u50ac\u5316N<\/em>-\u7532\u57fa\u4e09\u7ea7\u80fa\u4e2d\u4e00\u7ea7C(sp<\/em>3<\/sup>)\u2212H\u952e\u4e0e\u91cd\u6c2e\u5316\u5408\u7269\u7684\u9ad8\u5ea6\u4f4d\u70b9\u9009\u62e9\u6027\u4e0e\u5bf9\u6620\u9009\u62e9\u6027\u70f7\u57fa\u5316\u53cd\u5e94\uff0c\u5408\u6210\u4e86\u4e00\u7cfb\u5217\u03b2<\/em>-\u624b\u6027\u4e09\u7ea7\u80fa\u3002\u540c\u65f6\uff0c\u8be5\u7b56\u7565\u5177\u6709\u6536\u7387\u9ad8\u3001\u5e95\u7269\u8303\u56f4\u5e7f\u6cdb\u3001\u4f18\u826f\u7684\u5b98\u80fd\u56e2\u517c\u5bb9\u6027\u4ee5\u53ca\u4f18\u826f\u7684\u5bf9\u6620\u9009\u62e9\u6027\u7b49\u4f18\u52bf\u3002\u5176\u6b21\uff0c\u901a\u8fc7\u5bf9\u624b\u6027\u8377\u5305\u7261\u4e39\u78b1\u7684\u540e\u671f\u4fee\u9970\uff0c\u8fdb\u4e00\u6b65\u8bc1\u660e\u4e86\u53cd\u5e94\u7684\u5b9e\u7528\u6027\u3002<\/p>\n

\u53c2\u8003\u6587\u732e\uff1a<\/strong><\/h4>\n[1] J. Zhang, C. Liu, J. Wu, X. Tan, W. Wu, H. Jiang, Org. Lett. <\/em>2024<\/strong>, 26<\/em>, 4422. doi:10.1021\/acs.orglett.4c00880<\/a>.<\/p>\n[2] H. M. L. Davies, R. E. J. Beckwith, Chem. Rev. <\/em>2003<\/strong>, 103<\/em>, 2861. doi:10.1021\/cr0200217<\/a>.<\/p>\n[3] H. M. L. Davies, C. Venkataramani, Angew. Chem., Int. Ed. <\/em>2002<\/strong>, 41<\/em>, 2197. doi:10.1002\/1521-3773(20020617)41:12<2197::AID-ANIE2197>3.0.CO;2-N<\/a>.<\/p>\n[4] S. Yuan, J. Sun, X. Zhao, J. Zhu, S. Zheng, Angew. Chem., Int. Ed. <\/em>2024<\/strong>, 63<\/em>, No. e202404329. doi:10.1002\/anie.202404329<\/a>.<\/p>\n

\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

\u5173\u6ce8Chem-Station\u6296\u97f3\u53f7\uff1a79473891841<\/p>\n

\u8bf7\u767b\u9646TCI\u8bd5\u5242\u5b98\u7f51\u67e5\u770b\u66f4\u591a\u5185\u5bb9<\/h5>\n
https:\/\/www.tcichemicals.com\/CN\/zh\/<\/h5>\n","protected":false},"excerpt":{"rendered":"\u4f5c\u8005\uff1a\u6749\u6749 \u5bfc\u8bfb\uff1a \u8fd1\u65e5\uff0c\u540c\u6d4e\u5927\u5b66\u7684\u8d75\u6653\u660e\u7b49\u8bfe\u9898\u7ec4\u5728J. Am. Chem. Soc.\u4e2d\u53d1\u8868\u8bba\u6587\uff0c\u62a5\u9053\u4e00\u79cd\u8f74\u624b\u6027\u03b2-\u82b3\u57fa\u94f1\u535f\u5549\u914d\u5408\u7269\u50ac\u5316N-\u7532\u57fa\u4e09\u7ea7\u80fa\u4e2d\u4e00\u7ea7C(sp3)\u2212H\u952e\u4e0e\u91cd\u6c2e\u5316\u5408\u7269\u7684\u5bf9\u6620\u9009\u62e9\u6027\u70f7\u57fa\u5316\u53cd\u5e94\uff0c\u5408\u6210\u4e86\u4e00\u7cfb\u5217\u03b2-\u624b\u6027\u4e09\u7ea7\u80fa\uff0c\u5177\u6709\u4f18\u5f02\u7684\u5bf9\u6620\u9009\u62e9\u6027\u3002\u503c\u5f97\u6ce8\u610f\u7684\u662f\uff0c\u8be5\u7b56\u7565\u6210\u529f\u5e94\u7528\u4e8e\u624b\u6027\u8377\u5305\u7261\u4e39\u78b1(bicuculline)\u7684\u540e\u671f\u4fee\u9970\uff0c\u5177\u6709\u9ad8\u5ea6\u7684\u975e\u5bf9\u6620\u9009\u62e9\u6027\u3002\u6b64\u5916\uff0c\u901a\u8fc7\u6c18\u4ee3\u5b9e\u9a8c\u4e0eHRMS\u5206\u6790\u9274\u5b9a\u7684\u9633\u79bb\u5b50\u94f1\u914d\u5408\u7269\uff0c\u5e76\u63d0\u51fa\u4e86\u4e00\u79cd\u5408\u7406\u7684\u53cd\u5e94\u673a\u7406\u3002 Enantioselective Alkylation of Primary C(sp3)\u2212H Bonds in N\u2011Methyl Tertiary Amine Enabled by Iridium Complex of Axially Chiral \u03b2\u2011Aryl Porphyrins S. Yuan, S. Li, X. Zhao, Y. Lin, S. Zheng, J. Am. Chem. Soc. 2024, ASAP. doi: 10.1021\/jacs.4c12449. \u6b63\u6587\uff1a \u4e09\u7ea7\u80fa\u5e7f\u6cdb\u5b58\u5728\u4e8e\u5404\u7c7b\u836f\u7269\u3001\u751f\u7269\u78b1\u5929\u7136\u4ea7\u7269\u3001\u529f\u80fd\u6750\u6599\u3001\u914d\u4f53\u4e0e\u50ac\u5316\u5242\u7b49\u4e2d\u3002\u5176\u4e2d\uff0c\u80fa\u7c7b\u5316\u5408\u7269\u7684\u76f4\u63a5C-H\u5b98\u80fd\u56e2\u5316\u662f\u5408\u6210\u4e09\u7ea7\u80fa\u7684\u4e00\u79cd\u6709\u6548\u7684\u65b9\u6cd5\u3002\u8fc4\u4eca\u4e3a\u6b62\uff0c\u4e09\u7ea7\u80fa\u7684\u76f4\u63a5\u03b1-\u70f7\u57fa\u5316\u7ecf\u5386\u4e86\u5feb\u901f\u589e\u957f[1]\u3002\u5728\u8fd9\u4e9b\u65b9\u6cd5\u4e2d\uff0c\u91d1\u5c5e\u50ac\u5316\u4e09\u7ea7\u80fa\u4e2dC(sp3)\u2212H\u952e\u4e0e\u5361\u5bbe\u524d\u4f53\u7684\u70f7\u57fa\u5316\u5907\u53d7\u5173\u6ce8[2]\uff0c\u7279\u522b\u662f\u5728\u4e0d\u5bf9\u79f0\u5408\u6210\u4e2d\u7684\u5e94\u7528\u3002\u7136\u800c\uff0c\u6b64\u7c7b\u53cd\u5e94\u4ecd\u7136\u5b58\u5728\u4e24\u4e2a\u4e3b\u8981\u6311\u6218(Scheme 1a)\uff1a1)\u901a\u8fc7\u80fa\u5bf9\u5361\u5bbe\u4e2d\u5fc3\u7684\u4eb2\u6838\u653b\u51fb\u5f62\u6210N-\u53f6\u7acb\u5fb7\u7684\u7ade\u4e89\u53cd\u5e94\u53ef\u80fd\u4f1a\u8fdb\u884c\uff0c\u7279\u522b\u662f\u5bf9\u4e8e\u8102\u80aa\u65cf\u4e09\u7ea7\u80fa\uff0c\u8fd9\u4f7f\u5f97C-H\u6d3b\u5316\u96be\u4ee5\u5b9e\u73b0\uff1b2)\u4e0d\u540c\u7c7b\u578b\u7684C-H\u952e\uff0c\u5982\u4e00\u7ea7\u3001\u4e8c\u7ea7C(sp3)\u2212H\u952e\u6216C(sp2)\u2212H\u952e\uff0c\u53ef\u80fd\u4f1a\u9020\u6210\u9009\u62e9\u6027\u95ee\u9898\u3002\u4e3a\u4e86\u5e94\u5bf9\u8fd9\u4e9b\u6311\u6218\uff0c\u5f00\u53d1\u80fd\u591f\u5fae\u5999\u5730\u533a\u5206\u4e0d\u540c\u7c7b\u578bC-H\u952e\u4e4b\u95f4\u80fd\u969c\u7684\u65b0\u578b\u50ac\u5316\u5242\u662f\u975e\u5e38\u53ef\u53d6\u7684\u3002 1999\u5e74\uff0cDavies\u4e0eWinkler\u8bfe\u9898\u7ec4\u5206\u522b\u62a5\u9053\u4e86\u5728\u4e8c\u94d1\u914d\u5408\u7269\u5b58\u5728\u4e0b\uff0c\u73af\u80fa\u4e0e\u5361\u5bbe\u7684\u4e0d\u5bf9\u79f0C-H\u5b98\u80fd\u56e2\u5316\u53cd\u5e94\u3002\u5728\u4ed6\u4eec\u7684\u5f00\u521b\u6027\u7814\u7a76\u4e2d\uff0c\u5fc5\u987b\u4f7f\u7528N-Boc\u4fdd\u62a4\u7b56\u7565\u4f7f\u4e24\u79cd\u80fa\u5931\u6d3b\uff0c\u4ee5\u5e94\u5bf9\u53f6\u7acb\u5fb7\u5f62\u6210\u7684\u6311\u6218\u30022002\u5e74\uff0cDavies\u8bfe\u9898\u7ec4[3]\u53d1\u73b0\uff0c\u5373\u4f7f\u5728\u7535\u5b50\u4e0a\u66f4\u6709\u5229\u7684\u70ef\u4e19\u57fa\u4f4d\u70b9\u4e0a(R1 = allyl, Scheme 1b)\uff0c\u7a7a\u95f4\u8981\u6c42\u9ad8\u7684\u4e8c\u94d1\u914d\u5408\u7269\u4e5f\u4f1a\u5bfc\u81f4N-Me C-H\u63d2\u5165\u9009\u62e9\u6027\u3002\u7136\u800c\uff0cN-Boc\u4fdd\u62a4\u7b56\u7565\u4ecd\u7136\u662f\u5fc5\u8981\u7684\uff0c\u5e76\u4e14\u4e0d\u540c\u7684\u53d6\u4ee3\u4e25\u91cd\u5f71\u54cd\u53cd\u5e94\u7684\u5bf9\u6620\u9009\u62e9\u6027\u3002\u6b64\u5916\uff0c\u80fa\u4e2d\u6c2e\u4e0a\u7684\u03b1-\u4f4d\u82b3\u57fa\u4e5f\u53ef\u7528\u4e8eN-\u5931\u6d3b\uff0c\u4f34\u968f\u7740\u7ade\u4e89\u6027\u7684C(sp2)\u2212H\u952e\u6d3b\u5316\uff0c\u8fd9\u9700\u8981\u4f7f\u7528\u9644\u8fd1\u7684\u4fdd\u62a4\u57fa\u56e2\u6216\u5927\u4f53\u79ef\u57fa\u56e2\u6765\u907f\u514d\u4e0d\u5fc5\u8981\u7684\u53cd\u5e94(Scheme 1c)\u3002\u6700\u8fd1\uff0c\u8d75\u6653\u660e\u8bfe\u9898\u7ec4[4]\u62a5\u9053\u4e86\u4e00\u79cd\u65b0\u8bbe\u8ba1\u7684C4-\u5bf9\u79f0\u03b2-\u8f74\u5411\u624b\u6027\u535f\u5549(Por*)\uff0c\u5e76\u6210\u529f\u5e94\u7528\u4e8e\u94f1\u50ac\u53161,4-\u5df1\u4e8c\u70ef\u7684C-H\u70f7\u57fa\u5316\u53cd\u5e94\u4e2d\u3002\u8fd1\u65e5\uff0c\u540c\u6d4e\u5927\u5b66\u7684\u8d75\u6653\u660e\u7b49\u8bfe\u9898\u7ec4\u62a5\u9053\u4e00\u79cd\u03b2-\u8f74\u624b\u6027\u94f1\u535f\u5549\u914d\u5408\u7269\u50ac\u5316N-\u7532\u57fa\u4e09\u7ea7\u80fa\u4e2d\u4e00\u7ea7C(sp3)\u2212H\u952e\u4e0e\u91cd\u6c2e\u5316\u5408\u7269\u7684\u9ad8\u5ea6\u4f4d\u70b9\u9009\u62e9\u6027\u4e0e\u5bf9\u6620\u9009\u62e9\u6027\u70f7\u57fa\u5316\u53cd\u5e94\uff0c\u5408\u6210\u4e86\u4e00\u7cfb\u5217\u03b2-\u624b\u6027\u4e09\u7ea7\u80fa(Scheme 1d)\u3002 \u9996\u5148\uff0c\u4f5c\u8005\u91c7\u7528\u91cd\u6c2e\u4e59\u9178\u916f\u884d\u751f\u72691a\u4e0eN,N-\u4e8c\u7532\u57fa\u82ef\u80fa2a\u4f5c\u4e3a\u6a21\u578b\u5e95\u7269\uff0c\u8fdb\u884c\u76f8\u5173\u53cd\u5e94\u6761\u4ef6\u7684\u4f18\u5316\u7b5b\u9009 (Table 1)\u3002\u8fdb\u800c\u786e\u5b9a\u6700\u4f73\u7684\u53cd\u5e94\u6761\u4ef6\u4e3a\uff1a\u91c7\u75281aa\u4f5c\u4e3a\u5e95\u7269\uff0c4e\u4f5c\u4e3a\u50ac\u5316\u5242\uff0c5\u00c5 MS\u4f5c\u4e3a\u6dfb\u52a0\u5242\uff0c\u5728DCM\u53cd\u5e94\u6eb6\u5242\u4e2d\uff0c\u53cd\u5e94\u6e29\u5ea6\u4e3a\u5ba4\u6e29\uff0c\u6700\u7ec8\u83b7\u5f9792%\u6536\u7387\u7684\u4ea7\u72693aaa(94% ee)\u3002\u5176\u4e2d\uff0c\u4f7f\u7528\u8f74\u5411\u624b\u6027\u94f1\u535f\u5549Ir(Por*)(CO)(Cl)\u53ef\u4ee5\u6709\u6548\u5730\u63a7\u5236\u4f4d\u70b9\u9009\u62e9\u6027\u4e0e\u5bf9\u6620\u4f53\u9009\u62e9\u6027\u3002\u5f53\u4f7f\u7528\u5176\u4ed6\u91cd\u6c2e\u4e59\u9178\u916f1ab–1ad\u65f6\uff0c\u5bf9\u6620\u9009\u62e9\u6027\u6025\u5267\u4e0b\u964d\u3002 \u5728\u4e0a\u8ff0\u7684\u6700\u4f73\u53cd\u5e94\u6761\u4ef6\u4e0b\uff0c\u4f5c\u8005\u5bf9\u4e00\u7cfb\u5217\u91cd\u6c2e\u5e95\u7269(1)\u7684\u5e94\u7528\u8303\u56f4\u8fdb\u884c\u6df1\u5165\u7814\u7a76(Scheme 2)\u3002\u7814\u7a76\u7ed3\u679c\u8868\u660e\uff0c\u5f53\u91cd\u6c2e\u5e95\u7269\u4e2d\u542b\u6709\u4e0d\u540c\u7535\u6027\u53d6\u4ee3\u7684\u82b3\u57fa\u65f6\uff0c\u5747\u53ef\u987a\u5229\u8fdb\u884c\u53cd\u5e94\uff0c\u83b7\u5f97\u76f8\u5e94\u7684\u4ea7\u72693ab–3at\uff0c\u6536\u7387\u4e3a87-99%\uff0cee\u4e3a87-95%\u3002\u503c\u5f97\u6ce8\u610f\u7684\u662f\uff0c\u4e00\u7cfb\u5217\u6d3b\u6027\u7684\u57fa\u56e2\uff0c\u5982\u5364\u7d20\u3001\u70f7\u6c27\u7fb0\u57fa\u3001\u787c\u57fa\u3001\u7094\u57fa\u7b49\uff0c\u5747\u4e0e\u4f53\u7cfb\u517c\u5bb9\u3002\u540c\u65f6\uff0c\u542b\u6709\u82b4\u57fa\u4e0e\u6742\u73af\u53d6\u4ee3\u7684\u91cd\u6c2e\u916f\uff0c\u4e5f\u662f\u5408\u9002\u7684\u5e95\u7269\uff0c\u83b7\u5f97\u76f8\u5e94\u7684\u4ea7\u72693au–3ay\uff0c\u6536\u7387\u4e3a87-96%\uff0cee\u4e3a90-95%\u3002 \u968f\u540e\uff0c\u4f5c\u8005\u5bf9N-\u7532\u57fa\u4e09\u7ea7\u80fa(2)\u7684\u5e94\u7528\u8303\u56f4\u8fdb\u884c\u6df1\u5165\u7814\u7a76(Scheme 3)\u3002\u9996\u5148\uff0c\u5f53\u5e95\u7269N,N-\u4e8c\u7532\u57fa\u82ef\u80fa\u7684\u82b3\u57fa\u4e0a\u542b\u6709\u4e0d\u540c\u7535\u6027\u53d6\u4ee3\u57fa\u65f6\uff0c\u5747\u53ef\u987a\u5229\u8fdb\u884c\u53cd\u5e94\uff0c\u83b7\u5f97\u76f8\u5e94\u7684\u4ea7\u72693ba–3bk\uff0c\u6536\u7387\u4e3a60-98%\uff0cee\u4e3a87-95%\u3002\u5176\u6b21\uff0c\u975e\u5bf9\u79f0\u7684N-\u7532\u57fa-N-\u70f7\u57fa\u82b3\u57fa\u80fa\uff0c\u4e5f\u662f\u5408\u9002\u7684\u5e95\u7269\uff0c\u83b7\u5f97\u76f8\u5e94\u7684\u4ea7\u72693bl–3bn\uff0c\u6536\u7387\u4e3a85-90%\uff0cee\u4e3a95-96%\uff0c\u5177\u6709\u4f18\u5f02\u7684\u5bf9\u6620\u9009\u62e9\u6027\u3002\u503c\u5f97\u6ce8\u610f\u7684\u662f\uff0c\u5bf9\u4e8e\u6d3b\u6027\u7684\u4e8c\u7ea7\u82c4\u57fa\u6216\u70ef\u4e19\u57faC(sp3)\u2212H\u952e\u5728\u53cd\u5e94\u4e2d\u662f\u60f0\u6027\u7684\uff0c\u800c\u4e00\u7ea7C(sp3)\u2212H\u5bf9C(sp2)\u2212H\u70f7\u57fa\u5316\u4ea7\u7269\u7684\u9009\u62e9\u6027\u4e3a10\/1(3bl\/3bl\u2032\u22123bn\/3bn\u2032)\u3002\u8fd9\u79cd\u7279\u6b8a\u7684\u9009\u62e9\u6027\u8868\u73b0\u51fa\u7a7a\u95f4\u8981\u6c42\u9ad8\u7684\u8f74\u624b\u6027\u94f1\u535f\u5549\u7684\u4f18\u70b9\u3002\u6b64\u5916\uff0cN-\u7532\u57fa\u56db\u6c22\u55b9\u5549\u3001\u5432\u54da\u5549\u884d\u751f\u7269\u4e0eN-\u7532\u57fa\u6742\u82b3\u80fa\uff0c\u4e5f\u53ef\u987a\u5229\u8fdb\u884c\u53cd\u5e94\uff0c\u83b7\u5f97\u76f8\u5e94\u7684\u4ea7\u72693bo–3br\uff0c\u6536\u7387\u4e3a70-94%\uff0cee\u4e3a88-96%\u3002N-\u7532\u57fa\u70f7\u57fa\u4e09\u7ea7\u80fa\u5e95\u7269\uff0c\u4e5f\u662f\u5408\u9002\u7684\u5e95\u7269\uff0c\u83b7\u5f97\u76f8\u5e94\u7684\u4ea7\u72693bs-3bu\uff0c\u6536\u7387\u4e3a60-94%\uff0cee\u4e3a93-98%\u3002 \u6b64\u5916\uff0c\u8be5\u7b56\u7565\u8fd8\u53ef\u7528\u4e8eN-\u7532\u57fa\u751f\u7269\u78b1\u5929\u7136\u4ea7\u7269\u7684\u540e\u4fee\u9970\uff0c\u5982\u8377\u5305\u7261\u4e39\u78b1(Scheme 4)\u3002\u5f53\u4f7f\u7528\u5916\u6d88\u65cb\u94f1\u535f\u5549\u50ac\u5316\u5242\u65f6\uff0c\u53cd\u5e94\u8fdb\u884c\u987a\u5229\uff0c\u5f97\u52303bv\u4e0e3bw\u7684\u975e\u5bf9\u6620\u4f53\u6df7\u5408\u7269\uff0c\u603b\u6536\u7387\u4e3a76%\uff0cdr\u4e3a2\/1\u3002\u5728\u624b\u6027\u50ac\u5316\u52424e\u7684\u5b58\u5728\u4e0b\uff0c\u53ef\u4ee577%\u7684\u6536\u7387\u5f97\u5230\u4ea7\u72693bv\uff0c\u5177\u6709\u9ad8\u5ea6\u7684\u975e\u5bf9\u6620\u9009\u62e9\u6027(dr > 20\/1)\u3002\u76f8\u6bd4\u4e4b\u4e0b\uff0c\u5f53\u4f7f\u7528\u50ac\u5316\u52424e(ent–4e)\u7684\u5bf9\u6620\u5f02\u6784\u4f53\u65f6\uff0c\u53ef\u4ee576%\u7684\u6536\u7387\u5f97\u5230\u4ea7\u72693bw\uff0c\u5177\u6709\u540c\u6837\u9ad8\u5ea6\u7684\u975e\u5bf9\u6620\u9009\u62e9\u6027\u3002 \u540c\u65f6\uff0c1aa\u4e0e2d\u7684\u514b\u7ea7\u89c4\u6a21\u5b9e\u9a8c\uff0c\u540c\u6837\u53ef\u4ee590%\u7684\u6536\u7387\u5f97\u5230\u4ea7\u72693bd\uff0cee\u4e3a95% (Scheme 5a)\u3002\u5e76\u4e14\uff0c3bd\u901a\u8fc7\u8fdb\u4e00\u6b65\u7684\u8fd8\u539f\uff0c\u53ef\u4ee595%\u7684\u6536\u7387\u5f97\u5230\u76f8\u5e94\u7684\u6c28\u57fa\u9187\u5316\u5408\u72696\uff0cee\u4e3a95%\u3002\u5316\u5408\u72696\u901a\u8fc7\u8fdb\u4e00\u6b65\u7684\u884d\u751f\u5316\uff0c\u53ef\u83b7\u5f97\u5177\u6709\u4ef7\u503c\u7684\u624b\u60271,3-oxazinanes(7)\uff0c\u6536\u7387\u4e3a95%\uff0cee\u4e3a94% (Scheme 5b)\u3002 \u63a5\u4e0b\u6765\uff0c\u4f5c\u8005\u5bf9\u4e0a\u8ff0\u5bf9\u6620\u9009\u62e9\u6027\u70f7\u57fa\u5316\u8fc7\u7a0b\u7684\u53cd\u5e94\u673a\u7406\u8fdb\u884c\u8fdb\u4e00\u6b65\u7814\u7a76 (Scheme 6)\u3002\u6c18\u4ee3\u5b9e\u9a8c\u7ed3\u679c\u8868\u660e\uff0c\u5361\u5bbe\u63d2\u5165C(sp3)\u2212H\u952e\u53ef\u80fd\u662f\u4e00\u4e2a\u534f\u540c\u8fc7\u7a0b(Scheme 6a\u4e0eScheme 6b)\u3002KIE\u5b9e\u9a8c\u7ed3\u679c\u8868\u660e\uff0cC(sp3)\u2212H\u6d3b\u5316\u662f\u53cd\u5e94\u7684\u901f\u7387\u51b3\u5b9a\u6b65\u9aa4(Scheme 6c)\u3002HRMS\u5206\u6790\u8868\u660e\uff0c\u53cd\u5e94\u5f62\u6210\u4e86\u4e00\u79cd\u65b0\u578b\u7684\u94f1\u535f\u5549\u914d\u5408\u7269(4e\u2032)\uff0c\u5176\u662f\u4e00\u79cd\u9633\u79bb\u5b50\u94f1\u914d\u5408\u7269\uff0c\u4e5f\u662f\u5b9e\u9645\u7684\u50ac\u5316\u5242(Scheme 6d)\u3002 \u57fa\u4e8e\u4e0a\u8ff0\u7684\u5b9e\u9a8c\u7814\u7a76\u4ee5\u53ca\u524d\u671f\u76f8\u5173\u7684\u6587\u732e\u62a5\u9053[1]\uff0c\u4f5c\u8005\u63d0\u51fa\u5982\u4e0b\u5408\u7406\u7684\u53cd\u5e94\u673a\u7406 (Scheme 7)\u3002\u9996\u5148\uff0c\u91cd\u6c2e\u4e59\u9178\u916f1\u4e0e\u9884\u50ac\u5316\u5242Ir(Por*)(CO)(Cl) 4\/5\u4e2d\u7684Cl\u914d\u4f53\u4e4b\u95f4\u53d1\u751f\u914d\u4f53\u4ea4\u6362\uff0c\u901a\u8fc7N2\u7684\u91ca\u653e\uff0c\u751f\u6210\u94f1\u5361\u5bbe\u4e2d\u95f4\u4f53Int A\u3002\u5176\u6b21\uff0c\u5728\u5f62\u6210\u7684\u5361\u5bbe\u4e2d\u95f4\u4f53\u7684\u60c5\u51b5\u4e0b\uff0c\u03b1-N\u4e00\u7ea7C-H\u53d1\u751f\u6d3b\u5316\uff0c\u751f\u6210\u8fc7\u6e21\u6001Int B\u3002\u6700\u540e\uff0c\u4ece\u03b1-N\u4e00\u7ea7C-H\u952e\u5230\u624b\u6027\u4e2d\u5fc3\u7684\u534f\u540c\u6c22\u8f6c\u79fb\uff0c\u4ee5\u53ca\u9633\u79bb\u5b50\u94f1\u50ac\u5316\u5242\u7684\u5206\u79bb\uff0c\u4ece\u800c\u751f\u6210\u76ee\u6807\u7684\u624b\u6027\u4e09\u7ea7\u80fa\u4ea7\u72693\uff0c\u5e76\u5b8c\u6210\u50ac\u5316\u5faa\u73af\u7684\u8fc7\u7a0b\u3002 \u603b\u7ed3\uff1a \u540c\u6d4e\u5927\u5b66\u7684\u8d75\u6653\u660e\u7b49\u8bfe\u9898\u7ec4\u62a5\u9053\u4e00\u79cd\u8f74\u624b\u6027\u94f1\u535f\u5549\u914d\u5408\u7269\u50ac\u5316N-\u7532\u57fa\u4e09\u7ea7\u80fa\u4e2d\u4e00\u7ea7C(sp3)\u2212H\u952e\u4e0e\u91cd\u6c2e\u5316\u5408\u7269\u7684\u9ad8\u5ea6\u4f4d\u70b9\u9009\u62e9\u6027\u4e0e\u5bf9\u6620\u9009\u62e9\u6027\u70f7\u57fa\u5316\u53cd\u5e94\uff0c\u5408\u6210\u4e86\u4e00\u7cfb\u5217\u03b2-\u624b\u6027\u4e09\u7ea7\u80fa\u3002\u540c\u65f6\uff0c\u8be5\u7b56\u7565\u5177\u6709\u6536\u7387\u9ad8\u3001\u5e95\u7269\u8303\u56f4\u5e7f\u6cdb\u3001\u4f18\u826f\u7684\u5b98\u80fd\u56e2\u517c\u5bb9\u6027\u4ee5\u53ca\u4f18\u826f\u7684\u5bf9\u6620\u9009\u62e9\u6027\u7b49\u4f18\u52bf\u3002\u5176\u6b21\uff0c\u901a\u8fc7\u5bf9\u624b\u6027\u8377\u5305\u7261\u4e39\u78b1\u7684\u540e\u671f\u4fee\u9970\uff0c\u8fdb\u4e00\u6b65\u8bc1\u660e\u4e86\u53cd\u5e94\u7684\u5b9e\u7528\u6027\u3002 \u53c2\u8003\u6587\u732e\uff1a [1] J. Zhang, C. Liu, J. Wu, X. Tan, W. Wu, H. Jiang, Org. Lett. 2024, 26, 4422. doi:10.1021\/acs.orglett.4c00880. [2] H. M. 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