\u4f5c\u8005\uff1a\u77f3\u6cb9\u919a<\/strong><\/p>\n
\u672c\u671f\u70ed\u70b9\u7814\u7a76\uff0c\u6211\u4eec\u9080\u8bf7\u5230\u4e86\u672c\u6587\u5171\u540c\u7b2c\u4e00\u4f5c\u8005\uff0c\u6765\u81ea\u5df4\u585e\u5c14\u5927\u5b66\u7684\u535a\u58eb\u751f\u9648\u680b\u840d\u4e3a\u6211\u4eec\u5206\u4eab\u3002<\/p>\n
2024\u5e747\u670819\u65e5\uff0cNature Chemistry<\/em>\u5728\u7ebf\u53d1\u8868\u4e86\u6765\u81ea\u745e\u58eb\u5df4\u585e\u5c14\u5927\u5b66\u7684Thomas R. Ward\u6559\u6388\u8bfe\u9898\u7ec4\u9898\u4e3a\u300cAn Evolved Artificial Radical Cyclase Enables the Construction of Bicyclic Terpenoid Scaffolds via an H-Atom Transfer Pathway\u300d\u7684\u7814\u7a76\u8bba\u6587\u3002\u57fa\u4e8e\u751f\u7269\u7d20\u548c\u94fe\u9709\u4eb2\u548c\u7d20\u7684\u5f3a\u4eb2\u548c\u529b\uff0c\u4f5c\u8005\u901a\u8fc7\u5728\u5de5\u7a0b\u5316\u6539\u9020\u7684\u5d4c\u5408\u94fe\u9709\u4eb2\u548c\u7d20\u4e2d\u951a\u5b9a\u751f\u7269\u7d20[Co(schiff-base)] \u7684\u4eba\u9020\u8f85\u56e0\u5b50\u800c\u6784\u5efa\u4e86\u4eba\u5de5\u81ea\u7531\u57fa\u73af\u5316\u9176\uff08ARCase\uff09\u3002\u7ecf\u8fc7\u8ba1\u7b97\u8f85\u52a9\u7684\u86cb\u767d\u6539\u9020\u4ee5\u53ca\u4e24\u8f6e\u5b9a\u5411\u8fdb\u5316\u83b7\u5f97\u7684\u6700\u4f73\u7a81\u53d8\u4f53\u53ef\u4ee5\u987a\u5229\u5730\u50ac\u5316\u81ea\u7531\u57fa\u73af\u5316\u53cd\u5e94\uff0c\u4e00\u6b65\u5408\u6210\u5177\u6709cis<\/em>-5-6-\u7a20\u73af\u7ed3\u6784\u548c\u9ad8\u5bf9\u6620\u9009\u62e9\u6027\u7684\u53cc\u73af\u4ea7\u7269\u3002QM\/MM\u8ba1\u7b97\u4ee5\u53ca\u5355\u6676\u7ed3\u6784\u8bc1\u660e\u7a81\u53d8\u5f15\u5165\u7684\u7ec4\u6c28\u9178\u6b8b\u57fa\u4e0e\u50ac\u5316\u4e2d\u5fc3\u7684\u94b4\u539f\u5b50\u5177\u6709\u914d\u4f4d\u4f5c\u7528\u3002\u901a\u8fc7\u5bf9\u53cd\u5e94\u8fc7\u7a0b\u7684\u5b9e\u65f6\u76d1\u6d4b\uff0c\u63ed\u9732\u4e86ARCase \u6210\u529f\u5730\u50ac\u5316\u4e86\u4e00\u4e2a\u5305\u542b\u4e24\u6b65\u53cd\u5e94\u7684\u7ea7\u8054\u8fc7\u7a0b\uff0c\u5373\u94b4\u6c22\u4ecb\u5bfc\u7684\u81ea\u7531\u57fa\u73af\u5316\u548c\u5171\u8f6d\u8fd8\u539f\u53cd\u5e94\u3002\u6b64\u5916\uff0cARCase\u5bf9\u4e8c\u70ef\u916e\u5e95\u7269\u7684\u53d8\u5316\u8868\u73b0\u51fa\u8f83\u597d\u7684\u8010\u53d7\u6027\uff0c\u5e76\u4e14\u7ed3\u5408\u5316\u5b66\u5408\u6210\u4e0e\u9176\u5408\u6210\u7b56\u7565\uff0c\u53ef\u4ee5\u5feb\u901f\u5b9e\u73b0\u841c\u7c7b\u5316\u5408\u7269\u4e2d\u7684\u4e09\u73af\u9aa8\u67b6\u7684\u624b\u6027\u6784\u5efa\uff0c \u5c55\u793a\u4e86\u5176\u5728\u590d\u6742\u841c\u7c7b\u5316\u5408\u7269\u751a\u81f3\u836f\u7269\u5206\u5b50\u5408\u6210\u4e2d\u7684\u6f5c\u529b\u3002<\/p>\n
\n\u201cAn Evolved Artificial Radical Cyclase Enables the Construction of Bicyclic Terpenoid Scaffolds via an H-Atom Transfer Pathway.<\/p>\n
Dongping Chen\u2021, Xiang Zhang\u2021 Anastassia Andreevna Vorobieva, Ryo Tachibana, Alina Stein, Roman P. Jakob, Zhi Zou, Damian Alexander Graf, Ang Li, Timm Maier, Bruno E. Correia*, Thomas R. Ward*<\/p>\n
Nat.Chem.<\/em>\u00a02024<\/strong>. Doi:10.1038\/s41557-024-01562-5\u201d<\/a><\/p>\n<\/blockquote>\n
Q1. <\/strong>\u8bf7\u5bf9<\/strong>\u201cAn Evolved Artificial Radical Cyclase Enables the Construction of Bicyclic Terpenoid Scaffolds via an H-Atom Transfer Pathway\u201d<\/strong>\u4f5c<\/strong>\u4e00\u4e2a\u7b80\u5355\u4ecb\u7ecd\u3002<\/strong><\/h4>\n
\u81ea\u7136\u754c\u5229\u7528\u5929\u7136\u841c\u7c7b\u73af\u5316\u9176\u901a\u8fc7\u9633\u79bb\u5b50\u673a\u5236\u53ef\u4ee5\u4ea7\u751f\u590d\u6742\u7684\u841c\u7c7b\u5316\u5408\u7269\uff0c\u4f46\u5176\u4ed6\u7684\u53cd\u5e94\u9014\u5f84\u6bd4\u5982\u81ea\u7531\u57fa\u73af\u5316\u9014\u5f84\u5374\u5c1a\u672a\u5f97\u5230\u5145\u5206\u5730\u63a2\u7d22\u3002\u91d1\u5c5e\u50ac\u5316\u7684\u6c22\u539f\u5b50\u8f6c\u79fb\uff08M-HAT\uff09\u53cd\u5e94\u53ef\u4ee5\u9ad8\u6548\u5730\u5b9e\u73b0\u975e\u6d3b\u5316\u70ef\u70c3\u7684\u6c22\u5b98\u80fd\u56e2\u5316\uff0c\u8fdb\u800c\u4e3a\u4ece\u94fe\u72b6\u591a\u70ef\u524d\u4f53\u5230\u591a\u73af\u841c\u7c7b\u9aa8\u67b6\u63d0\u4f9b\u4e86\u4e00\u79cd\u6709\u6548\u7684\u8f6c\u5316\u7b56\u7565\u3002\u4eba\u5de5\u91d1\u5c5e\u9176\u662f\u4e00\u79cd\u53ef\u4ee5\u5c06\u5747\u76f8\u50ac\u5316\u4f53\u7cfb\u9ad8\u6548\u5730\u5f15\u5165\u5230\u57fa\u56e0\u53ef\u63a7\u7684\u86cb\u767d\u8d28\u9aa8\u67b6\u4e2d\u7684\u50ac\u5316\u6a21\u5f0f\uff0c\u4e3a\u5c06\u975e\u5929\u7136\u7684 M-HAT \u53cd\u5e94\u5f15\u5165\u8fdb\u81ea\u7136\u754c\u7684\u751f\u7269\u50ac\u5316\u63d0\u4f9b\u4e86\u4e00\u4e2a\u53ef\u9760\u7684\u7b56\u7565\u3002\u5728\u8be5\u5de5\u4f5c\u4e2d\uff0c\u4f9d\u8d56\u4e8e\u751f\u7269\u7d20\u548c\u94fe\u9709\u4eb2\u548c\u7d20\u7684\u5f3a\u4eb2\u548c\u529b\uff0c\u6211\u4eec\u62a5\u9053\u4e86\u57fa\u4e8eM-HAT \u53cd\u5e94\u7684\u4eba\u5de5\u81ea\u7531\u57fa\u73af\u5316\u9176\uff08ARCase\uff09\u7684\u8bbe\u8ba1\u548c\u6784\u5efa\u3002\u6211\u4eec\u9996\u5148\u8bbe\u8ba1\u5e76\u5408\u6210\u4e86\u591a\u4e2a\u751f\u7269\u7d20\u8fde\u63a5\u7684\u3001Salophen\u4f5c\u4e3a\u914d\u4f53\u7684\u94b4\u91d1\u5c5e\u5316\u5408\u7269\uff0c\u5e76\u901a\u8fc7\u6761\u4ef6\u4f18\u5316\u83b7\u5f97\u4e86\u8868\u73b0\u6700\u4f73\u7684\u91d1\u5c5e\u5316\u5408\u7269\u4f5c\u4e3aARCase\u7684\u4eba\u5de5\u8f85\u56e0\u5b50\u3002\u6211\u4eec\u8fdb\u4e00\u6b65\u4e0e\u745e\u58eb\u6d1b\u6851\u7406\u5de5\u5b66\u9662\u7684Correia\u8bfe\u9898\u7ec4\u5408\u4f5c\uff0c\u8bbe\u8ba1\u5e76\u6784\u5efa\u4e86\u5d4c\u5408\u578b\u7684\u94fe\u9709\u4eb2\u548c\u7d20\u7684\u86cb\u767d\u9aa8\u67b6\u5e93\uff0c\u901a\u8fc7\u5728\u6d3b\u5316\u4e2d\u5fc3\u4e0a\u65b9\u5f15\u5165\u957f\u5ea6\u4e0d\u4e00\u3001\u5f62\u72b6\u5404\u5f02\u7684\u73af\u7247\u6bb5\u6765\u589e\u5f3a\u5176\u5bc6\u95ed\u6027\u3002\u501f\u52a9\u57fa\u4e8e\u7ec6\u80de\u88c2\u89e3\u6db2\u7684\u5feb\u901f\u7b5b\u9009\u548c\u7eaf\u5316\u86cb\u767d\u7684\u8fdb\u4e00\u6b65\u9a8c\u8bc1\uff0c\u6211\u4eec\u6210\u529f\u83b7\u5f97\u4e86\u6d3b\u6027\u548c\u9009\u62e9\u6027\u5747\u8fdb\u4e00\u6b65\u63d0\u9ad8\u7684\u5d4c\u5408\u94fe\u9709\u4eb2\u548c\u7d20ARCase\u7684\u86cb\u767d\u9aa8\u67b6\uff0c\u5e76\u53d1\u73b0\u8be5\u9aa8\u67b6\u6210\u529f\u5730\u5d4c\u5165\u4e8616\u4e2a\u6c28\u57fa\u9178\u5e8f\u5217\u7684\u3001\u542b\u03b1\u87ba\u65cb\u7ed3\u6784\u7684\u73af\u7247\u6bb5\u3002\u7ecf\u8fc7\u4e24\u8f6e\u86cb\u767d\u6539\u9020\uff0c\u6211\u4eec\u53d1\u73b0\u4e86\u4e00\u4e2a\u542b\u53cc\u7a81\u53d8\u4f53\u7684ARCase\u53ef\u4ee5\u6784\u5efa\u5177\u6709cis<\/em>-5-6-\u7a20\u73af\u7ed3\u6784\u7684\u53cc\u73af\u73af\u5316\u4ea7\u7269\uff0c \u5e76\u4e14\u9009\u62e9\u6027\u9ad8\u8fbe 97% ee\u3002\u901a\u8fc7QM\/MM\u8ba1\u7b97\u4ee5\u53ca\u5355\u6676\u7ed3\u6784\u89e3\u6790\uff0c \u6211\u4eec\u786e\u8ba4\u4e86\u7a81\u53d8\u5f15\u5165\u7684\u7ec4\u6c28\u9178\u6b8b\u57fa\u4e0e\u50ac\u5316\u4e2d\u5fc3\u7684\u94b4\u539f\u5b50\u7684\u914d\u4f4d\u4f5c\u7528\u3002\u6211\u4eec\u63a8\u6d4b\u8be5\u914d\u4f4d\u4f5c\u7528\u4e0d\u4ec5\u53ef\u4ee5\u8fdb\u4e00\u6b65\u7a33\u5b9a\u4eba\u5de5\u8f85\u56e0\u5b50\u5728\u86cb\u767d\u73af\u5883\u4e2d\u7684\u6784\u8c61\uff0c\u800c\u4e14\u8fd8\u53ef\u4ee5\u589e\u5f3a\u5176\u7684\u7535\u5b50\u4e91\u5bc6\u5ea6\uff0c\u4ece\u800c\u6781\u5927\u5730\u63d0\u9ad8\u4e86M-HAT\u53cd\u5e94\u6d3b\u6027\u3002\u8fdb\u4e00\u6b65\u901a\u8fc7\u5bf9\u53cd\u5e94\u8fc7\u7a0b\u7684\u5b9e\u65f6\u76d1\u6d4b\uff0c\u6211\u4eec\u53d1\u73b0ARCase \u6210\u529f\u5730\u50ac\u5316\u4e86\u4e00\u4e2a\u542b\u4e24\u6b65\u53cd\u5e94\u7684\u7ea7\u8054\u8fc7\u7a0b\uff0c\u5373\u94b4\u6c22\u4ecb\u5bfc\u7684\u81ea\u7531\u57fa\u73af\u5316\u548c\u5171\u8f6d\u8fd8\u539f\u53cd\u5e94\u3002\u5728\u5e95\u7269\u62d3\u5c55\u4e2d\uff0c ARCase\u5bf9\u4e8c\u70ef\u916e\u5e95\u7269\u7684\u53d8\u5316\u8868\u73b0\u51fa\u8f83\u597d\u7684\u8010\u53d7\u6027\uff0c\u5e76\u4e14\u7ed3\u5408\u5316\u5b66\u5408\u6210\u4e0e\u9176\u5408\u6210\u7b56\u7565\uff0c\u53ef\u4ee5\u5feb\u901f\u5b9e\u73b0\u841c\u7c7b\u5316\u5408\u7269\u4e2d\u7684\u4e09\u73af\u9aa8\u67b6\u7684\u624b\u6027\u6784\u5efa\uff0c \u5c55\u793a\u4e86\u5176\u5728\u590d\u6742\u841c\u7c7b\u5316\u5408\u7269\u751a\u81f3\u836f\u7269\u5206\u5b50\u5408\u6210\u4e2d\u7684\u6f5c\u529b\u3002<\/p>\n
Q2.<\/strong>\u5728\u7814\u7a76\u7684\u65f6\u5019\u9047\u5230\u8fc7\u600e\u6837\u7684\u56f0\u96be\u5462\uff1f\u53c8\u662f\u600e\u6837\u514b\u670d\u7684\u5462\uff1f<\/strong><\/h4>\n
10.1021\/jacs.3c10133<\/a><\/p>\n<\/blockquote>\n\u5f53\u6211\u4eec\u53d1\u73b0\u53cc\u7a81\u53d8\u4f53\u80fd\u591f\u5f97\u5230\u4e0d\u9519\u7684\u9009\u62e9\u6027\u65f6\uff0c\u6211\u4eec\u8fdb\u884c\u4e86\u4e00\u7cfb\u5217\u7684\u4f18\u5316\uff0c\u7136\u800c\u6536\u7387\u8fd8\u662f\u4e0d\u80fd\u63d0\u9ad8\u3002\u4e3a\u6b64\uff0c\u6211\u4eec\u82e6\u607c\u4e86\u4e00\u6bb5\u65f6\u95f4\u3002\u6211\u4eec\u5c1d\u8bd5\u4ece\u751f\u7269\u50ac\u5316\u7684\u89d2\u5ea6\u601d\u8003\uff0c\u662f\u4e0d\u662f\u53ef\u80fd\u5b58\u5728\u4ea7\u7269\u8fdb\u4e00\u6b65\u8f6c\u5316\u3002\u4e3a\u6b64\uff0c\u6211\u4eec\u628a\u6d88\u65cb\u7684\u6807\u51c6\u4ea7\u7269\u6295\u5165\u5230\u53cd\u5e94\u4f53\u7cfb\u4e2d\uff0c\u53d1\u73b0\u4e86\u4ea7\u7269\u88ab\u8fdb\u4e00\u6b65\u6d88\u8017\uff0c\u5e76\u4e14\u51fa\u73b0\u52a8\u529b\u5b66\u62c6\u5206\u7684\u73b0\u8c61\u3002\u56e0\u6b64\uff0c\u6211\u4eec\u628a\u53ef\u80fd\u751f\u6210\u7684\u526f\u4ea7\u7269\u901a\u8fc7\u5316\u5b66\u65b9\u6cd5\u5408\u6210\u51fa\u6765\uff0c \u4e0e\u9176\u50ac\u5316\u53cd\u5e94\u4f53\u7cfb\u8fdb\u884c\u6bd4\u8f83\uff0c\u6700\u7ec8\u786e\u8ba4\u662f\u76ee\u6807\u4ea7\u7269\u7684\u70ef\u916e\u5b98\u80fd\u56e2\u4f1a\u88ab\u8fdb\u4e00\u6b65\u8fd8\u539f\uff0c\u800c\u5bf9\u53cd\u5e94\u8fc7\u7a0b\u7684\u5b9e\u65f6\u76d1\u6d4b\u4e5f\u8fdb\u4e00\u6b65\u9a8c\u8bc1\u4e86\u6211\u4eec\u7684\u731c\u60f3\u3002\u901a\u8fc7\u5bf9\u53cd\u5e94\u7ed3\u679c\u7684\u601d\u8003\u548c\u7814\u7a76\uff0c\u6211\u4eec\u987a\u5229\u5730\u63ed\u9732\u4e86ARCase\u53ef\u4ee5\u5b9e\u73b0\u57fa\u4e8eM-HAT\u7684\u542b\u4e24\u6b65\u53cd\u5e94\u7684\u7ea7\u8054\u8fc7\u7a0b\u7684\u6709\u8da3\u73b0\u8c61\u3002<\/p>\n
Q3.<\/strong>\u672c\u6b21\u7814\u7a76\u4e3b\u4f53\uff0c\u6709\u6ca1\u6709\u4ec0\u4e48\u8ba9\u60a8\u611f\u89c9\u7279\u522b\u8f9b\u82e6\u548c\u70e7\u8111\u5462\uff1f<\/strong><\/h4>\n
10.1038\/s41586-024-07757-7<\/a>.\u201d<\/p>\n<\/blockquote>\n\u6211\u4eec\u7684\u5de5\u4f5c\u4ece\u5f00\u59cb\u5230\u7ed3\u675f\uff0c\u5904\u5728\u7ec4\u91cc\u9752\u9ec4\u4e0d\u63a5\u7684\u8fc7\u6e21\u671f\uff0c\u5c24\u5176\u662f\u751f\u7269\u65b9\u9762\u7684\u6280\u80fd\u6025\u9700\u6709\u4eba\u80fd\u591f\u63a8\u52a8\u8bfe\u9898\u524d\u8fdb\uff0c\u4e3a\u6b64\u6211\u4e5f\u6cae\u4e27\u4e86\u4e00\u6bb5\u65f6\u95f4\uff0c\u8fd9\u4e5f\u903c\u8feb\u6211\u6362\u4e00\u4e2a\u89d2\u5ea6\u601d\u8003\uff0c\u5b66\u4e60\u5e76\u638c\u63e1\u63a8\u52a8\u8fd9\u4e2a\u8bfe\u9898\u524d\u8fdb\u6240\u9700\u8981\u7684\u751f\u7269\u77e5\u8bc6\u3002<\/p>\n
Q4. <\/strong>\u5c06\u6765\u60f3\u7ee7\u7eed\u7814\u7a76\u5316\u5b66\u7684\u54ea\u4e2a\u65b9\u5411\u5462\uff1f<\/strong><\/h4>\n
\u76ee\u524d\uff0c\u535a\u58eb\u5373\u5c06\u6bd5\u4e1a\u3002\u5e0c\u671b\u4ee5\u540e\u80fd\u591f\u4ece\u4e8b\u4eba\u5de5\u91d1\u5c5e\u9176\uff0c\u86cb\u767d\u8bbe\u8ba1\uff0c\u5408\u6210\u751f\u7269\u5b66\u7684\u76f8\u5173\u5de5\u4f5c\u3002<\/p>\n
Q5. <\/strong>\u6700\u540e\uff0c\u6709\u4ec0\u4e48\u60f3\u5bf9\u5404\u4f4d\u8bfb\u8005\u8bf4\u7684\u5417\uff1f<\/strong><\/h4>\n
\u79d1\u5b66\u7814\u7a76\u662f\u4e00\u4e2a\u9700\u8981\u4e0d\u65ad\u8bd5\u9519\u3001\u4e0d\u65ad\u63a2\u7d22\u7684\u65c5\u9014\uff0c\u5927\u90e8\u5206\u65f6\u95f4\u5e76\u4e0d\u4e00\u5b9a\u80fd\u591f\u5982\u5df1\u6240\u613f\uff0c\u4f46\u8d35\u5728\u575a\u6301\uff0c\u6211\u4eec\u53ef\u4ee5\u4ece\u8fd9\u4e2a\u65c5\u9014\u4e2d\u5f97\u5230\u591a\u4e2a\u7ef4\u5ea6\u7684\u8bad\u7ec3\uff0c\u800c\u8fd9\u4e9b\u7ecf\u9a8c\u6559\u8bad\u5bf9\u4ee5\u540e\u7684\u7814\u7a76\u5de5\u4f5c\u6765\u8bf4\u662f\u4e00\u4e2a\u5b9d\u8d35\u7684\u8d22\u5bcc\u3002\u6211\u5f88\u611f\u6fc0\u5728\u8fd9\u4e2a\u9879\u76ee\u7684\u63a2\u7d22\u8fc7\u7a0b\u4e2d\uff0c\u6211\u7684\u5bfc\u5e08Prof. Thomas R. Ward\u5bf9\u6211\u7684\u8010\u5fc3\u6307\u5bfc\uff0c\u65e0\u6761\u4ef6\u5730\u652f\u6301\u548c\u6781\u5927\u7684\u9f13\u52b1\uff0c\u4fc3\u4f7f\u6211\u5feb\u901f\u6210\u957f\u5e76\u79ef\u6781\u63a8\u52a8\u8bfe\u9898\u524d\u8fdb\u3002\u5f88\u611f\u6fc0\u6211\u4eec\u56e2\u961f\u91cc\u7684\u6bcf\u4e00\u4e2a\u6210\u5458\u7684\u52aa\u529b\uff0c\u4ed6\u4eec\u4e5f\u4e3a\u8fd9\u4efd\u5de5\u4f5c\u7684\u53d1\u8868\u505a\u51fa\u4e86\u5de8\u5927\u8d21\u732e\u3002\u8fd9\u4efd\u5de5\u4f5c\u5c06\u4f1a\u6210\u4e3a\u6211\u7684\u4e2a\u4eba\u6210\u957f\u548c\u804c\u4e1a\u53d1\u5c55\u4e2d\u975e\u5e38\u91cd\u8981\u7684\u7ecf\u5386\u3002<\/p>\n
\u4f5c\u8005\u6559\u80b2\u80cc\u666f\u7b80\u4ecb<\/strong><\/h4>\n
<\/strong><\/p>\n
\u6559\u80b2\u80cc\u666f\uff1a<\/strong><\/h4>\n
2020.08-\u73b0\u5728\uff0c\u535a\u58eb\u5728\u8bfb\uff0c\u5df4\u585e\u5c14\u5927\u5b66\uff0c Prof. Thomas R Ward<\/p>\n
2014.09-2017.07\uff0c \u7855\u58eb\uff0c\u4e0a\u6d77\u6709\u673a\u5316\u5b66\u7814\u7a76\u6240\uff0c \u6c64\u6587\u519b\u7814\u7a76\u5458<\/p>\n
2010.09-2014.06\uff0c\u5b66\u58eb\uff0c\u5357\u4eac\u5de5\u4e1a\u5927\u5b66<\/p>\n
\u83b7\u5956\u7ecf\u5386\uff1a<\/strong><\/h4>\n
2024\uff0c Swiss Chemistry Travel Award<\/p>\n
\u672c\u6587\u7248\u6743\u5c5e\u4e8e Chem-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\uff1a\u77f3\u6cb9\u919a \u672c\u671f\u70ed\u70b9\u7814\u7a76\uff0c\u6211\u4eec\u9080\u8bf7\u5230\u4e86\u672c\u6587\u5171\u540c\u7b2c\u4e00\u4f5c\u8005\uff0c\u6765\u81ea\u5df4\u585e\u5c14\u5927\u5b66\u7684\u535a\u58eb\u751f\u9648\u680b\u840d\u4e3a\u6211\u4eec\u5206\u4eab\u3002 2024\u5e747\u670819\u65e5\uff0c Nature Chemistry\u5728\u7ebf\u53d1\u8868\u4e86\u6765\u81ea\u745e\u58eb\u5df4\u585e\u5c14\u5927\u5b66\u7684Thomas R. Ward\u6559\u6388\u8bfe\u9898\u7ec4\u9898\u4e3a\u300cAn Evolved Artificial Radical Cyclase Enables the Construction of Bicyclic Terpenoid Scaffolds via an H-Atom Transfer Pathway\u300d\u7684\u7814\u7a76\u8bba\u6587\u3002\u57fa\u4e8e\u751f\u7269\u7d20\u548c\u94fe\u9709\u4eb2\u548c\u7d20\u7684\u5f3a\u4eb2\u548c\u529b\uff0c\u4f5c\u8005\u901a\u8fc7\u5728\u5de5\u7a0b\u5316\u6539\u9020\u7684\u5d4c\u5408\u94fe\u9709\u4eb2\u548c\u7d20\u4e2d\u951a\u5b9a\u751f\u7269\u7d20[Co(schiff-base)] \u7684\u4eba\u9020\u8f85\u56e0\u5b50\u800c\u6784\u5efa\u4e86\u4eba\u5de5\u81ea\u7531\u57fa\u73af\u5316\u9176\uff08ARCase\uff09\u3002\u7ecf\u8fc7\u8ba1\u7b97\u8f85\u52a9\u7684\u86cb\u767d\u6539\u9020\u4ee5\u53ca\u4e24\u8f6e\u5b9a\u5411\u8fdb\u5316\u83b7\u5f97\u7684\u6700\u4f73\u7a81\u53d8\u4f53\u53ef\u4ee5\u987a\u5229\u5730\u50ac\u5316\u81ea\u7531\u57fa\u73af\u5316\u53cd\u5e94\uff0c\u4e00\u6b65\u5408\u6210\u5177\u6709cis-5-6-\u7a20\u73af\u7ed3\u6784\u548c\u9ad8\u5bf9\u6620\u9009\u62e9\u6027\u7684\u53cc\u73af\u4ea7\u7269\u3002QM\/MM\u8ba1\u7b97\u4ee5\u53ca\u5355\u6676\u7ed3\u6784\u8bc1\u660e\u7a81\u53d8\u5f15\u5165\u7684\u7ec4\u6c28\u9178\u6b8b\u57fa\u4e0e\u50ac\u5316\u4e2d\u5fc3\u7684\u94b4\u539f\u5b50\u5177\u6709\u914d\u4f4d\u4f5c\u7528\u3002\u901a\u8fc7\u5bf9\u53cd\u5e94\u8fc7\u7a0b\u7684\u5b9e\u65f6\u76d1\u6d4b\uff0c\u63ed\u9732\u4e86ARCase \u6210\u529f\u5730\u50ac\u5316\u4e86\u4e00\u4e2a\u5305\u542b\u4e24\u6b65\u53cd\u5e94\u7684\u7ea7\u8054\u8fc7\u7a0b\uff0c\u5373\u94b4\u6c22\u4ecb\u5bfc\u7684\u81ea\u7531\u57fa\u73af\u5316\u548c\u5171\u8f6d\u8fd8\u539f\u53cd\u5e94\u3002\u6b64\u5916\uff0cARCase\u5bf9\u4e8c\u70ef\u916e\u5e95\u7269\u7684\u53d8\u5316\u8868\u73b0\u51fa\u8f83\u597d\u7684\u8010\u53d7\u6027\uff0c\u5e76\u4e14\u7ed3\u5408\u5316\u5b66\u5408\u6210\u4e0e\u9176\u5408\u6210\u7b56\u7565\uff0c\u53ef\u4ee5\u5feb\u901f\u5b9e\u73b0\u841c\u7c7b\u5316\u5408\u7269\u4e2d\u7684\u4e09\u73af\u9aa8\u67b6\u7684\u624b\u6027\u6784\u5efa\uff0c \u5c55\u793a\u4e86\u5176\u5728\u590d\u6742\u841c\u7c7b\u5316\u5408\u7269\u751a\u81f3\u836f\u7269\u5206\u5b50\u5408\u6210\u4e2d\u7684\u6f5c\u529b\u3002 \u201cAn Evolved Artificial Radical Cyclase Enables the Construction of Bicyclic Terpenoid Scaffolds via an H-Atom Transfer Pathway. Dongping Chen\u2021, Xiang Zhang\u2021 Anastassia Andreevna Vorobieva, Ryo Tachibana, Alina Stein, Roman P. Jakob, Zhi Zou, Damian Alexander Graf, Ang Li, Timm Maier, Bruno E. Correia*, Thomas R. Ward* Nat.Chem.\u00a02024. 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\u672c\u6587\u4f5c\u8005\uff1aAzathoth <\/strong>\u00a0\u00a0\u00a0\u00a0\u00a0\u00a0\u00a0\u00a0\u00a0\u00a0\u00a0\u00a0\u00a0\u00a0\u00a0\u00a0\u00a0\u00a0\u00a0\u00a0\u00a0\u00a0\u00a0\u00a0\u00a0\u00a0\u00a0\u00a0\u00a0\u5199\u4f5c\u6307\u5bfc\uff1aCyclization Xu<\/strong><\/p>\n
\u5bfc\u8bfb<\/strong>\uff1a<\/h4>\n
\u672c\u6587\u4ecb\u7ecd\u4e86\u9530\u50ac\u5316\u6c22\u5316\u9886\u57df\u7684\u7814\u7a76\u8fdb\u5c55\u3002\u6587\u4e2d\u63cf\u8ff0\u4e86\u4e0d\u540c\u7c7b\u578b\u9530\u50ac\u5316\u5242\u7684\u8bbe\u8ba1\u4e0e\u6027\u80fd\uff0c\u901a\u8fc7\u5206\u6790\u4e0d\u540c\u914d\u4f53\u548c\u53cd\u5e94\u6761\u4ef6\u5bf9\u50ac\u5316\u6548\u7387\u548c\u9009\u62e9\u6027\u7684\u5f71\u54cd\uff0c\u5c55\u793a\u4e86\u9530\u50ac\u5316\u5242\u5728\u4e0d\u5bf9\u79f0\u6c22\u5316\u53cd\u5e94\u4e2d\u7684\u6f5c\u529b\u3002\u6e05\u534e\u5927\u5b66\u5218\u5f3a\u56e2\u961f\u63d0\u51fa\u4e86\u5173\u4e8e\u9530\u50ac\u5316\u6c22\u5316\u7684\u591a\u79cd\u6d3b\u5316\u6a21\u578b\uff0c\u5e76\u5c06\u5176\u5e94\u7528\u5728\u50ac\u5316\u5242\u7684\u8bbe\u8ba1\u4e0a\uff0c\u63a8\u52a8\u4e86\u8be5\u9886\u57df\u7684\u5feb\u901f\u53d1\u5c55\u3002<\/p>\n
\u6b63\u6587<\/strong>\uff1a<\/h4>\n
\u9530\u662f\u4ec5\u6b21\u4e8e\u94c1\u3001\u949b\uff0c\u50a8\u91cf\u6392\u7b2c\u4e09\u4f4d\u7684\u8fc7\u6e21\u91d1\u5c5e\uff0c\u5177\u6709\u5f88\u5927\u7684\u5e94\u7528\u4ef7\u503c\u3002\u63d0\u5230\u9530\u50ac\u5316\u7684\u4e0d\u5bf9\u79f0\u53cd\u5e94\uff0c\u6211\u4eec\u9996\u5148\u60f3\u5230\u7684\u5c31\u662f\u8bfe\u672c\u4e0a\u7684Jacobsen\u2013Katsuki\u4e0d\u5bf9\u79f0\u73af\u6c27\u5316\u3002\u4f46\u662f\u5747\u76f8\u9530\u50ac\u5316\u7684\u6c22\u5316\u4e00\u76f4\u52302016\u5e74\u624d\u5f00\u59cb\u53d1\u5c55\uff0c\u5c5e\u4e8e\u4e00\u4e2a\u6bd4\u8f83\u65b0\u7684\u9886\u57df\u3002\u76ee\u524d\u7684\u5df2\u77e5\u7684\u9530\u50ac\u5316\u6c22\u5316\u90fd\u662f\u5916\u7403\u673a\u7406\uff0c\u5bf9\u4e8e\u5916\u7403\u673a\u7406\u7684\u91d1\u5c5e\u50ac\u5316\u4e0d\u5bf9\u79f0\u6c22\u5316\u800c\u8a00\uff0c\u53cd\u5e94\u6700\u91cd\u8981\u7684\u4e24\u6b65\u662f\u91d1\u5c5e\u6c22\u7269\u79cd\u7684\u751f\u6210\u548c\u6c22\u8d1f\u7684\u8f6c\u79fb\u3002\u4f46\u8fd9\u4e24\u6b65\u7684\u5f71\u54cd\u56e0\u7d20\u5f80\u5f80\u662f\u76f8\u4e92\u77db\u76fe\u7684\uff0c\u91d1\u5c5e\u6c22\u7269\u79cd\u7684\u6d3b\u6027\u8d8a\u9ad8\uff0c\u6c22\u8d1f\u8d8a\u5bb9\u6613\u8f6c\u79fb\uff0c\u7136\u800c\u4e5f\u610f\u5473\u7740\u91d1\u5c5e\u6c22\u7269\u79cd\u4e5f\u5c31\u8d8a\u96be\u751f\u6210\u3002\u5bf9\u4e8e\u948c\u94d1\u7b49\u9760\u540e\u7684\u8fc7\u6e21\u91d1\u5c5e\u800c\u8a00\uff0c\u5b83\u4eec\u7684\u91d1\u5c5e\u6c22\u7269\u79cd\u751f\u6210\u548c\u6c22\u8d1f\u8f6c\u79fb\u6070\u597d\u8fbe\u5230\u4e86\u4e00\u4e2a\u5e73\u8861\uff0c\u91d1\u5c5e\u6c22\u7269\u79cd\u65e2\u5bb9\u6613\u751f\u6210\u4e5f\u5bb9\u6613\u4e0e\u5e95\u7269\u53d1\u751f\u53cd\u5e94\u3002\u800c\u5bf9\u4e8e\u7b2c\u4e00\u884c\u8fc7\u6e21\u91d1\u5c5e\u800c\u8a00\uff0c\u91d1\u5c5e\u6c22\u7269\u79cd\u7684\u6d3b\u6027\u975e\u5e38\u9ad8\uff0c\u867d\u7136\u8fd9\u610f\u5473\u7740\u5f3a\u5927\u7684\u53cd\u5e94\u6d3b\u6027\uff0c\u4f46\u540c\u65f6\u4e5f\u5bfc\u81f4\u4e86\u91d1\u5c5e\u6c22\u7269\u79cd\u975e\u5e38\u96be\u4ee5\u751f\u6210\u3002
<\/p>\n
Fig.1.<\/strong> Typical outer-sphere mechanism catalytic hydrogenation<\/p>\n
\u76ee\u524d\u516c\u8ba4\u6700\u65e9\u7684\u5747\u76f8\u9530\u50ac\u5316\u6c22\u5316\u662f\u7531Beller \u7b49\u4eba\u5b9e\u73b0\u7684[1]<\/sup>\uff0c\u4ed6\u4eec\u7528PNP\u4e09\u9f7f\u914d\u4f53\u548c\u9530\u7684\u7edc\u5408\u7269\u5b9e\u73b0\u4e86\u82ef\u8148\u3001\u919b\u3001\u916e\u7684\u6c22\u5316\u3002Beller\u7684\u7814\u7a76\u8868\u660e\uff0c\u9530\u50ac\u5316\u5242\u5fc5\u987b\u8981\u6709\u4e00\u6c27\u5316\u78b3\u914d\u4f4d\uff0c\u901a\u8fc7\u53cd\u4f4d\u6548\u5e94\u6765\u7a33\u5b9a\u9530-\u6c22\u952e\uff0c\u5426\u5219\u9530\u6c22\u7269\u79cd\u7684\u80fd\u91cf\u4f1a\u975e\u5e38\u9ad8\uff0c\u96be\u4ee5\u751f\u6210\uff0c\u4ece\u800c\u65e0\u6cd5\u5b9e\u73b0\u50ac\u5316\u6c22\u5316\u3002
<\/p>\n
Scheme 1. <\/strong>One of the earliest homogeneous manganese-catalyzed hydrogenation reactions: hydrogenation of nitriles.
Fig.2. <\/strong>Mechanism of manganese-catalyzed hydrogenation<\/p>\n
\u5f71\u54cd\u53cd\u5e94\u6d3b\u6027\u65e0\u5916\u4e4e\u4e24\u4e2a\u4e3b\u8981\u539f\u56e0\uff1a\u7a7a\u95f4\u4f4d\u963b\u548c\u7535\u5b50\u6548\u5e94\u3002\u5bf9\u4e8e\u5747\u76f8\u7684\u9530\u50ac\u5316\u6c22\u5316\u53cd\u5e94\u800c\u8a00\uff0c\u5728\u4e00\u5b9a\u7a0b\u5ea6\u4e0a\u66f4\u5bcc\u7535\u5b50\u3001\u66f4\u5c0f\u4f4d\u963b\u7684\u50ac\u5316\u5242\u62e5\u6709\u76f8\u5bf9\u66f4\u9ad8\u7684\u6d3b\u6027\u3002\u5c0f\u7684\u4f4d\u963b\u6709\u5229\u4e8e\u50ac\u5316\u5242\u4e0e\u5e95\u7269\u63a5\u8fd1\uff0c\u800c\u5bcc\u7535\u5b50\u6709\u5229\u4e8e\u63d0\u9ad8\u91d1\u5c5e\u6c22\u7269\u79cd\u7684\u4eb2\u6838\u80fd\u529b\u3002\u5982Kempt\u7684\u5de5\u4f5c\u6240\u793a\uff0c\u5f53\u5421\u5576\u914d\u4f4d\u57fa\u56e2\u7684\u5bf9\u4f4d\u6709\u6c28\u57fa\u53d6\u4ee3\u65f6\uff0c\u50ac\u5316\u5242\u7684\u6d3b\u6027\u4f1a\u5f97\u5230\u63d0\u5347[2]<\/sup>\u3002Beller\u540e\u7eed\u7684\u5de5\u4f5c\u4e5f\u663e\u793a\u4e86\u4f4d\u963b\u5bf9\u50ac\u5316\u5242\u6d3b\u6027\u7684\u5f71\u54cd[3]<\/sup>\u3002
Scheme 2. <\/strong>The enhancement of the electron-donating ability of the ligand is beneficial for improving catalytic activity.
<\/p>\n
Scheme 3. <\/strong>The reduction of ligand steric hindrance is beneficial for improving catalytic activity.<\/p>\n
Beller \u3001Clarke\u3001Rueping\u3001Balskus\u7b49\u4eba\u5206\u522b\u4ee5\u54aa\u5511\u3001\u5421\u5576\u4e3a\u914d\u4f4d\u57fa\u56e2\u8bbe\u8ba1\u4e86PNN\u914d\u4f53[4] [5] [6]<\/sup>\uff0cPNN-Mn\u7684\u50ac\u5316\u6d3b\u6027\u76f8\u5bf9\u4e8ePNP-Mn\u50ac\u5316\u5242\u6709\u5de8\u5927\u7684\u63d0\u5347\u3002PNN-Mn\u50ac\u5316\u5242\u53ef\u4ee5\u6c22\u5316\u5982\u9170\u80fa\u3001\u916f\u548c\u78b3\u9178\u916f\u8fd9\u4e9b\u5177\u6709\u5f88\u5927\u6311\u6218\u6027\u7684\u5e95\u7269\uff0c\u8fd9\u662f\u5f88\u591aPNP-Mn\u50ac\u5316\u5242\u96be\u4ee5\u5b9e\u73b0\u7684\u3002
<\/p>\n
Scheme 4. <\/strong>In most cases, PNN ligands exhibit higher reaction activity than PNP ligands.<\/p>\n
\u540e\u6765\u6e05\u534e\u5927\u5b66\u5218\u5f3a\u548c\u91cd\u5e86\u5927\u5b66\u84dd\u5b87\u89e3\u91ca\u4e86PNN-Mn\u7edc\u5408\u7269\u6d3b\u6027\u5f3a\u4e8ePNP-Mn\u7edc\u5408\u7269\u7684\u539f\u56e0\uff1a\u4ed6\u4eec\u8ba4\u4e3aPNN\u914d\u4f53\u76f8\u5bf9\u4e8ePNP\u914d\u4f53\u7684\u4f18\u52bf\u5728\u4e8e\u4f4d\u963b\u5c0f\u3001\u5bcc\u7535\u5b50\uff0c\u5927\u5927\u964d\u4f4e\u4e86\u6c22\u5316\u53cd\u5e94\u7684\u80fd\u5792[7]<\/sup>\u3002
<\/p>\n
Fig.3. <\/strong>Reasons for higher activity of PNN ligands: reduced steric hindrance, electron-rich nature, lowering the energy of substrate-catalyst adducts, facilitating easier reactions.<\/p>\n
\u968f\u7740\u4ee5\u4e0a\u7814\u7a76\u7684\u6df1\u5165\uff0c\u4ed6\u4eec\u901a\u8fc7\u5206\u79bb\u4e2d\u95f4\u4f53\u8fdb\u884c\u6c22\u5316\u5b9e\u9a8c\u7b49\u65b9\u5f0f\u53d1\u73b0\uff0c\u914d\u4f53\u4e0e\u78b1\u5f62\u6210\u6c2e\u8d1f\u79bb\u5b50-\u78b1\u91d1\u5c5e\u76d0\u4e4b\u540e\u5f80\u5f80\u53cd\u5e94\u6d3b\u6027\u66f4\u9ad8\u3002\u56e0\u4e3a\u78b1\u91d1\u5c5e\u79bb\u5b50\u53ef\u4ee5\u7a33\u5b9a\u91d1\u5c5e\u6c22\u7269\u79cd\u4e0e\u5e95\u7269\u7684\u52a0\u5408\u7269\uff0c\u800c\u4e14\u8d1f\u79bb\u5b50\u7684\u5f62\u6210\u8fd8\u80fd\u4f7f\u5f97\u914d\u4f53\u66f4\u5bcc\u7535\u5b50\uff0c\u589e\u5f3a\u4e86\u91d1\u5c5e\u4e0a\u6c22\u8d1f\u7684\u4eb2\u6838\u80fd\u529b\uff0c\u5b9e\u73b0\u4e86\u78b1\u91d1\u5c5e\u79bb\u5b50\u4ecb\u5bfc\u7684\u03c0\u8f68\u9053\u65b9\u5411\u6d3b\u5316[8]<\/sup>\u3002
<\/strong><\/p>\n
Fig.4. <\/strong>Alkali metal ion-mediated \u03c0-activation with the C=N\/C=O double bond in the substrate,<\/p>\n
\u4f7f\u7528Lewis\u9178\u6216\u8d28\u5b50\u9178\u6765\u6d3b\u5316\u6781\u6027\u53cc\u952e\u662f\u975e\u5e38\u5e38\u89c1\u7684\u505a\u6cd5\uff0c\u5728\u5916\u7403\u673a\u7406\u6a21\u578b\u548c\u78b1\u91d1\u5c5e\u79bb\u5b50\u4ecb\u5bfc\u7684\u03c0\u8f68\u9053\u65b9\u5411\u6d3b\u5316\u6a21\u578b\u4e2d\uff0c\u50ac\u5316\u5242\u4e2d\u7684\u8d28\u5b50\u6c22\u6216\u8005\u78b1\u91d1\u5c5e\u79bb\u5b50\u76f4\u63a5\u4e0e\u5e95\u7269\u6781\u6027\u53cc\u952e\u4e2d\u7684\u6c2e\/\u6c27\u4f5c\u7528\uff0c\u6709\u4f5c\u4e3a\u9178\u6d3b\u5316\u6781\u6027\u53cc\u952e\u7684\u53ef\u80fd\u6027\u3002\u4f46\u662f\u4e0a\u8ff0\u4e24\u79cd\u6a21\u578b\u4e2d\u8d28\u5b50\u6c22\u6216\u78b1\u91d1\u5c5e\u79bb\u5b50\u901a\u5e38\u53ea\u80fd\u548c\u5e95\u7269\u7684\u03c0\u8f68\u9053\u65b9\u5411\u800c\u4e0d\u662f\u03c3-\u8f68\u9053\u65b9\u5411\u4f5c\u7528\uff0c\u96be\u4ee5\u53d1\u6325\u51fa\u9178\u7684\u529f\u80fd\u3002\u57fa\u4e8e\u6b64\u6e05\u534e\u5927\u5b66\u5218\u5f3a\u63d0\u51fa\u4e86\u03c3-\u8bf1\u5bfc\u6d3b\u5316[9]<\/sup>\uff0c\u5373\u901a\u8fc7\u8c03\u63a7\u91d1\u5c5e\u9633\u79bb\u5b50\uff0c\u4f7f\u5176\u4e0e\u5e95\u7269\u6c2e\/\u6c27\u7684\u03c3-\u952e\u65b9\u5411\u5b64\u7535\u5b50\u5bf9\u4f5c\u7528\uff0c\u63d0\u9ad8\u4e86\u5e95\u7269\u7684\u4eb2\u7535\u80fd\u529b\uff0c\u5927\u5927\u63d0\u5347\u4e86\u6c22\u8d1f\u8f6c\u79fb\u7684\u6548\u7387\u3002
<\/strong><\/p>\n
<\/strong><\/p>\n
Fig. 5. <\/strong>Comparison of catalytic activity of HMn-NH, HMn-NLi, and HMn-NAl systems.<\/p>\n
\u4e0a\u8ff0\u673a\u7406\u4e0a\u7684\u94fa\u57ab\u542f\u53d1\u7740\u79d1\u5b66\u5bb6\u4eec\u5bf9\u4e8e\u4e0d\u5bf9\u79f0\u53cd\u5e94\u7684\u63a2\u7d22\u3002\u5411\u9530\u7edc\u5408\u7269\u4e2d\u5f15\u5165\u624b\u6027\u5143\u7d20\uff0c\u4fbf\u6709\u673a\u4f1a\u5b9e\u73b0\u9530\u50ac\u5316\u7684\u4e0d\u5bf9\u79f0\u6c22\u5316\u3002\u5411\u9530\u7edc\u5408\u7269\u4e2d\u5f15\u5165\u624b\u6027\u5143\u7d20\u4e3b\u8981\u6709\u4e24\u79cd\u65b9\u5f0f\uff0cBeller\u3001\u4e01\u594e\u5cad\u7b49[10] [11]<\/sup>\u5c06\u914d\u4f53\u81a6\u7684\u90e8\u5206\u505a\u6210\u624b\u6027\u7684BPE\u7247\u6bb5\uff0c\u5f97\u5230\u4e86\u7ecf\u5f0f\u914d\u4f4d\u7684\u9530\u7edc\u5408\u7269\uff1bKirchner\u3001\u5218\u5f3a[12] [13] [14] [15]<\/sup>\u7b49\u5219\u4ee5\u4e8c\u8302\u94c1\u4e3a\u57fa\u7840\uff0c\u7531\u4e8c\u8302\u94c1\u5f15\u5bfc\u914d\u4f53\u5728\u91d1\u5c5e\u4e0a\u53d1\u751f\u9762\u5f0f\u6298\u53e0\uff0c\u5b9e\u73b0\u914d\u4f53\u9762\u624b\u6027\u5230\u91d1\u5c5e\u7684\u4e2d\u5fc3\u624b\u6027\u518d\u5230\u4ea7\u7269\u624b\u6027\u7684\u4f20\u9012\u3002
<\/strong><\/p>\n
Fig. 6. <\/strong>Some design of chiral ligands<\/p>\n
\u5218\u5f3a\u8bfe\u9898\u7ec4\u6839\u636e\u201c\u5c0f\u4f4d\u963b\uff0c\u5bcc\u7535\u5b50\u201d\u8fd9\u4e00\u539f\u5219\u53d1\u5c55\u4e86\u9ad8\u6d3b\u6027\u7684PNN-Mn\u7edc\u5408\u7269\uff0c\u5b9e\u73b0\u4e86\u55b9\u5549\u30013,3-\u4e8c\u53d6\u4ee33-H\u5432\u54da\u3001\u55b9\u5594\u5549\u7b49\u5e95\u7269\u7684\u4e0d\u5bf9\u79f0\u6c22\u5316[12] [13]<\/sup>[14]<\/sup>\u3002<\/p>\n
\u5728\u5bf9\u55b9\u5549\u8fdb\u884c\u4e0d\u5bf9\u79f0\u6c22\u5316\u65f6\uff0c\u914d\u4f53\u4e0a\u7684N-H\u90e8\u5206\u53ef\u4ee5\u901a\u8fc7\u91d1\u5c5e-\u914d\u4f53\u534f\u540c\u4f5c\u7528\u663e\u8457\u5f71\u54cd\u50ac\u5316\u6c22\u5316\u53cd\u5e94\u7684\u53cd\u5e94\u6027\uff0c\u5f53\u914d\u4f53\u70f7\u57fa\u6c2e\u4e0a\u7684\u6c22\u88ab\u7532\u57fa\u53d6\u4ee3\u65f6\uff0c\u50ac\u5316\u5242\u7684\u53cd\u5e94\u6d3b\u6027\u6025\u5267\u4e0b\u964d\u3002\u800c\u54aa\u5511\u6c2e\u4e0a\u7684\u6c22\u88ab\u7532\u57fa\u53d6\u4ee3\u65f6\u53cd\u5e94\u6d3b\u6027\u548c\u9009\u62e9\u6027\u4e5f\u53d1\u751f\u4e86\u4e0b\u964d\u3002\u54aa\u5511\u4e0e\u55b9\u5549\u7684\u82ef\u5e76\u73af\u4e4b\u95f4\u5b58\u5728\u03c0-\u03c0\u76f8\u4e92\u4f5c\u7528\uff0c\u5b9e\u73b0\u4e86\u55b9\u5549\u50ac\u5316\u6c22\u5316\u7684\u624b\u6027\u63a7\u5236\u3002
<\/strong><\/p>\n
Fig. 7. <\/strong>Manganese-Catalyzed Asymmetric Hydrogenation of Quinolines Enabled by \u03c0\u2013\u03c0 Interaction<\/p>\n
\u4f7f\u7528Noyori-Ikariya\u50ac\u5316\u5242\u6c22\u53163,3-\u4e8c\u53d6\u4ee33-H\u5432\u54da\u65f6\uff0c\u751f\u6210\u91d1\u5c5e\u6c22\u7269\u79cd\u7684\u540c\u65f6\u4f1a\u751f\u6210\u7b49\u91cf\u7684\u8d28\u5b50\uff0c\u4f7f\u4e9a\u80fa\u6c2e\u88ab\u8d28\u5b50\u5316\u3002\u8d28\u5b50\u5316\u7684\u4e9a\u80fa\u6d3b\u6027\u6bd4\u8f83\u9ad8\uff0c\u5f88\u5feb\u5c31\u4f1a\u88ab\u948c-\u6c22\u7269\u79cd\u6c22\u5316\u3002\u5982\u679c\u5e95\u7269\u4e2d\u542b\u6709\u5421\u5576\u57fa\u56e2\uff0c\u751f\u6210\u7684\u8d28\u5b50\u4f1a\u8f6c\u79fb\u5230\u5421\u5576\u6c2e\u4e0a\uff0c\u964d\u4f4e\u4e86\u5e95\u7269\u7684\u6d3b\u6027\uff0c\u8fd9\u65f6\u4f7f\u7528Noyori-Ikariya\u578b\u50ac\u5316\u5242\u5c31\u96be\u4ee5\u5b9e\u73b0\u5bf93,3-\u4e8c\u53d6\u4ee33-H\u5432\u54da\u7684\u6c22\u5316\u3002\u800c\u4f7f\u7528PNN-Mn\u50ac\u5316\u5242\u65f6\uff0c\u56e0\u4e3a\u9530-\u6c22\u7269\u79cd\u6d3b\u6027\u9ad8\uff0c\u4e0d\u9700\u8981\u5c06\u4e9a\u80fa\u8d28\u5b50\u5316\u5c31\u80fd\u5b9e\u73b0\u5e95\u7269\u7684\u6c22\u5316\u3002
<\/strong><\/p>\n
Fig. 8.<\/strong> Manganese-Catalyzed Asymmetric Hydrogenation of\u00a03H<\/em>-Indoles<\/p>\n
\u5218\u5f3a\u8bfe\u9898\u7ec4\u53d1\u73b0\u4f7f\u7528PNN-Mn\u7edc\u5408\u7269\u8fdb\u884c\u55b9\u5594\u5549\u4e0d\u5bf9\u79f0\u6c22\u5316\u65f6\uff0c\u901a\u8fc7\u63a7\u5236\u53cd\u5e94\u6761\u4ef6\u53ef\u4ee5\u5b9e\u73b0\u5206\u522b\u5f97\u5230\u987a\u5f0f\u6216\u53cd\u5f0f\u7684\u6c22\u5316\u4ea7\u7269\uff0c\u53cd\u5e94\u5206\u4e24\u6b65\u5c06\u4e24\u4e2a\u53cc\u952e\u5206\u522b\u6c22\u5316\uff0c\u7b2c\u4e8c\u6b65\u6c22\u5316\u65f6\u50ac\u5316\u5242\u8fdb\u653b\u7684\u9762\u51b3\u5b9a\u4e86\u4ea7\u7269\u7684\u987a\u53cd\u3002\u4f7f\u7528\u666e\u901a\u6eb6\u5242\u65f6\u94a0\u79bb\u5b50\u5728\u914d\u4f53\u7684\u54aa\u5511\u73af\u548c\u5e95\u7269\u7684\u82ef\u5e76\u73af\u4e4b\u95f4\u7684\u9633\u79bb\u5b50-\u03c0\u76f8\u4e92\u4f5c\u7528\u8d77\u5230\u4e86\u5b9a\u4f4d\u7684\u529f\u80fd\uff0c\u914d\u4f53\u63a7\u5236\u4e86\u53e6\u4e00\u4e2a\u53cc\u952e\u6c22\u5316\u7684\u624b\u6027\u5c31\u5f97\u5230\u4e86\u53cd\u5f0f\u4ea7\u7269\u3002\u800c\u4f7f\u752815-\u51a0-5\u4f5c\u4e3a\u6eb6\u5242\u65f6\uff0c\u94a0\u79bb\u5b50\u88ab\u675f\u7f1a\uff0c\u9633\u79bb\u5b50-\u03c0\u4f5c\u7528\u6d88\u5931\uff0c\u7b2c\u4e8c\u6b65\u53cc\u952e\u6c22\u5316\u66f4\u503e\u5411\u4e8e\u4ece\u4f4d\u963b\u5c0f\u7684\u4e00\u4fa7\u63a5\u8fd1\uff0c\u4ece\u800c\u751f\u6210\u987a\u5f0f\u7684\u4ea7\u7269\u3002
<\/strong><\/p>\n
Fig. 9. <\/strong>Stereodivergent asymmetric hydrogenation of quinoxalines<\/p>\n
\u8fd1\u65e5\uff0c\u5218\u5f3a\u8bfe\u9898\u7ec4\u6210\u529f\u5c06\u03c3-\u8bf1\u5bfc\u6d3b\u5316\u4f5c\u7528\u5f15\u5165\u4e86\u4e0d\u5bf9\u79f0\u6c22\u5316\u53cd\u5e94\u4e2d\uff0c\u5b9e\u73b0\u4e86\u5728\u4e9a\u80fa\u7684\u4e0d\u5bf9\u79f0\u6c22\u5316\u4e2d\u7532\u57fa\u4e59\u57fa\u3001\u4ee5\u53ca\u6bd4\u7532\u57fa\u4e59\u57fa\u66f4\u96be\u7684\u4e19\u57fa\u4e01\u57fa\u7684\u533a\u5206[15]<\/sup>\u3002<\/p>\n
<\/strong><\/p>\n
Fig. 10. <\/strong>Control experiments including sodium cation capture, the change of base and solvent<\/p>\n
\u5411\u4f53\u7cfb\u4e2d\u52a0\u516515-\u51a0-5\u4f1a\u4f7f\u4f7fee\u503c\u5927\u5e45\u964d\u4f4e\uff0c\u91d1\u5c5e\u79bb\u5b50\u7531\u94a0\u6362\u6210\u94be\u4e5f\u5bfc\u81f4\u4e86ee\u503c\u7684\u964d\u4f4e\uff0c\u8bf4\u660e\u94a0\u79bb\u5b50\u5728\u624b\u6027\u63a7\u5236\u4e2d\u8d77\u5230\u4e86\u6781\u4e3a\u91cd\u8981\u7684\u4f5c\u7528\u3002<\/p>\n
<\/strong><\/p>\n
Fig. 11. <\/strong>Four hydride transfer transition states involving sodium cations. For hydride transfer transition states via \u03c3-coordination interactions, Z-S-TS4 is favored over E-R-TS6 by 2.2 kcal mol-1<\/sup>; For hydride transfer transition states via cation-\u03c0 interactions, the energy barriers via E-S-TS8 and Z-R-TS9 are 15.4 kcal mol-1<\/sup> higher than that via the favorable transition state Z-S-TS4.<\/p>\n
\u8ba1\u7b97\u8868\u660e\uff0c\u94a0\u79bb\u5b50\u4e0e\u914d\u4f53\u7684\u54aa\u5511\u57fa\u56e2\u5e76\u4e0d\u5904\u4e8e\u540c\u4e00\u5e73\u9762\u5185\uff0c\u800c\u662f\u7565\u9ad8\u4e8e\u54aa\u5511\u73af\u7684\u5e73\u9762\uff0c\u4ece\u800c\u5b9e\u73b0\u4e86\u5728\u5e95\u7269\u6c2e\u5728\u03c3-\u952e\u65b9\u5411\u4e0a\u7684\u03c3-\u8bf1\u5bfc\u6d3b\u5316\uff0c\u9664\u6b64\u4ee5\u5916\uff0c\u5e95\u7269\u82ef\u73af\u4e0a\u7684\u7532\u6c27\u57fa\u4e0e\u94a0\u79bb\u5b50\u7684\u914d\u4f4d\u4e5f\u5bf9\u5e95\u7269\u53d6\u5411\u6709\u91cd\u8981\u7684\u4f5c\u7528\u3002\u540c\u65f6\u914d\u4f53\u6c2e\u4e0a\u7684\u6c22\u4e0e\u91d1\u5c5e\u6c22\u4ece\u03c0\u952e\u7684\u65b9\u5411\u63a5\u8fd1\u5e95\u7269\uff0c\u5b9e\u73b0\u4e86\u5e95\u7269\u5728\u03c0-\u952e\u65b9\u5411\u7684\u6d3b\u5316\u3002\u4e8c\u6c27\u516d\u73af\u4e0e\u94a0\u79bb\u5b50\u914d\u4f4d\u5f62\u6210\u4e86\u5de8\u5927\u7684\u4f4d\u963b\uff0c\u8ba9\u5e95\u7269\u4e2d\u8f83\u5927\u7684\u57fa\u56e2\u8fdc\u79bb\u94a0\u79bb\u5b50\u7684\u65b9\u5411\u3002\u50ac\u5316\u5242\u5728\u4e9a\u80faC=N\u53cc\u952e\u03c3-\u8f68\u9053\u65b9\u5411\u548c\u03c0-\u8f68\u9053\u65b9\u5411\u5171\u540c\u5bf9\u5e95\u7269\u4f5c\u7528\uff0c\u5b9e\u73b0\u4e86\u5f3a\u5927\u7684\u6d3b\u5316\u80fd\u529b\u548c\u7acb\u4f53\u63a7\u5236\u80fd\u529b\u3002\u800c\u5f53\u91d1\u5c5e\u79bb\u5b50\u6362\u6210\u94be\u65f6\uff0c\u7531\u4e8e\u94be\u7684\u534a\u5f84\u66f4\u5927\uff0c\u50ac\u5316\u5242\u7684\u7acb\u4f53\u63a7\u5236\u80fd\u529b\u968f\u4e4b\u964d\u4f4e\uff0c\u4e0d\u5bf9\u79f0\u6c22\u5316\u7684\u7acb\u4f53\u9009\u62e9\u6027\u4e5f\u968f\u4e4b\u4e0b\u964d\u3002<\/p>\n
\u603b\u7ed3<\/strong><\/h4>\n
\u9530\u50ac\u5316\u6c22\u5316\u867d\u7136\u53d1\u5c55\u6bd4\u8f83\u665a\uff0c\u4f46\u662f\u8fd1\u51e0\u5e74\u7684\u53d1\u5c55\u4e5f\u6bd4\u8f83\u8fc5\u901f\uff0c\u4eba\u4eec\u5bf9\u673a\u7406\u7684\u8ba4\u8bc6\u4ece\u6700\u65e9\u7b80\u5355\u7684\u5916\u7403\u673a\u7406\uff0c\u5230\u78b1\u91d1\u5c5e\u79bb\u5b50\u4ecb\u5bfc\u7684\u03c0-\u8f68\u9053\u65b9\u5411\u6d3b\u5316\uff0c\u518d\u5230\u03c3-\u8bf1\u5bfc\u6d3b\u5316\uff0c\u914d\u4f53\u4e5f\u4ece\u7b80\u5355\u7684\u6d88\u65cbPNP\u914d\u4f53\u9010\u6b65\u53d1\u5c55\u4e3a\u5177\u6709\u5f3a\u5927\u7acb\u4f53\u9009\u62e9\u6027\u548c\u50ac\u5316\u6d3b\u6027\u7684\u4e8c\u8302\u94c1PNN\u914d\u4f53\uff0c\u5747\u76f8\u9530\u50ac\u5316\u4e0d\u5bf9\u79f0\u6c22\u5316\u53cd\u5e94\u5728\u53cd\u5e94\u6d3b\u6027\u548c\u4e0d\u5bf9\u79f0\u9009\u62e9\u6027\u4e0a\u663e\u793a\u4e86\u5de8\u5927\u7684\u6f5c\u529b\u3002<\/p>\n
\u00a0<\/strong>\uff08\u975e\u5e38\u611f\u8c22\u5218\u5f3a\u6559\u6388\u8bfe\u9898\u7ec4\u738b\u660e\u626c\u535a\u58eb\u5bf9\u672c\u6587\u7684\u6307\u5bfc\uff09<\/strong><\/p>\n
\u53c2\u8003\u6587\u732e<\/strong>\uff1a<\/h4>\n
\n
- [1]\u00a0 Saravanakumar Elangovan, Christoph Topf, Steffen Fischer, Haijun Jiao, Anke Spannenberg, Wolfgang Baumann, Ralf Ludwig, Kathrin Junge, and Matthias Beller*, Selective Catalytic Hydrogenations of Nitriles, Ketones, and Aldehydes by Well-Defined Manganese Pincer Complexes,J. Am. Chem. Soc.<\/em>2016<\/strong>, 138, 8809\u20138814.<\/li>\n
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- [4]\u00a0 Marcel Garbe, Kathrin Junge, Svenja Walker, Zhihong Wei, Haijun Jiao, Anke Spannenberg, Stephan Bachmann, Michelangelo Scalone, Matthias Beller*, Manganese(I)-Catalyzed Enantioselective Hydrogenation of Ketones Using a Defined Chiral PNP Pincer Ligand,Angew. Chem. Int. Ed.<\/em>2017<\/strong>, 56, 11237\u201311241.<\/li>\n
- [5]\u00a0 Magnus B. Widegren, Gavin J. Harkness, Alexandra M. Z. Slawin*, David B. Cordes*, Matthew L. Clarke*, A Highly Active Manganese Catalyst for Enantioselective Ketone and Ester Hydrogenation,Angew. Chem. Int. Ed.<\/em>2017<\/strong>, 56, 5825\u20135828.<\/li>\n
- [6]\u00a0 M.\u2005Sc. Viktoriia Zubar, Yury Lebedev, Luis Miguel Azofra, Luigi Cavallo*, Osama El-Sepelgy*, Magnus Rueping*,\u00a0Hydrogenation of CO2-Derived Carbonates and Polycarbonates to Methanol and Diols by Metal\u2013Ligand Cooperative Manganese Catalysis,Angew. Chem. Int. Ed.<\/em>\u00a02018<\/strong>,\u00a057, 13439.<\/li>\n
- [7]\u00a0 Yujie Wang, Lei Zhu, Zhihui Shao, Gang Li, Yu Lan*, and Qiang Liu*, Unmasking the Ligand Effect in Manganese-Catalyzed Hydrogenation: Mechanistic Insight and Catalytic Application,J. Am. Chem. Soc.<\/em>2019<\/strong>,141<\/em>, 17337\u201317349.<\/li>\n
- [8]\u00a0 Yujie Wang, Shihan Liu, Haobo Yang, Hengxu Li, Yu Lan*, and Qiang Liu*, Structure, reactivity and catalytic properties of manganese-hydride amidate complexes,Nat. Chem.<\/em>2022<\/strong>,14<\/em>, 1233\u20131241.<\/li>\n
- [9]\u00a0 Shihan Liu, Haobo Yang, Ya-Nan Wang, Qiaoqiao Zhao, Yujie Wang*, Ruopeng Bai*, Qiang Liu*, and Yu Lan*, \u00a0Enhancing Hydride Transfer in Catalytic Hydrogenation via \u03c3-Electron-Induced Polarization of Imines,J. Am. Chem. Soc.<\/em>2024<\/strong>, 146, 24, 16357\u201316362.<\/li>\n
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- [12] Chenguang Liu, Mingyang Wang, Shihan Liu, Yujie Wang, Yong Peng, Yu Lan*, Qiang Liu*, Manganese-Catalyzed Asymmetric Hydrogenation of Quinolines Enabled by \u03c0\u2013\u03c0 Interaction,Angew. Chem. Int. Ed.<\/em>2021<\/strong>, 60, 5108\u20135113.<\/li>\n
- [13] Chenguang Liu, Mingyang Wang, Yihan Xu, Yibiao Li, Qiang Liu*, Manganese-Catalyzed Asymmetric Hydrogenation of 3H-Indoles,Angew. Chem. Int. Ed.<\/em>2022<\/strong>, 61, e202202814.<\/li>\n
- [14] Chenguang Liu, Xufang Liu, Qiang Liu*,Chem<\/em>2023<\/strong>, 9, 2585\u20132600.<\/li>\n
- [15] Mingyang Wang, Shihan Liu, Hao Liu, Yujie Wang, Yu Lan* and Qiang Liu*, Asymmetric hydrogenation of ketimines with minimally different alkyl groups,Nature <\/em>2024<\/strong>, 1\u20132.<\/li>\n<\/ul>\n
\u672c\u6587\u7248\u6743\u5c5e\u4e8e Chem-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":"\u672c\u6587\u4f5c\u8005\uff1aAzathoth \u00a0\u00a0\u00a0\u00a0\u00a0\u00a0\u00a0\u00a0\u00a0\u00a0\u00a0\u00a0\u00a0\u00a0\u00a0\u00a0\u00a0\u00a0\u00a0\u00a0\u00a0\u00a0\u00a0\u00a0\u00a0\u00a0\u00a0\u00a0\u00a0\u5199\u4f5c\u6307\u5bfc\uff1aCyclization Xu \u5bfc\u8bfb\uff1a \u672c\u6587\u4ecb\u7ecd\u4e86\u9530\u50ac\u5316\u6c22\u5316\u9886\u57df\u7684\u7814\u7a76\u8fdb\u5c55\u3002\u6587\u4e2d\u63cf\u8ff0\u4e86\u4e0d\u540c\u7c7b\u578b\u9530\u50ac\u5316\u5242\u7684\u8bbe\u8ba1\u4e0e\u6027\u80fd\uff0c\u901a\u8fc7\u5206\u6790\u4e0d\u540c\u914d\u4f53\u548c\u53cd\u5e94\u6761\u4ef6\u5bf9\u50ac\u5316\u6548\u7387\u548c\u9009\u62e9\u6027\u7684\u5f71\u54cd\uff0c\u5c55\u793a\u4e86\u9530\u50ac\u5316\u5242\u5728\u4e0d\u5bf9\u79f0\u6c22\u5316\u53cd\u5e94\u4e2d\u7684\u6f5c\u529b\u3002\u6e05\u534e\u5927\u5b66\u5218\u5f3a\u56e2\u961f\u63d0\u51fa\u4e86\u5173\u4e8e\u9530\u50ac\u5316\u6c22\u5316\u7684\u591a\u79cd\u6d3b\u5316\u6a21\u578b\uff0c\u5e76\u5c06\u5176\u5e94\u7528\u5728\u50ac\u5316\u5242\u7684\u8bbe\u8ba1\u4e0a\uff0c\u63a8\u52a8\u4e86\u8be5\u9886\u57df\u7684\u5feb\u901f\u53d1\u5c55\u3002 \u6b63\u6587\uff1a \u9530\u662f\u4ec5\u6b21\u4e8e\u94c1\u3001\u949b\uff0c\u50a8\u91cf\u6392\u7b2c\u4e09\u4f4d\u7684\u8fc7\u6e21\u91d1\u5c5e\uff0c\u5177\u6709\u5f88\u5927\u7684\u5e94\u7528\u4ef7\u503c\u3002\u63d0\u5230\u9530\u50ac\u5316\u7684\u4e0d\u5bf9\u79f0\u53cd\u5e94\uff0c\u6211\u4eec\u9996\u5148\u60f3\u5230\u7684\u5c31\u662f\u8bfe\u672c\u4e0a\u7684Jacobsen\u2013Katsuki\u4e0d\u5bf9\u79f0\u73af\u6c27\u5316\u3002\u4f46\u662f\u5747\u76f8\u9530\u50ac\u5316\u7684\u6c22\u5316\u4e00\u76f4\u52302016\u5e74\u624d\u5f00\u59cb\u53d1\u5c55\uff0c\u5c5e\u4e8e\u4e00\u4e2a\u6bd4\u8f83\u65b0\u7684\u9886\u57df\u3002\u76ee\u524d\u7684\u5df2\u77e5\u7684\u9530\u50ac\u5316\u6c22\u5316\u90fd\u662f\u5916\u7403\u673a\u7406\uff0c\u5bf9\u4e8e\u5916\u7403\u673a\u7406\u7684\u91d1\u5c5e\u50ac\u5316\u4e0d\u5bf9\u79f0\u6c22\u5316\u800c\u8a00\uff0c\u53cd\u5e94\u6700\u91cd\u8981\u7684\u4e24\u6b65\u662f\u91d1\u5c5e\u6c22\u7269\u79cd\u7684\u751f\u6210\u548c\u6c22\u8d1f\u7684\u8f6c\u79fb\u3002\u4f46\u8fd9\u4e24\u6b65\u7684\u5f71\u54cd\u56e0\u7d20\u5f80\u5f80\u662f\u76f8\u4e92\u77db\u76fe\u7684\uff0c\u91d1\u5c5e\u6c22\u7269\u79cd\u7684\u6d3b\u6027\u8d8a\u9ad8\uff0c\u6c22\u8d1f\u8d8a\u5bb9\u6613\u8f6c\u79fb\uff0c\u7136\u800c\u4e5f\u610f\u5473\u7740\u91d1\u5c5e\u6c22\u7269\u79cd\u4e5f\u5c31\u8d8a\u96be\u751f\u6210\u3002\u5bf9\u4e8e\u948c\u94d1\u7b49\u9760\u540e\u7684\u8fc7\u6e21\u91d1\u5c5e\u800c\u8a00\uff0c\u5b83\u4eec\u7684\u91d1\u5c5e\u6c22\u7269\u79cd\u751f\u6210\u548c\u6c22\u8d1f\u8f6c\u79fb\u6070\u597d\u8fbe\u5230\u4e86\u4e00\u4e2a\u5e73\u8861\uff0c\u91d1\u5c5e\u6c22\u7269\u79cd\u65e2\u5bb9\u6613\u751f\u6210\u4e5f\u5bb9\u6613\u4e0e\u5e95\u7269\u53d1\u751f\u53cd\u5e94\u3002\u800c\u5bf9\u4e8e\u7b2c\u4e00\u884c\u8fc7\u6e21\u91d1\u5c5e\u800c\u8a00\uff0c\u91d1\u5c5e\u6c22\u7269\u79cd\u7684\u6d3b\u6027\u975e\u5e38\u9ad8\uff0c\u867d\u7136\u8fd9\u610f\u5473\u7740\u5f3a\u5927\u7684\u53cd\u5e94\u6d3b\u6027\uff0c\u4f46\u540c\u65f6\u4e5f\u5bfc\u81f4\u4e86\u91d1\u5c5e\u6c22\u7269\u79cd\u975e\u5e38\u96be\u4ee5\u751f\u6210\u3002 Fig.1. Typical outer-sphere mechanism catalytic hydrogenation \u76ee\u524d\u516c\u8ba4\u6700\u65e9\u7684\u5747\u76f8\u9530\u50ac\u5316\u6c22\u5316\u662f\u7531Beller \u7b49\u4eba\u5b9e\u73b0\u7684[1]\uff0c\u4ed6\u4eec\u7528PNP\u4e09\u9f7f\u914d\u4f53\u548c\u9530\u7684\u7edc\u5408\u7269\u5b9e\u73b0\u4e86\u82ef\u8148\u3001\u919b\u3001\u916e\u7684\u6c22\u5316\u3002Beller\u7684\u7814\u7a76\u8868\u660e\uff0c\u9530\u50ac\u5316\u5242\u5fc5\u987b\u8981\u6709\u4e00\u6c27\u5316\u78b3\u914d\u4f4d\uff0c\u901a\u8fc7\u53cd\u4f4d\u6548\u5e94\u6765\u7a33\u5b9a\u9530-\u6c22\u952e\uff0c\u5426\u5219\u9530\u6c22\u7269\u79cd\u7684\u80fd\u91cf\u4f1a\u975e\u5e38\u9ad8\uff0c\u96be\u4ee5\u751f\u6210\uff0c\u4ece\u800c\u65e0\u6cd5\u5b9e\u73b0\u50ac\u5316\u6c22\u5316\u3002 Scheme 1. One of the earliest homogeneous manganese-catalyzed hydrogenation reactions: hydrogenation of nitriles.Fig.2. Mechanism of manganese-catalyzed hydrogenation \u5f71\u54cd\u53cd\u5e94\u6d3b\u6027\u65e0\u5916\u4e4e\u4e24\u4e2a\u4e3b\u8981\u539f\u56e0\uff1a\u7a7a\u95f4\u4f4d\u963b\u548c\u7535\u5b50\u6548\u5e94\u3002\u5bf9\u4e8e\u5747\u76f8\u7684\u9530\u50ac\u5316\u6c22\u5316\u53cd\u5e94\u800c\u8a00\uff0c\u5728\u4e00\u5b9a\u7a0b\u5ea6\u4e0a\u66f4\u5bcc\u7535\u5b50\u3001\u66f4\u5c0f\u4f4d\u963b\u7684\u50ac\u5316\u5242\u62e5\u6709\u76f8\u5bf9\u66f4\u9ad8\u7684\u6d3b\u6027\u3002\u5c0f\u7684\u4f4d\u963b\u6709\u5229\u4e8e\u50ac\u5316\u5242\u4e0e\u5e95\u7269\u63a5\u8fd1\uff0c\u800c\u5bcc\u7535\u5b50\u6709\u5229\u4e8e\u63d0\u9ad8\u91d1\u5c5e\u6c22\u7269\u79cd\u7684\u4eb2\u6838\u80fd\u529b\u3002\u5982Kempt\u7684\u5de5\u4f5c\u6240\u793a\uff0c\u5f53\u5421\u5576\u914d\u4f4d\u57fa\u56e2\u7684\u5bf9\u4f4d\u6709\u6c28\u57fa\u53d6\u4ee3\u65f6\uff0c\u50ac\u5316\u5242\u7684\u6d3b\u6027\u4f1a\u5f97\u5230\u63d0\u5347[2]\u3002Beller\u540e\u7eed\u7684\u5de5\u4f5c\u4e5f\u663e\u793a\u4e86\u4f4d\u963b\u5bf9\u50ac\u5316\u5242\u6d3b\u6027\u7684\u5f71\u54cd[3]\u3002Scheme 2. The enhancement of the electron-donating ability of the ligand is beneficial for improving catalytic activity. Scheme 3. The reduction of ligand steric hindrance is beneficial for improving catalytic activity. Beller \u3001Clarke\u3001Rueping\u3001Balskus\u7b49\u4eba\u5206\u522b\u4ee5\u54aa\u5511\u3001\u5421\u5576\u4e3a\u914d\u4f4d\u57fa\u56e2\u8bbe\u8ba1\u4e86PNN\u914d\u4f53[4] [5] [6]\uff0cPNN-Mn\u7684\u50ac\u5316\u6d3b\u6027\u76f8\u5bf9\u4e8ePNP-Mn\u50ac\u5316\u5242\u6709\u5de8\u5927\u7684\u63d0\u5347\u3002PNN-Mn\u50ac\u5316\u5242\u53ef\u4ee5\u6c22\u5316\u5982\u9170\u80fa\u3001\u916f\u548c\u78b3\u9178\u916f\u8fd9\u4e9b\u5177\u6709\u5f88\u5927\u6311\u6218\u6027\u7684\u5e95\u7269\uff0c\u8fd9\u662f\u5f88\u591aPNP-Mn\u50ac\u5316\u5242\u96be\u4ee5\u5b9e\u73b0\u7684\u3002 Scheme 4. In most cases, PNN ligands exhibit higher reaction activity than PNP ligands. \u540e\u6765\u6e05\u534e\u5927\u5b66\u5218\u5f3a\u548c\u91cd\u5e86\u5927\u5b66\u84dd\u5b87\u89e3\u91ca\u4e86PNN-Mn\u7edc\u5408\u7269\u6d3b\u6027\u5f3a\u4e8ePNP-Mn\u7edc\u5408\u7269\u7684\u539f\u56e0\uff1a\u4ed6\u4eec\u8ba4\u4e3aPNN\u914d\u4f53\u76f8\u5bf9\u4e8ePNP\u914d\u4f53\u7684\u4f18\u52bf\u5728\u4e8e\u4f4d\u963b\u5c0f\u3001\u5bcc\u7535\u5b50\uff0c\u5927\u5927\u964d\u4f4e\u4e86\u6c22\u5316\u53cd\u5e94\u7684\u80fd\u5792[7]\u3002 Fig.3. Reasons for higher activity of PNN ligands: reduced steric hindrance, electron-rich nature, lowering the energy of substrate-catalyst adducts, facilitating easier reactions. \u968f\u7740\u4ee5\u4e0a\u7814\u7a76\u7684\u6df1\u5165\uff0c\u4ed6\u4eec\u901a\u8fc7\u5206\u79bb\u4e2d\u95f4\u4f53\u8fdb\u884c\u6c22\u5316\u5b9e\u9a8c\u7b49\u65b9\u5f0f\u53d1\u73b0\uff0c\u914d\u4f53\u4e0e\u78b1\u5f62\u6210\u6c2e\u8d1f\u79bb\u5b50-\u78b1\u91d1\u5c5e\u76d0\u4e4b\u540e\u5f80\u5f80\u53cd\u5e94\u6d3b\u6027\u66f4\u9ad8\u3002\u56e0\u4e3a\u78b1\u91d1\u5c5e\u79bb\u5b50\u53ef\u4ee5\u7a33\u5b9a\u91d1\u5c5e\u6c22\u7269\u79cd\u4e0e\u5e95\u7269\u7684\u52a0\u5408\u7269\uff0c\u800c\u4e14\u8d1f\u79bb\u5b50\u7684\u5f62\u6210\u8fd8\u80fd\u4f7f\u5f97\u914d\u4f53\u66f4\u5bcc\u7535\u5b50\uff0c\u589e\u5f3a\u4e86\u91d1\u5c5e\u4e0a\u6c22\u8d1f\u7684\u4eb2\u6838\u80fd\u529b\uff0c\u5b9e\u73b0\u4e86\u78b1\u91d1\u5c5e\u79bb\u5b50\u4ecb\u5bfc\u7684\u03c0\u8f68\u9053\u65b9\u5411\u6d3b\u5316[8]\u3002 Fig.4. Alkali metal ion-mediated \u03c0-activation […]","protected":false},"author":26,"featured_media":50997,"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":[624,4419,4418,4417],"jetpack_publicize_connections":[],"jetpack_featured_media_url":"https:\/\/assets.www.gsbet888.com\/uploads\/2024\/08\/2382c315a6ba396be1932dd8dafaff52-1.png","jetpack_shortlink":"https:\/\/wp.me\/p96op1-dgw","jetpack_sharing_enabled":true,"_links":{"self":[{"href":"\/\/www.gsbet888.com\/wp-json\/wp\/v2\/posts\/50996"}],"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\/26"}],"replies":[{"embeddable":true,"href":"\/\/www.gsbet888.com\/wp-json\/wp\/v2\/comments?post=50996"}],"version-history":[{"count":7,"href":"\/\/www.gsbet888.com\/wp-json\/wp\/v2\/posts\/50996\/revisions"}],"predecessor-version":[{"id":51038,"href":"\/\/www.gsbet888.com\/wp-json\/wp\/v2\/posts\/50996\/revisions\/51038"}],"wp:featuredmedia":[{"embeddable":true,"href":"\/\/www.gsbet888.com\/wp-json\/wp\/v2\/media\/50997"}],"wp:attachment":[{"href":"\/\/www.gsbet888.com\/wp-json\/wp\/v2\/media?parent=50996"}],"wp:term":[{"taxonomy":"category","embeddable":true,"href":"\/\/www.gsbet888.com\/wp-json\/wp\/v2\/categories?post=50996"},{"taxonomy":"post_tag","embeddable":true,"href":"\/\/www.gsbet888.com\/wp-json\/wp\/v2\/tags?post=50996"}],"curies":[{"name":"wp","href":"https:\/\/api.w.org\/{rel}","templated":true}]}},{"id":50990,"date":"2024-08-26T08:34:54","date_gmt":"2024-08-26T00:34:54","guid":{"rendered":"\/\/www.gsbet888.com\/?p=50990"},"modified":"2024-08-26T08:37:52","modified_gmt":"2024-08-26T00:37:52","slug":"%e7%bb%b4%e5%b0%94%e8%8c%a8%e5%a0%a1%e5%a4%a7%e5%ad%a6jake-l-greenfield%e7%bb%84%e6%8b%9b%e8%81%98%e5%90%af%e4%ba%8b","status":"publish","type":"post","link":"\/\/www.gsbet888.com\/chemnews\/%e6%8b%9b%e8%81%98%e4%bf%a1%e6%81%af\/2024\/08\/%e7%bb%b4%e5%b0%94%e8%8c%a8%e5%a0%a1%e5%a4%a7%e5%ad%a6jake-l-greenfield%e7%bb%84%e6%8b%9b%e8%81%98%e5%90%af%e4%ba%8b.html","title":{"rendered":"\u7ef4\u5c14\u8328\u5821\u5927\u5b66Jake L.Greenfield\u7ec4\u62db\u8058\u542f\u4e8b"},"content":{"rendered":"
\u4e00\u3001\u8bfe\u9898\u7ec4\u957f\u4ecb\u7ecd<\/strong><\/h4>\n
Jake L. Greenfield<\/strong>\u535a\u58eb\u4e8e2011-2015\u5e74\u4f26\u6566\u5e1d\u56fd\u7406\u5de5\u5b66\u9662\u5b8c\u6210\u672c\u79d1\u4e0e\u7855\u58eb\u5b66\u4e60\uff08\u672c\u7855\u5b66\u4e60\uff0c2011-2015\uff0cProf. Milo S. P. Shaffer\uff09\uff0c\u5e76\u5728\u4f50\u6cbb\u4e9a\u7406\u5de5\u5b66\u9662\uff082014\uff0cProf. Christopher W. Jones\uff09\u8fdb\u884c\u4e86\u4e3a\u671f5\u4e2a\u6708\u7684\u5168\u989d\u8d44\u52a9\u7814\u7a76\u3002Jake\u5728\u5251\u6865\u5927\u5b66Prof. Jonathan R. Nitschke\uff08\u5316\u5b66\u535a\u58eb\uff0c2015-2019\uff09\u7684\u6307\u5bfc\u4e0b\u83b7\u5f97\u535a\u58eb\u5b66\u4f4d\u30022019\u5e74\u535a\u58eb\u6bd5\u4e1a\u540e\uff0cJake\u56de\u5230\u5e1d\u56fd\u7406\u5de5\u5b66\u9662\uff0c\u5728Matthew J. Fuchter\u6559\u6388\u8bfe\u9898\u7ec4\u505a\u535a\u540e\u7814\u7a76\u30022022\u5e74\uff0cJake\u642c\u5230\u7ef4\u5c14\u8328\u5821\uff08\u5fb7\u56fd\uff09\u4e0eFrank W\u00fcrthner\u6559\u6388\u5408\u4f5c\uff0c\u6700\u521d\u662f\u7531\u6d2a\u5821\u8d44\u52a9\u7684\u535a\u540e\uff0c\u4e0d\u4e45\u4e4b\u540e\uff0c\u57282023\u5e74\uff0cJake\u83b7\u5f97\u4e86\u7531\u5316\u5b66\u5de5\u4e1a\u57fa\u91d1\u4f1a\u8d44\u52a9\u7684Liebig\u5956\u91d1\uff0c\u5f00\u59cb\u4e86\u72ec\u7acb\u7684\u7814\u7a76\u751f\u6daf\uff0c\u540c\u65f6\u6210\u4e3a\u5b66\u9662\u7684Emil Fischer\u7814\u7a76\u5458\u3002<\/p>\n
\u8bfe\u9898\u7ec4\u7f51\u9875\uff1aDr Jake Greenfield – (uni-wuerzburg.de)<\/a><\/p>\n
\u4e8c\u3001\u8bfe\u9898\u7ec4\u7b80\u4ecb<\/strong><\/h4>\n
Jake\u8bfe\u9898\u7ec4\u4e8e2023\u5e74\u6b63\u5f0f\u6210\u7acb\uff0c\u4e3b\u8981\u7814\u7a76\u65b9\u5411\u4e3a\u5149\u54cd\u5e94\u52a8\u6001\u5171\u4ef7\u5316\u5b66\u3002\u76ee\u524d\uff0cJake\u5c0f\u7ec4\u7684\u524d\u4e24\u7bc7\u8bba\u6587\u5206\u522b\u53d1\u8868\u5728Chem. Sci.<\/em> (
Chem. Sci.<\/em>, 2024,15<\/strong>, 3872\u20133878<\/a>) \u548cJACS<\/em> (J. Am. Chem. Soc.<\/em>, 2024,146<\/strong>, 20720\u201320727<\/a>)\u4e0a\uff0c\u4e3b\u8981\u4e13\u6ce8\u4e8e\u5f00\u53d1\u4e00\u7c7b\u65b0\u578b\u7684\u4e9a\u80fa\u5149\u5f00\u5173\u3002\u81ea20\u4e16\u7eaa50\u5e74\u4ee3\u4ee5\u6765\uff0c\u5149\u5207\u6362\u4e9a\u80fa\u7684\u6784\u5efa\u4e00\u76f4\u4ee5\u6765\u662f\u4e00\u4e2a\u91cd\u5927\u6311\u6218\uff0c\u7279\u522b\u662f\u919b\u4e9a\u80fa\u3002\u7136\u800c\uff0c\u57282024\u5e74\uff0cJake\u5c0f\u7ec4\u53d1\u73b0\u4e86\u4e00\u7c7b\u65b0\u578b\u7684\u5149\u5207\u6362\u4e9a\u80fa\uff0c\u5176\u5728\u53ef\u89c1\u5149\u7167\u5c04\u4e0b\u5b9e\u53ef\u4ee5\u5b9e\u73b0>95%\u7684Z<\/em>-\u5f02\u6784\u4f53\uff0c\u5e76\u4e14\u6781\u5927\u7684\u63d0\u9ad8Z<\/em>-\u5f02\u6784\u4f53\u7684\u534a\u8870\u671f(19.2 h)\u3002\u57fa\u4e8e\u52a8\u6001\u5171\u4ef7\u548c\u5149\u54cd\u5e94\u7279\u6027\u7684\u5149\u5207\u6362\u4e9a\u80fa\uff0c\u5728\u8fde\u7eed\u7167\u5c04\u4e0b\u53ef\u88ab\u8fdb\u4e00\u6b65\u7528\u4e8e\u4ea7\u751f\u201c\u4fe1\u606f\u68d8\u8f6e\u201d\u3002\u76ee\u524d\uff0cJake\u5c0f\u7ec4\u5bf9\u5149\u5207\u6362\u4e9a\u80fa\u7684\u5404\u4e2a\u65b9\u9762\u7684\u7814\u7a76\u8fdb\u884c\u4e86\u63a2\u7d22(\u57fa\u7840\u548c\u5e94\u7528\u8fdb\u884c\u7814\u7a76)\uff0c\u5e76\u4e0e\u5176\u4ed6\u76f8\u5173\u8bfe\u9898\u7ec4\u548c\u884c\u4e1a\u7b49\u5efa\u7acb\u4e86\u8bb8\u591a\u611f\u5174\u8da3\u7684\u5408\u4f5c\u3002<\/p>\n\u76ee\u524d\uff0cJake\u5c0f\u7ec4\u7684\u56e2\u961f\u9ad8\u5ea6\u56fd\u9645\u5316\uff0c\u6210\u5458\u5206\u522b\u6765\u81ea\u82f1\u56fd\u3001\u4e2d\u56fd\u3001\u5370\u5ea6\u548c\u5fb7\u56fd\u3002\u4ed6\u4eec\u662f\u4e00\u4e2a\u96c4\u5fc3\u52c3\u52c3\u7684\u56e2\u4f53\uff0c\u975e\u5e38\u9002\u5408\u60f3\u8981\u8ffd\u6c42\u5b66\u672f\u751f\u6daf\u7684\u5b66\u751f\u3002Jake\u5c0f\u7ec4\u7684\u5b9e\u9a8c\u5ba4\u4f4d\u4e8e\u5fb7\u56fd\u7ef4\u5c14\u8328\u5821\u5927\u5b66\u6709\u673a\u5316\u5b66\u7814\u7a76\u6240\uff0c\u53ef\u4ee5\u4f7f\u7528\u7ef4\u5c14\u8328\u5821\u201c\u7eb3\u7c73\u7cfb\u7edf\u5316\u5b66\u4e2d\u5fc3\uff08CNC\uff09\u201d\u7684\u6700\u5148\u8fdb\u8bbe\u65bd\u3002\u6b64\u5916\uff0c\u867d\u7136Jake\u7ec4\u662f\u72ec\u7acb\u7684\uff0c\u4f46\u4e0eFrank W\u00fcrthner\u6559\u6388\u7684\u56e2\u961f\u5171\u4eab\u5b9e\u9a8c\u5ba4\u7a7a\u95f4\u548c\u7ec4\u4f1a\uff0c\u4ece\u800c\u5e7f\u6cdb\u63a5\u89e6\u4e0d\u540c\u7c7b\u578b\u7684\u5316\u5b66\u3002<\/p>\n
\u5982\u679c\u60a8\u5bf9\u8be5\u56e2\u961f\u7684\u535a\u58eb\u751f\u751a\u81f3\u535a\u58eb\u540e\u7814\u7a76\u611f\u5174\u8da3\uff0c\u8bf7\u5c3d\u65e9\u901a\u8fc7\u7535\u5b50\u90ae\u4ef6\u8054\u7cfbJake\u6559\u6388(
Jake.Greenfield@uni-wuerzburg.de<\/a>)\u3002\u4f60\u6240\u63d0\u4ea4\u7533\u8bf7\u6750\u6599\u5e94\u8be5\u5305\u62ec\u7b80\u5386\uff0c\u5de5\u4f5c\u603b\u7ed3\uff0c\u4e24\u5c01\u63a8\u8350\u4fe1\u3002\u4f60\u4e5f\u53ef\u4ee5\u5728\u7533\u8bf7\u524d\u901a\u8fc7\u975e\u6b63\u5f0f\u7684\u90ae\u4ef6\u8fdb\u884c\u8054\u7cfb\u3002<\/p>\nOur research group was officially established in 2023 and have the general interest in photoresponsive dynamic-covalent chemistry. Our group\u2019s first two papers, published inChem. Sci.<\/em> (Chem. Sci.<\/em>, 2024,15<\/strong>, 3872\u20133878) andJACS<\/em> (J. Am. Chem. Soc.<\/em>, 2024,146<\/strong>, 20720\u201320727), focused on exploring a new class of imine-based photoswitches that we discovered, the aryliminopyrazoles. Achieving photoswitchable imines, specifically aldimines, has been a long-standing challenge since the 1950\u2019s. However, in 2024,\u00a0 we discovered a new class of photoswitchable imines that can achieve >95% Z-isomer under visible light irradiation and have a thermal half-life of 19.2 h compared to the previously reported time of less than 1 min at room temperature. These photoswitchable imines, combining dynamic covalent and photoresponsive properties, were further used to generate an \u201cinformation ratchet\u201d under continuous irradiation. Currently, we are working on all aspects of using our photoswitchable imines (fundamentals and applications) and are also interested in establishing collaborations.<\/p>\n
Our team is highly international, with members from the U.K., China, India, and Germany. We are an ambitious group well suited for students who want to pursue an academic career. Our lab is based in the Institute of Organic Chemistry at the University of W\u00fcrzburg, Germany. We have access to the state of the art facilities of the \u201cCenter for Nanosystems Chemistry\u201d here in W\u00fcrzburg. Moreover, while we are independent, we share lab space and group meetings with the group of Prof. Frank W\u00fcrthner, thus giving a broad exposure to different types of chemistry.<\/p>\n
If you are interested in doctoral studies in the group, or even post-doctoral, please get in touch as early as possible. We are interested in candidates who have a high level of motivation, good level of spoken English, and who take pride in their work. Your application should consist of your CV, a cover letter stating two academics who can be contacted to provide a reference letter on your behalf. You can also reach out informally by email.<\/p>\n
Email: \u00a0
Jake.Greenfield@uni-wuerzburg.de<\/a><\/p>\n\u4ee3\u8868\u6027\u8457\u4f5c\uff1a<\/h4>\n
Publications from the group, other publications can be found on Google Scholar:<\/p>\n
\n
- J. Wu, L. Kreimendahl, S. Tao, O. Anhalt and J. L. Greenfield,Chem. Sci.<\/em>,2024<\/strong>, 15, 3872\u20133878.<\/li>\n
- J. Wu and J. L. Greenfield,J. Am. <\/em>Chem. Soc.<\/em>,2024<\/strong>, 146, 20720\u201320727.<\/li>\n<\/ul>\n","protected":false},"excerpt":{"rendered":"\u4e00\u3001\u8bfe\u9898\u7ec4\u957f\u4ecb\u7ecd Jake L. Greenfield\u535a\u58eb\u4e8e2011-2015\u5e74\u4f26\u6566\u5e1d\u56fd\u7406\u5de5\u5b66\u9662\u5b8c\u6210\u672c\u79d1\u4e0e\u7855\u58eb\u5b66\u4e60\uff08\u672c\u7855\u5b66\u4e60\uff0c2011-2015\uff0cProf. Milo S. P. Shaffer\uff09\uff0c\u5e76\u5728\u4f50\u6cbb\u4e9a\u7406\u5de5\u5b66\u9662\uff082014\uff0cProf. Christopher W. Jones\uff09\u8fdb\u884c\u4e86\u4e3a\u671f5\u4e2a\u6708\u7684\u5168\u989d\u8d44\u52a9\u7814\u7a76\u3002Jake\u5728\u5251\u6865\u5927\u5b66Prof. Jonathan R. Nitschke\uff08\u5316\u5b66\u535a\u58eb\uff0c2015-2019\uff09\u7684\u6307\u5bfc\u4e0b\u83b7\u5f97\u535a\u58eb\u5b66\u4f4d\u30022019\u5e74\u535a\u58eb\u6bd5\u4e1a\u540e\uff0cJake\u56de\u5230\u5e1d\u56fd\u7406\u5de5\u5b66\u9662\uff0c\u5728Matthew J. Fuchter\u6559\u6388\u8bfe\u9898\u7ec4\u505a\u535a\u540e\u7814\u7a76\u30022022\u5e74\uff0cJake\u642c\u5230\u7ef4\u5c14\u8328\u5821\uff08\u5fb7\u56fd\uff09\u4e0eFrank W\u00fcrthner\u6559\u6388\u5408\u4f5c\uff0c\u6700\u521d\u662f\u7531\u6d2a\u5821\u8d44\u52a9\u7684\u535a\u540e\uff0c\u4e0d\u4e45\u4e4b\u540e\uff0c\u57282023\u5e74\uff0cJake\u83b7\u5f97\u4e86\u7531\u5316\u5b66\u5de5\u4e1a\u57fa\u91d1\u4f1a\u8d44\u52a9\u7684Liebig\u5956\u91d1\uff0c\u5f00\u59cb\u4e86\u72ec\u7acb\u7684\u7814\u7a76\u751f\u6daf\uff0c\u540c\u65f6\u6210\u4e3a\u5b66\u9662\u7684Emil Fischer\u7814\u7a76\u5458\u3002 \u8bfe\u9898\u7ec4\u7f51\u9875\uff1aDr Jake Greenfield – (uni-wuerzburg.de) Dr. Jake L. Greenfield completed his undergraduate studies at Imperial College London (MSci in Chemistry, 2011-2015, under the supervision of Prof. Milo S. P. Shaffer, UK) and carried out a fully funded 5-month research stay at Georgia Institute of Technology (Atlanta, Georgia, USA in 2014, under the supervision of Prof. Christopher W. Jones).Jake conducted his graduate studies at the University of Cambridge, under the supervision of Prof. Jonathan R. Nitschke (PhD in Chemistry, 2015-2019, Cambridge, UK). In 2019, he then returned to Imperial as a Research Associate […]","protected":false},"author":26,"featured_media":50991,"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":[2235],"tags":[],"jetpack_publicize_connections":[],"jetpack_featured_media_url":"https:\/\/assets.www.gsbet888.com\/uploads\/2024\/08\/2382c315a6ba396be1932dd8dafaff52.jpg","jetpack_shortlink":"https:\/\/wp.me\/p96op1-dgq","jetpack_sharing_enabled":true,"_links":{"self":[{"href":"\/\/www.gsbet888.com\/wp-json\/wp\/v2\/posts\/50990"}],"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\/26"}],"replies":[{"embeddable":true,"href":"\/\/www.gsbet888.com\/wp-json\/wp\/v2\/comments?post=50990"}],"version-history":[{"count":3,"href":"\/\/www.gsbet888.com\/wp-json\/wp\/v2\/posts\/50990\/revisions"}],"predecessor-version":[{"id":50993,"href":"\/\/www.gsbet888.com\/wp-json\/wp\/v2\/posts\/50990\/revisions\/50993"}],"wp:featuredmedia":[{"embeddable":true,"href":"\/\/www.gsbet888.com\/wp-json\/wp\/v2\/media\/50991"}],"wp:attachment":[{"href":"\/\/www.gsbet888.com\/wp-json\/wp\/v2\/media?parent=50990"}],"wp:term":[{"taxonomy":"category","embeddable":true,"href":"\/\/www.gsbet888.com\/wp-json\/wp\/v2\/categories?post=50990"},{"taxonomy":"post_tag","embeddable":true,"href":"\/\/www.gsbet888.com\/wp-json\/wp\/v2\/tags?post=50990"}],"curies":[{"name":"wp","href":"https:\/\/api.w.org\/{rel}","templated":true}]}},{"id":50977,"date":"2024-08-24T06:01:04","date_gmt":"2024-08-23T22:01:04","guid":{"rendered":"\/\/www.gsbet888.com\/?p=50977"},"modified":"2024-08-24T06:01:18","modified_gmt":"2024-08-23T22:01:18","slug":"%e3%80%8cspotlight-research%e3%80%8didpi%e5%82%ac%e5%8c%96%e4%b8%8d%e5%af%b9%e7%a7%b0%e5%a4%9a%e7%83%af%e7%83%83%e7%8e%af%e5%8c%96%e5%88%b6%e5%a4%87%e9%be%99%e6%b6%8e%e9%a6%99","status":"publish","type":"post","link":"\/\/www.gsbet888.com\/interview\/2024\/08\/%e3%80%8cspotlight-research%e3%80%8didpi%e5%82%ac%e5%8c%96%e4%b8%8d%e5%af%b9%e7%a7%b0%e5%a4%9a%e7%83%af%e7%83%83%e7%8e%af%e5%8c%96%e5%88%b6%e5%a4%87%e9%be%99%e6%b6%8e%e9%a6%99.html","title":{"rendered":"\u300cSpotlight Research\u300dIDPi\u50ac\u5316\u4e0d\u5bf9\u79f0\u591a\u70ef\u70c3\u73af\u5316\u5236\u5907\u9f99\u6d8e\u9999"},"content":{"rendered":"
\u4f5c\u8005\uff1a\u77f3\u6cb9\u919a<\/strong><\/p>\n
\u672c\u671f\u70ed\u70b9\u7814\u7a76\uff0c\u6211\u4eec\u9080\u8bf7\u5230\u4e86\u672c\u6587\u5171\u540c\u7b2c\u4e00\u4f5c\u8005\uff0c\u6765\u81ea\u5fb7\u56fd\u9a6c\u514b\u601d\u666e\u6717\u514b\u7164\u70ad\u7814\u7a76\u6240\u7684\u7f57\u5a1c\u535a\u58eb\u4e3a\u6211\u4eec\u5206\u4eab\u3002<\/p>\n
2024\u5e747\u670831\u65e5\uff0cNature<\/em><\/strong>\u5728\u7ebf\u53d1\u8868\u4e86\u6765\u81ea\u5fb7\u56fd\u9a6c\u514b\u601d\u666e\u6717\u514b\u7164\u70ad\u7814\u7a76\u6240Benjamin List\u8bfe\u9898\u7ec4\u9898\u4e3a\u300cThe catalytic asymmetric polyenecyclization of homofarnesol to ambrox.\u300d\u7684\u7814\u7a76\u8bba\u6587\u3002\u4f5c\u8005\u53d1\u73b0\u5728\u6c1f\u4ee3\u6eb6\u5242\u5b58\u5728\u4e0b\uff0c\u7ed3\u5408\u5177\u6709\u5f3aBr\u00f8nsted\u9178\u6027\u548c\u7a7a\u95f4\u53d7\u9650\u7684\u4e9a\u6c28\u57fa\u53cc\u78f7\u9170\u4e9a\u80fa\u916fIDPi\u50ac\u5316\uff0c\u901a\u8fc7\u4e0d\u5bf9\u79f0\u591a\u70ef\u70c3\u73af\u5316\uff0c\u6210\u529f\u4ee5\u826f\u597d\u7684\u4ea7\u7387\u3001\u4f18\u5f02\u7684\u5bf9\u6620\u548c\u975e\u5bf9\u6620\u9009\u62e9\u6027\u5408\u6210\u4e50\uff08-\uff09-\u9f99\u6d8e\u9999\u919a\u548c\u500d\u534a\u841c\u5185\u916f\u5929\u7136\u4ea7\u7269\uff08+\uff09-\u9999\u7d2b\u82cf\u5185\u916f\u3002<\/p>\n
\n\u201cThe catalytic asymmetric polyenecyclization of homofarnesol to ambrox.<\/p>\n
Na Luo, Mathias Turberg, Markus Leutzsch, Benjamin Mitschke, Sebastian Brunen, Vijay N. Wakchaure, Nils N\u00f6thling, Mathias Schelwies, Ralf Pelzer, Benjamin List*.<\/p>\n
Nature<\/em>\uff0c<\/em>2024<\/strong>, <\/em>632, 795\u2013801. Doi:
Q1. <\/strong>\u8bf7\u5bf9<\/strong>\u201cThe catalytic asymmetric polyenecyclization of homofarnesol to ambrox.\u201d<\/strong>\u4f5c<\/strong>\u4e00\u4e2a\u7b80\u5355\u4ecb\u7ecd\u3002<\/strong><\/h4>\n
10.1039\/D4QO00996G<\/a><\/p>\n<\/blockquote>\n\u591a\u70ef\u73af\u5316\u53cd\u5e94\u662f\u6307\u5c06\u7b80\u5355\u7684\u975e\u73af\u72b6\u524d\u4f53\u901a\u8fc7\u4e00\u6b65\u53cd\u5e94\u6784\u5efa\u5177\u6709\u591a\u4e2a\u78b3\u78b3\u952e\u4ee5\u53ca\u591a\u4e2a\u7acb\u4f53\u4e2d\u5fc3\u7684\u591a\u73af\u4ea7\u7269\u7684\u53cd\u5e94\u3002\u5728\u6b64\u53cd\u5e94\u4e2d\u540c\u65f6\u5b9e\u73b0\u4ea7\u7269\u5206\u5e03\u548c\u7acb\u4f53\u5316\u5b66\u7684\u7cbe\u786e\u63a7\u5236\u5bf9\u5316\u5b66\u5bb6\u6765\u8bf4\u662f\u4e00\u9879\u8270\u5de8\u7684\u4efb\u52a1\uff0c\u5c24\u5176\u5c06(3E,<\/em>7E<\/em>)-homofarnesol\u901a\u8fc7\u591a\u70ef\u73af\u5316\u8f6c\u5316\u4e3a\u5177\u6709\u9f99\u6d8e\u9999\u5473\u7684(\u2212)-ambrox\u662f\u5316\u5b66\u5408\u6210\u4e2d\u4e00\u76f4\u4ee5\u6765\u7684\u6311\u6218\u3002\u6211\u4eec\u53d1\u73b0\u5728\u6c1f\u4ee3\u6eb6\u5242\u4e2d\uff0c\u7ed3\u5408\u5177\u6709\u5f3aBr\u00f8nsted\u9178\u6027\u548c\u53d7\u9650\u7a7a\u95f4\u7684\u4e9a\u6c28\u57fa\u53cc\u78f7\u9170\u4e9a\u80fa\u916fIDPi\u4f5c\u4e3a\u50ac\u5316\u5242\u80fd\u591f\u4ee5\u826f\u597d\u7684\u4ea7\u7387\u4ee5\u53ca\u4f18\u5f02\u7684\u5bf9\u6620\u9009\u62e9\u6027\u3001\u975e\u5bf9\u6620\u9009\u62e9\u6027\u5408\u6210\uff08-\uff09-\u9f99\u6d8e\u9999\u919a\u548c\u500d\u534a\u841c\u5185\u916f\u5929\u7136\u4ea7\u7269\uff08+\uff09-\u9999\u7d2b\u82cf\u5185\u916f\u3002\u5b9e\u9a8c\u8868\u660e\u8be5\u53cd\u5e94\u4e3b\u8981\u901a\u8fc7\u534f\u540c\u9014\u5f84\u8fdb\u884c\uff0c\u7b26\u5408Stork-Eschenmoser\u5047\u8bbe\u3002IDPi\u50ac\u5316\u5242\u7684\u5fae\u578b\u7a7a\u8154\u73af\u5883\u5bf9\u5b9e\u73b0\u53cd\u5e94\u7684\u9009\u62e9\u6027\u975e\u5e38\u91cd\u8981\uff0c\u800c\u8fd9\u5728\u6b64\u4e4b\u524d\u53ea\u6709\u9176\u50ac\u5316\u80fd\u5b9e\u73b0\u8fd9\u79cd\u9ad8\u9009\u62e9\u6027\u3002<\/p>\n
Q2.<\/strong>\u5728\u7814\u7a76\u7684\u65f6\u5019\u9047\u5230\u8fc7\u600e\u6837\u7684\u56f0\u96be\u5462\uff1f\u53c8\u662f\u600e\u6837\u514b\u670d\u7684\u5462\uff1f<\/strong><\/h4>\n
\u672c\u90e8\u5206\u7814\u7a76\u5de5\u4f5c\u4e2d\uff0c\u5728\u7b5b\u9009\u50ac\u5316\u53cd\u5e94\u6761\u4ef6\u8c03\u63a7\u533a\u57df\u9009\u62e9\u6027\u548c\u5bf9\u6620\u9009\u62e9\u6027\u7684\u8fc7\u7a0b\u4e2d\uff0c\u6211\u4ed8\u51fa\u4e86\u8270\u8f9b\u7684\u5de5\u4f5c\uff0c\u66fe\u5c1d\u8bd5\u4e86\u65e0\u6570\u79cd\u6761\u4ef6\u4e0e\u8bd5\u5242\u3002\u5728\u6b64\u671f\u95f4\u6211\u66fe\u6570\u6b21\u6000\u7591\u81ea\u5df1\uff0c\u7ecf\u5386\u591a\u6b21\u5931\u8d25\u4f7f\u81ea\u5df1\u60c5\u7eea\u4f4e\u843d\u3002\u7814\u7a76\u5de5\u4f5c\u4e5f\u4e00\u5ea6\u8fdb\u5c55\u7f13\u6162\uff0c\u4f46\u6b63\u662f\u8fd9\u65f6\u6765\u81ea\u7537\u670b\u53cb\u548c\u5bb6\u4eba\u7684\u9f13\u52b1\u548c\u652f\u6301\u8ba9\u6211\u53ca\u65f6\u8c03\u6574\u4e86\u72b6\u6001\uff0c\u6700\u7ec8\u4e5f\u662f\u9010\u6e10\u5c1d\u8bd5\u51fa\u542b\u6c1f\u70f7\u70c3\u4f5c\u4e3a\u5173\u952e\u8bd5\u5242\uff0c\u987a\u5229\u83b7\u5f97\u4e86\u7406\u60f3\u7684\u53cd\u5e94\u7ed3\u679c\u3002<\/p>\n
Q3. <\/strong>\u672c\u6b21\u7814\u7a76\u4e3b\u4f53\uff0c\u6709\u6ca1\u6709\u4ec0\u4e48\u8ba9\u60a8\u611f\u89c9\u7279\u522b\u8f9b\u82e6\u548c\u70e7\u8111\u5462\uff1f<\/strong><\/h4>\n
\u6709\u673a\u5408\u6210\u4f5c\u4e3a\u5b9e\u9a8c\u5b66\u79d1\uff0c\u5728\u7814\u7a76\u5de5\u4f5c\u4e2d\u4e0d\u4ec5\u5f97\u7ecf\u5e38\u9762\u5bf9\u7e41\u6742\u7684\u5b9e\u9a8c\u5de5\u4f5c\uff0c\u4e5f\u5f97\u5728\u4f17\u591a\u6d4b\u8bd5\u6570\u636e\u4e2d\u5206\u6790\u5f52\u7eb3\u51fa\u6709\u610f\u4e49\u7684\u7ed3\u8bba\u3002\u5728\u6211\u7684\u7814\u7a76\u5de5\u4f5c\u4e2d\uff0c\u7ecf\u5e38\u6d89\u53ca\u53cd\u5e94\u7269\u5b58\u5728\u591a\u4e2a\u53cd\u5e94\u4f4d\u70b9\u4e0e\u624b\u6027\u4e2d\u5fc3\u7684\u60c5\u51b5\uff0c\u5bfc\u81f4\u4ea7\u7269\u53ef\u80fd\u5b58\u5728\u6570\u5341\u4e2a\u5f02\u6784\u4f53\uff0c\u7ecf\u5e38\u4e3a\u4e86\u786e\u8ba4\u5f02\u6784\u4f53\u7684\u7ed3\u6784\u82b1\u8d39\u5927\u91cf\u7684\u65f6\u95f4\u3002\u540c\u65f6\u4e5f\u5f97\u8fdb\u4e00\u6b65\u5408\u6210\u4e0d\u540c\u6027\u80fd\u7684\u50ac\u5316\u5242\u8c03\u63a7\u53cd\u5e94\u7684\u9009\u62e9\u6027\u3002\u6700\u7ec8\u5f97\u5230\u53cd\u5e94\u7ed3\u679c\u540e\u4ecd\u7136\u9700\u8981\u5229\u7528\u5305\u62ec\u7406\u8bba\u8ba1\u7b97\u5728\u5185\u7684\u5404\u79cd\u624b\u6bb5\u8fdb\u884c\u53cd\u5e94\u673a\u7406\u9a8c\u8bc1\u3002\u5728\u4ee5\u4e0a\u6574\u4e2a\u8fc7\u7a0b\u4e2d\u4e0d\u4ec5\u9700\u8981\u5145\u8db3\u7684\u63a2\u7a76\u7cbe\u795e\uff0c\u4e5f\u9700\u8981\u5bf9\u5408\u6210\u7b56\u7565\u3001\u7269\u7406\u6709\u673a\u4ee5\u53ca\u4eea\u5668\u79d1\u5b66\u7b49\u65b9\u9762\u7684\u5b66\u79d1\u77e5\u8bc6\u66f4\u4e3a\u6df1\u539a\u7684\u7406\u89e3\uff0c\u8fd9\u4e5f\u662f\u76ee\u524d\u6211\u4ecd\u9700\u8981\u52a0\u5f3a\u7684\u65b9\u5411\u3002<\/p>\n
Q4. <\/strong>\u5c06\u6765\u60f3\u7ee7\u7eed\u7814\u7a76\u5316\u5b66\u7684\u54ea\u4e2a\u65b9\u5411\u5462\uff1f<\/strong><\/h4>\n
\u76ee\u524d\u6211\u4e3b\u8981\u4ece\u4e8b\u50ac\u5316\u4e0d\u5bf9\u79f0\u5408\u6210\u5de5\u4f5c\uff0c\u672a\u6765\u6211\u60f3\u62d3\u5c55\u51fa\u66f4\u591a\u65b0\u7b56\u7565\u3001\u65b0\u53cd\u5e94\uff0c\u5e76\u4e14\u529b\u6c42\u5f00\u53d1\u51fa\u6709\u8db3\u591f\u6f5c\u529b\u5e94\u7528\u4e8e\u5de5\u4e1a\u5c4a\u7684\u521b\u65b0\u5408\u6210\u65b9\u6cd5\u4e0e\u65b0\u9896\u7ed3\u6784<\/p>\n
Q5. <\/strong>\u6700\u540e\uff0c\u6709\u4ec0\u4e48\u60f3\u5bf9\u5404\u4f4d\u8bfb\u8005\u8bf4\u7684\u5417\uff1f<\/strong><\/h4>\n
\u9009\u62e9\u505a\u79d1\u5b66\u7814\u7a76\u6ce8\u5b9a\u4e0d\u662f\u4e00\u6761\u5bb9\u6613\u7684\u8def\uff0c\u52bf\u5fc5\u4f1a\u7ecf\u5386\u65e0\u6570\u574e\u5777\u4e0e\u632b\u6298\u3002\u4f46\u662f\u8bf7\u76f8\u4fe1\uff0c\u53ea\u8981\u80af\u575a\u6301\u81ea\u5df1\u7684\u7406\u60f3\uff0c\u4e00\u5f80\u65e0\u524d\u5730\u6295\u5165\u5230\u81ea\u5df1\u7684\u4e8b\u4e1a\u4e2d\uff0c\u4e00\u5b9a\u53ef\u4ee5\u505a\u51fa\u4e00\u756a\u6210\u5c31\uff01<\/p>\n
\u4f5c\u8005\u6559\u80b2\u80cc\u666f\u7b80\u4ecb<\/strong><\/h4>\n
<\/strong><\/p>\n
\u6559\u80b2\u80cc\u666f\uff1a<\/strong><\/h4>\n
2012-2016\u00a0 \u6e58\u6f6d\u5927\u5b66\u00a0 \u9ad8\u5206\u5b50\u6750\u6599\u4e0e\u5de5\u7a0b\u4e13\u4e1a\u00a0 \u5b66\u58eb\u5b66\u4f4d<\/p>\n
2016-2021\u00a0 \u4e2d\u56fd\u79d1\u5b66\u9662\u5316\u5b66\u7814\u7a76\u6240\u00a0 \u6709\u673a\u5316\u5b66\u4e13\u4e1a\u00a0 \u535a\u58eb\u5b66\u4f4d\u00a0 \u5bfc\u5e08\uff1a \u738b\u5176\u5f3a \u7814\u7a76\u5458<\/p>\n
2022-\u81f3\u4eca\u00a0 \u9a6c\u514b\u601d\u666e\u6717\u514b\u7164\u70ad\u7814\u7a76\u6240\u00a0 \u535a\u58eb\u540e \u5408\u4f5c\u5bfc\u5e08\uff1a Prof. Benjamin List<\/p>\n
\u83b7\u5956\u7ecf\u5386\uff1a<\/strong><\/h4>\n
\u6e56\u5357\u7701\u4f18\u79c0\u6bd5\u4e1a\u751f<\/p>\n
\u535a\u58eb\u751f\u56fd\u5bb6\u5956\u5b66\u91d1<\/p>\n
\u5317\u4eac\u5e02\u4f18\u79c0\u6bd5\u4e1a\u751f<\/p>\n
2024\u5e74\u83b7\u5f97\u6d2a\u5821\u57fa\u91d1\u4f1a\u8d44\u52a9<\/p>\n
\u672c\u6587\u7248\u6743\u5c5e\u4e8e Chem-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\uff1a\u77f3\u6cb9\u919a \u672c\u671f\u70ed\u70b9\u7814\u7a76\uff0c\u6211\u4eec\u9080\u8bf7\u5230\u4e86\u672c\u6587\u5171\u540c\u7b2c\u4e00\u4f5c\u8005\uff0c\u6765\u81ea\u5fb7\u56fd\u9a6c\u514b\u601d\u666e\u6717\u514b\u7164\u70ad\u7814\u7a76\u6240\u7684\u7f57\u5a1c\u535a\u58eb\u4e3a\u6211\u4eec\u5206\u4eab\u3002 2024\u5e747\u670831\u65e5\uff0cNature\u5728\u7ebf\u53d1\u8868\u4e86\u6765\u81ea\u5fb7\u56fd\u9a6c\u514b\u601d\u666e\u6717\u514b\u7164\u70ad\u7814\u7a76\u6240Benjamin List\u8bfe\u9898\u7ec4\u9898\u4e3a\u300cThe catalytic asymmetric polyenecyclization of homofarnesol to ambrox.\u300d\u7684\u7814\u7a76\u8bba\u6587\u3002\u4f5c\u8005\u53d1\u73b0\u5728\u6c1f\u4ee3\u6eb6\u5242\u5b58\u5728\u4e0b\uff0c\u7ed3\u5408\u5177\u6709\u5f3aBr\u00f8nsted\u9178\u6027\u548c\u7a7a\u95f4\u53d7\u9650\u7684\u4e9a\u6c28\u57fa\u53cc\u78f7\u9170\u4e9a\u80fa\u916fIDPi\u50ac\u5316\uff0c\u901a\u8fc7\u4e0d\u5bf9\u79f0\u591a\u70ef\u70c3\u73af\u5316\uff0c\u6210\u529f\u4ee5\u826f\u597d\u7684\u4ea7\u7387\u3001\u4f18\u5f02\u7684\u5bf9\u6620\u548c\u975e\u5bf9\u6620\u9009\u62e9\u6027\u5408\u6210\u4e50\uff08-\uff09-\u9f99\u6d8e\u9999\u919a\u548c\u500d\u534a\u841c\u5185\u916f\u5929\u7136\u4ea7\u7269\uff08+\uff09-\u9999\u7d2b\u82cf\u5185\u916f\u3002 \u201cThe catalytic asymmetric polyenecyclization of homofarnesol to ambrox. Na Luo, Mathias Turberg, Markus Leutzsch, Benjamin Mitschke, Sebastian Brunen, Vijay N. Wakchaure, Nils N\u00f6thling, Mathias Schelwies, Ralf Pelzer, Benjamin List*. Nature\uff0c2024, 632, 795\u2013801. Doi: 10.1038\/s41586-024-07757-7.\u201d Q1. \u8bf7\u5bf9\u201cThe catalytic asymmetric polyenecyclization of homofarnesol to ambrox.\u201d\u4f5c\u4e00\u4e2a\u7b80\u5355\u4ecb\u7ecd\u3002 \u591a\u70ef\u73af\u5316\u53cd\u5e94\u662f\u6307\u5c06\u7b80\u5355\u7684\u975e\u73af\u72b6\u524d\u4f53\u901a\u8fc7\u4e00\u6b65\u53cd\u5e94\u6784\u5efa\u5177\u6709\u591a\u4e2a\u78b3\u78b3\u952e\u4ee5\u53ca\u591a\u4e2a\u7acb\u4f53\u4e2d\u5fc3\u7684\u591a\u73af\u4ea7\u7269\u7684\u53cd\u5e94\u3002\u5728\u6b64\u53cd\u5e94\u4e2d\u540c\u65f6\u5b9e\u73b0\u4ea7\u7269\u5206\u5e03\u548c\u7acb\u4f53\u5316\u5b66\u7684\u7cbe\u786e\u63a7\u5236\u5bf9\u5316\u5b66\u5bb6\u6765\u8bf4\u662f\u4e00\u9879\u8270\u5de8\u7684\u4efb\u52a1\uff0c\u5c24\u5176\u5c06(3E,7E)-homofarnesol\u901a\u8fc7\u591a\u70ef\u73af\u5316\u8f6c\u5316\u4e3a\u5177\u6709\u9f99\u6d8e\u9999\u5473\u7684(\u2212)-ambrox\u662f\u5316\u5b66\u5408\u6210\u4e2d\u4e00\u76f4\u4ee5\u6765\u7684\u6311\u6218\u3002\u6211\u4eec\u53d1\u73b0\u5728\u6c1f\u4ee3\u6eb6\u5242\u4e2d\uff0c\u7ed3\u5408\u5177\u6709\u5f3aBr\u00f8nsted\u9178\u6027\u548c\u53d7\u9650\u7a7a\u95f4\u7684\u4e9a\u6c28\u57fa\u53cc\u78f7\u9170\u4e9a\u80fa\u916fIDPi\u4f5c\u4e3a\u50ac\u5316\u5242\u80fd\u591f\u4ee5\u826f\u597d\u7684\u4ea7\u7387\u4ee5\u53ca\u4f18\u5f02\u7684\u5bf9\u6620\u9009\u62e9\u6027\u3001\u975e\u5bf9\u6620\u9009\u62e9\u6027\u5408\u6210\uff08-\uff09-\u9f99\u6d8e\u9999\u919a\u548c\u500d\u534a\u841c\u5185\u916f\u5929\u7136\u4ea7\u7269\uff08+\uff09-\u9999\u7d2b\u82cf\u5185\u916f\u3002\u5b9e\u9a8c\u8868\u660e\u8be5\u53cd\u5e94\u4e3b\u8981\u901a\u8fc7\u534f\u540c\u9014\u5f84\u8fdb\u884c\uff0c\u7b26\u5408Stork-Eschenmoser\u5047\u8bbe\u3002IDPi\u50ac\u5316\u5242\u7684\u5fae\u578b\u7a7a\u8154\u73af\u5883\u5bf9\u5b9e\u73b0\u53cd\u5e94\u7684\u9009\u62e9\u6027\u975e\u5e38\u91cd\u8981\uff0c\u800c\u8fd9\u5728\u6b64\u4e4b\u524d\u53ea\u6709\u9176\u50ac\u5316\u80fd\u5b9e\u73b0\u8fd9\u79cd\u9ad8\u9009\u62e9\u6027\u3002 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Q4. \u5c06\u6765\u60f3\u7ee7\u7eed\u7814\u7a76\u5316\u5b66\u7684\u54ea\u4e2a\u65b9\u5411\u5462\uff1f \u76ee\u524d\u6211\u4e3b\u8981\u4ece\u4e8b\u50ac\u5316\u4e0d\u5bf9\u79f0\u5408\u6210\u5de5\u4f5c\uff0c\u672a\u6765\u6211\u60f3\u62d3\u5c55\u51fa\u66f4\u591a\u65b0\u7b56\u7565\u3001\u65b0\u53cd\u5e94\uff0c\u5e76\u4e14\u529b\u6c42\u5f00\u53d1\u51fa\u6709\u8db3\u591f\u6f5c\u529b\u5e94\u7528\u4e8e\u5de5\u4e1a\u5c4a\u7684\u521b\u65b0\u5408\u6210\u65b9\u6cd5\u4e0e\u65b0\u9896\u7ed3\u6784 Q5. \u6700\u540e\uff0c\u6709\u4ec0\u4e48\u60f3\u5bf9\u5404\u4f4d\u8bfb\u8005\u8bf4\u7684\u5417\uff1f 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\u4f5c\u8005\uff1a\u77f3\u6cb9\u919a<\/strong><\/p>\n
\u5bfc\u8bfb\uff1a<\/strong><\/h4>\n
\u8fd1\u671f\uff0c\u6d59\u6c5f\u5e08\u8303\u5927\u5b66\u7684\u5f20\u5ca9\u8bfe\u9898\u7ec4\u5728Org. Chem. Front.<\/em><\/strong>\u4e0a\u53d1\u8868\u8bba\u6587\uff0c\u5229\u7528\u5149\u8bf1\u5bfcC-C\u6d3b\u5316\u548c\u5e94\u53d8\u5f20\u529b\u91ca\u653e\u7684\u7b56\u7565\uff0c\u5b9e\u73b0\u4e86\u73af\u5916\u78b3\u81ea\u7531\u57fa\u5f62\u6210\u5f15\u53d1\u73af\u4e01\u70f7\u5f00\u73af\u5408\u6210\u03b3\uff0c\u03b4-\u4e0d\u9971\u548c\u916e\u3002<\/p>\n
\n\u201cPhotoredox-enabled ring-opening of cyclobutanes via the formation of a carbon radical.<\/p>\n
Chunhang Zhao, Wenjing Ma, Kairui Liu, Ruoyang Xu, Xiuya Ma and Yan Zhang *.<\/p>\n
Org. Chem. Front.,<\/em>2024,<\/strong>11, 4663-4670. Doi: DOI:
<\/p>\n
\u7814\u7a76\u80cc\u666f<\/strong><\/h4>\n
Angew. Chem. Int. Ed<\/em>.2023<\/strong>,62<\/em>, e202300166<\/a>\uff09\u3002\u4e25\u683c\u6765\u8bf4\uff0c\u6b64\u6b21\u62a5\u9053\u7684\u5de5\u4f5c\u662f\u5bf9\u524d\u671f\u7814\u7a76\u53d1\u73b0\u7684\u5f88\u597d\u8865\u5145\u3002\u901a\u8fc7\u6539\u53d8\u53cd\u5e94\u7269\u7ed3\u6784\u7684\u8c03\u6574\uff0c\u6210\u529f\u5b9e\u73b0\u4e86\u7528\u4f20\u7edf\u65b9\u6cd5\u96be\u4ee5\u5408\u6210\u7684\u03b3,\u03b4-\u4e0d\u9971\u548c\u916e\u7c7b\u5316\u5408\u7269\u3002\u73af\u4e01\u70f7\u53ca\u5176\u53d6\u4ee3\u7684\u73af\u4e01\u70f7\u5728\u7ed3\u6784\u4e0a\u662f\u5177\u6709\u8f83\u9ad8\u73af\u5f20\u529b\u7684\u9aa8\u67b6\uff0c\u53ef\u5229\u7528\u5176\u9009\u62e9\u6027C\u2013C\u952e\u6d3b\u5316\u53d1\u751f\u6269\u73af\u6216\u8005\u5f00\u73af\uff0c\u7528\u4ee5\u5b9e\u73b0\u5b98\u80fd\u56e2\u8f6c\u5316\u6216\u8005\u590d\u6742\u5206\u5b50\u7684\u5408\u6210\u3002\u4e8b\u5b9e\u4e0a\u5b9e\u73b0\u5f62\u5f0f\u4e0a\u7684\u73af\u4e01\u70f7\u9aa8\u67b6\u6269\u73af\u6709\u591a\u79cd\u65b9\u5f0f\uff0c\u9996\u5148\u53ef\u4ee5\u5229\u7528\u82e5\u5e72\u4eba\u540d\u53cd\u5e94\u4e2d\u78b3\u6b63\u79bb\u5b50\u7684\u91cd\u6392\u8fc7\u7a0b\uff0c\u5982Demjanov\u91cd\u6392\u3001Wagner-Meerwein\u53cd\u5e94\u3001Baeyer-Villiger \u53cd\u5e94\u4ee5\u53caPinacol\u91cd\u6392\u3002\u4f46\u6bcf\u4e00\u79cd\u65b9\u6cd5\u90fd\u9700\u4f7f\u7528\u7ed3\u6784\u9650\u5b9a\u7684\u53cd\u5e94\u7269\uff0c\u56e0\u6b64\u53d1\u5c55\u51fa\u66f4\u591a\u6709\u4ef7\u503c\u7684\u5b9e\u73b0\u73af\u4e01\u70f7\u4e2d\u60f0\u6027C\u2013C\u952e\u6d3b\u5316\u7684\u5408\u6210\u7b56\u7565\u4ecd\u662f\u5341\u5206\u5fc5\u8981\u7684\u3002\u5176\u4e2d\uff0c\u901a\u8fc7\u5355\u7535\u5b50\u8f6c\u79fb\u5f15\u53d1\u7684\u81ea\u7531\u57fa\u53cd\u5e94\u5b9e\u73b0\u73af\u4e01\u9187\u5f00\u73af\u4ee3\u8868\u7740\u4e00\u7c7b\u7ecf\u5178\u7684\u5408\u6210\u7b56\u7565\uff0c\u5176\u4e3b\u8981\u7279\u70b9\u662f\u73af\u4e01\u9187\u6c27\u5316\u5f62\u6210\u9ad8\u6d3b\u6027\u73af\u4e01\u6c27\u81ea\u7531\u57fa\u5e76\u8bf1\u53d1\u90bb\u4f4dC\u2013C\u952e\u65ad\u88c2\u3002\u4f46\u4e3a\u5b9e\u73b0\u73af\u4e01\u70f7\u5f00\u73af\u4ea7\u751f\u4e30\u5bcc\u7684\u7ed3\u6784\u591a\u6837\u6027\uff0c\u5bfb\u627e\u65b0\u6a21\u5f0f\u4e0b\u7684\u5b9e\u73b0\u73af\u4e01\u70f7C\u2013C\u952e\u6d3b\u5316\u7684\u81ea\u7531\u57fa\u53cd\u5e94\u8f6c\u5316\u7b56\u7565\u4ecd\u662f\u6781\u5bcc\u6311\u6218\u6027\u7684\u7814\u7a76\u8bfe\u9898\u3002
<\/p>\n
\u7814\u7a76\u5185\u5bb9<\/strong><\/h4>\n
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\u540c\u6837\u7684\uff0c\u8bfe\u9898\u7ec4\u4ecd\u7136\u8003\u5bdf\u4e86\u81ea\u7531\u57fa\u7247\u6bb5\u7684\u53ef\u79fb\u9664\u6027\u3002\u5e76\u4e14\u65e0\u8bba\u53cd\u5e94\u7269\u7684\u70ef\u57fa\u7247\u6bb5\u662fZ<\/em>\u8fd8\u662fE<\/em>\u6784\u578b\uff0c\u5728\u5149\u50ac\u5316\u8131\u53bb\u81ea\u7531\u57fa\u7247\u6bb5\u4e4b\u540e\u90fd\u4f1a\u53d8\u4e3aE<\/em>\u578b\u4ea7\u7269\u3002\u6700\u540e\uff0c\u4f5c\u8005\u8fd8\u5bf9\u4ea7\u54c1\u7684\u7ed3\u6784\u8fdb\u884c\u4e86\u82e5\u5e72\u884d\u751f\u5316\u5b9e\u9a8c\uff0c\u8f6c\u53d8\u4e3a\u5176\u4ed6\u6709\u4ef7\u503c\u76841,4-\u53cc\u5b98\u80fd\u56e2\u4ea7\u54c1\u3002
<\/p>\n
\u603b\u7ed3\u5c55\u671b<\/strong><\/h4>\n
chenduozhi@mail.kib.ac.cn<\/a><\/p>\n\u603b\u4e4b\uff0c\u672c\u7814\u7a76\u5de5\u4f5c\u4e2d\u4fc3\u8fdb\u5f00\u73af\u6216\u8005\u8bf4\u5b9e\u73b0\u73af\u4e01\u70f7C\u2013C\u952e\u6d3b\u5316\u7684\u56e0\u7d20\u4e3b\u8981\u6709\u4e24\u4e2a\uff0c\u4e00\u662f\u73af\u4e01\u70f7\u9aa8\u67b6\u7684\u5f20\u529b\u9a71\u52a8\uff1b\u4e8c\u662f\u5f62\u6210\u4e86\u7531\u7a33\u5b9a\u5316\u57fa\u56e2\u4f5c\u7528\u7684\u70ed\u529b\u5b66\u66f4\u4e3a\u7a33\u5b9a\u7684\u65b0\u81ea\u7531\u57fa\u7269\u79cd\u3002\u8bfe\u9898\u7ec4\u6240\u5efa\u6784\u8d77\u6765\u7684\u73af\u4e01\u70f7\u5f00\u73af\u7684\u65b0\u7684\u8f6c\u5316\u6a21\u5f0f\uff0c\u5c06\u4e3a\u81ea\u7531\u57fa\u5f15\u53d1\u76841,4-\u53cc\u5b98\u80fd\u56e2\u5316\u53cd\u5e94\u7684\u53d1\u5c55\u63d0\u4f9b\u65b0\u7684\u601d\u8def\u548c\u542f\u793a\u3002<\/p>\n
\uff08\u975e\u5e38\u611f\u8c22\u5f20\u5ca9\u6559\u6388\u5bf9<\/strong>Chem-Station<\/em><\/strong>\u7684\u652f\u6301<\/strong>\uff09<\/p>\n
\u901a\u8baf\u4f5c\u8005\u7b80\u4ecb<\/strong><\/h4>\n
<\/strong><\/p>\n
\u5f20\u5ca9\uff0c\u6d59\u6c5f\u5e08\u8303\u5927\u5b66\u5316\u6750\u5b66\u9662\uff0c\u526f\u6559\u6388\uff0c\u7855\u5bfc\u30022016\u5e74\u6bd5\u4e1a\u4e8e\u6d59\u6c5f\u5927\u5b66\u836f\u5b66\u9662\uff0c2019\u5e74\u4f5c\u4e3a\u56fd\u5bb6\u516c\u6d3e\u8bbf\u95ee\u5b66\u8005\u524d\u5f80\u5fb7\u56fd\u54e5\u5ef7\u6839\u5927\u5b66\u5b66\u4e60\u3002\u5b9e\u9a8c\u5ba4\u7814\u7a76\u65b9\u5411\u96c6\u4e2d\u4e8e\u5149\u6216\u7535\u50ac\u5316\u4fc3\u8fdb\u7684\u81ea\u7531\u57fa\u7eff\u8272\u751f\u6210\u65b9\u6cd5\u53ca\u5176\u8f6c\u5316\u3002\u81ea\u72ec\u7acb\u5de5\u4f5c\u4ee5\u6765\uff0c\u4ee5\u7b2c\u4e00\u4f5c\u8005\u6216\u8005\u901a\u8baf\u4f5c\u8005\u5728\u56fd\u9645\u9876\u7ea7\u53ca\u6743\u5a01\u671f\u520a\u53d1\u8868\u8bba\u658719\u7bc7\uff0c\u5305\u62ecAngew. Chem. Int. Ed<\/em>.\uff082\u7bc7\uff09,Chem. Sci.<\/em>\uff083\u7bc7\uff09,Green Chem<\/em>.(1\u7bc7)\uff0cSci. China Chem<\/em>.(1\u7bc7)\uff0cOrg. Lett.<\/em>(4\u7bc7)\u4ee5\u53caOrg. Chem. <\/em>Front. <\/em>(2\u7bc7)\u7b49\u3002\u6388\u6743\u53d1\u660e\u4e13\u522912\u9879\uff08\u542b2\u9879\u7f8e\u56fd\u53d1\u660e\u4e13\u5229\uff09\u3002<\/p>\n
\u672c\u6587\u7248\u6743\u5c5e\u4e8e Chem-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
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caomingming@mail.kib.ac.cn<\/a><\/p>\n\u5730\u5740\uff1a\u4e91\u5357\u7701\u6606\u660e\u5e02\u84dd\u9ed1\u8def132\u53f7\uff0c\u4e2d\u56fd\u79d1\u5b66\u9662\u6606\u660e\u690d\u7269\u7814\u7a76\u6240<\/p>\n
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\u4f5c\u8005\uff1a\u6749\u6749<\/p>\n
\u5bfc\u8bfb\uff1a<\/h4>\n
\u8fd1\u671f\uff0c\u65e5\u672c\u4eac\u90fd\u5927\u5b66\u7684Hirohisa Ohmiya\u4e0eKazunori Nagao\u8bfe\u9898\u7ec4\u5728J. Am. Chem. Soc.<\/em>\u4e2d\u53d1\u8868\u8bba\u6587\uff0c\u62a5\u9053\u4e00\u79cd\u5168\u65b0\u7684\u53cc\u91cd\u94b4\/\u5149\u6c27\u5316\u8fd8\u539f\u50ac\u5316\u8102\u80aa\u65cf\u70ef\u70c3\u4e0ecollidine\u00b7HX\u76d0\u7684\u6c22\u5364\u5316\u53cd\u5e94\u65b9\u6cd5\u5b66\uff0c\u8fdb\u800c\u6210\u529f\u5b8c\u6210\u4e00\u7cfb\u5217\u9ad8\u5ea6\u5b98\u80fd\u56e2\u5316\u7684\u70f7\u57fa\u5364\u5206\u5b50\u7684\u6784\u5efa\u3002<\/p>\n
\nA Dual Cobalt and Photoredox Catalysis for Hydrohalogenation of Alkenes<\/p>\n
S. Shibutani, K. Nagao, H. Ohmiya,J. Am. Chem. Soc.<\/em>2024<\/strong>,146<\/em>, 4375. doi:
<\/a><\/p>\n
\u6b63\u6587\uff1a<\/h4>\n
\u70f7\u57fa\u5364\u9aa8\u67b6\u662f\u4e00\u79cd\u5e38\u89c1\u7684\u5076\u8054\u8bd5\u5242\uff0c\u5e76\u5e7f\u6cdb\u5b58\u5728\u4e8e\u5404\u7c7b\u5929\u7136\u4ea7\u7269\u4ee5\u53ca\u836f\u7269\u5206\u5b50\u4e2d\u3002\u5e76\u4e14\uff0c\u5728\u8fc7\u53bb\u7684\u51e0\u5341\u5e74\u91cc\uff0c\u8bf8\u591a\u7814\u7a76\u56e2\u961f\u5df2\u7ecf\u6210\u529f\u8bbe\u8ba1\u51fa\u591a\u79cd\u5229\u7528\u70ef\u70c3\u7684\u6c22\u5364\u5316\u53cd\u5e94\u65b9\u6cd5\u5b66\u6784\u5efa\u70f7\u57fa\u5364\u5206\u5b50\u7684\u5408\u6210\u8f6c\u5316\u7b56\u7565[1]<\/sup> (Scheme 1A, left and middle)\u3002\u7136\u800c\uff0c\u6b64\u7c7b\u7b56\u7565\u5b58\u5728\u5b98\u80fd\u56e2\u517c\u5bb9\u6027\u5dee\u4ee5\u53ca\u539f\u5b50\u7ecf\u6d4e\u6027\u5dee\u7b49\u5f0a\u7aef\u3002\u53d7\u5230\u8fd1\u5e74\u6765\u53cc\u91cd\u94b4\/\u5149\u6c27\u5316\u8fd8\u539f\u50ac\u5316\u53cd\u5e94\u65b9\u6cd5\u5b66[2]<\/sup>\u4ee5\u53ca\u5149\u6c27\u5316\u8fd8\u539f\u50ac\u5316\u70ef\u70c3\u6c22\u5364\u5316\u53cd\u5e94\u65b9\u6cd5\u5b66[3]<\/sup>\u76f8\u5173\u7814\u7a76\u62a5\u9053\u7684\u542f\u53d1\uff0c\u8fd9\u91cc\uff0c\u65e5\u672c\u4eac\u90fd\u5927\u5b66\u7684Hirohisa Ohmiya\u4e0eKazunori Nagao\u8bfe\u9898\u7ec4\u62a5\u9053\u4e00\u79cd\u5168\u65b0\u7684\u53cc\u91cd\u94b4\/\u5149\u6c27\u5316\u8fd8\u539f\u50ac\u5316\u8102\u80aa\u65cf\u70ef\u70c3\u4e0ecollidine\u00b7HX\u76d0\u7684\u6c22\u5364\u5316\u53cd\u5e94\u65b9\u6cd5\u5b66\uff0c\u8fdb\u800c\u6210\u529f\u5b8c\u6210\u4e00\u7cfb\u5217\u9ad8\u5ea6\u5b98\u80fd\u56e2\u5316\u7684\u70f7\u57fa\u5364\u5206\u5b50\u7684\u6784\u5efa\uff0c\u6d89\u53ca\u5173\u952e\u7684\u6781\u6027\u53cd\u8f6c\u7684\u8fc7\u7a0b (Scheme 1B)\u3002
<\/p>\n
\u9996\u5148\uff0c\u4f5c\u8005\u91c7\u75284-\u82ef\u57fa-1-\u4e01\u70ef1a<\/strong>\u4e0ecollidine\u00b7HBr\u76d02a<\/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\u7528Co-1<\/strong>\u4f5c\u4e3a\u50ac\u5316\u5242\uff0cIr(ppy)3<\/sub>\u4f5c\u4e3a\u5149\u50ac\u5316\u5242\uff0c34W\u84dd\u8272LED (0.5 cm away)\u4f5c\u4e3a\u5149\u6e90\uff0c\u5728THF\u53cd\u5e94\u6eb6\u5242\u4e2d\uff0c\u6700\u7ec8\u83b7\u5f9771%\u5206\u79bb\u6536\u7387\u7684\u4ea7\u72693aa<\/strong>\u3002
<\/p>\n
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\u6b64\u5916\uff0c\u5bf9\u4e8eC\u2212X\u952e\u7684\u5f62\u6210\u53ef\u80fd\u5b58\u5728\u4e24\u79cd\u53ef\u80fd\u7684\u673a\u7406\uff0c\u5373\u70f7\u57fa\u81ea\u7531\u57fa\u6216\u70f7\u57fa\u94b4(III)\u4e0e\u5364\u5316\u94b4(III)\u7684SH<\/sub>2\u53cd\u5e94 (Scheme 1B)\u4ee5\u53ca\u5364\u5316\u7269\u9634\u79bb\u5b50\u4e0e\u70f7\u57fa\u94b4(IV)\u914d\u5408\u7269\u4e4b\u95f4\u7684SN<\/sub>2\u53cd\u5e94\u3002\u4e3a\u4e86\u533a\u5206\u4e0a\u8ff0\u7684\u53cd\u5e94\u673a\u7406\uff0c\u4f5c\u8005\u5bf9\u4e0a\u8ff0\u6c22\u5364\u5316\u8fc7\u7a0b\u7684\u53cd\u5e94\u673a\u7406\u8fdb\u884c\u8fdb\u4e00\u6b65\u7814\u7a76 \u00a0(Figure 2)\u3002
\u603b\u7ed3\uff1a<\/p>\n
\u65e5\u672c\u4eac\u90fd\u5927\u5b66\u7684Hirohisa Ohmiya\u4e0eKazunori Nagao\u8bfe\u9898\u7ec4\u62a5\u9053\u4e00\u79cd\u5168\u65b0\u7684\u53cc\u91cd\u94b4\/\u5149\u6c27\u5316\u8fd8\u539f\u50ac\u5316\u8102\u80aa\u65cf\u70ef\u70c3\u4e0ecollidine\u00b7HX\u76d0\u7684\u6c22\u5364\u5316\u53cd\u5e94\u65b9\u6cd5\u5b66\uff0c\u8fdb\u800c\u6210\u529f\u5b8c\u6210\u4e00\u7cfb\u5217\u9ad8\u5ea6\u5b98\u80fd\u56e2\u5316\u7684\u70f7\u57fa\u5364\u5206\u5b50\u7684\u6784\u5efa\u3002\u8fd9\u4e00\u5168\u65b0\u7684\u6c22\u5364\u5316\u5408\u6210\u8f6c\u5316\u7b56\u7565\u5177\u6709\u5e95\u7269\u8303\u56f4\u5e7f\u6cdb\u3001\u4f18\u826f\u7684\u5b98\u80fd\u56e2\u517c\u5bb9\u6027\u4ee5\u53ca\u4f18\u826f\u7684\u539f\u5b50\u7ecf\u6d4e\u6027\u7b49\u4f18\u52bf\u3002<\/p>\n
\u53c2\u8003\u6587\u732e\uff1a<\/strong><\/h4>\n
10.1021\/acs.chemrev.6b00334<\/a>.<\/li>\n\n
- [1] S. W. M. Crossley, C. Obradors, R. M. Martinez, R. A. Shenvi,Chem. Rev. <\/em>2016<\/strong>,116<\/em>, 8912. doi:
[2] D. J. Wilger, J. M. M. Grandjean, T. R. Lammert, D. A. Nicewicz,Nat. Chem. <\/em>2014<\/strong>,6<\/em>, 720. doi: 10.1038\/nchem.2000<\/a>.<\/li>\n[3] J. Kim, X. Sun, B. A. van der Worp, T. Ritter,Nat. Catal. <\/em>2023<\/strong>,6<\/em>, 196. doi: 10.1038\/s41929-023-00914-7<\/a>.<\/li>\n<\/ul>\n\u672c\u6587\u7248\u6743\u5c5e\u4e8e Chem-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\uff1a\u6749\u6749 \u5bfc\u8bfb\uff1a \u8fd1\u671f\uff0c\u65e5\u672c\u4eac\u90fd\u5927\u5b66\u7684Hirohisa Ohmiya\u4e0eKazunori Nagao\u8bfe\u9898\u7ec4\u5728J. Am. Chem. Soc.\u4e2d\u53d1\u8868\u8bba\u6587\uff0c\u62a5\u9053\u4e00\u79cd\u5168\u65b0\u7684\u53cc\u91cd\u94b4\/\u5149\u6c27\u5316\u8fd8\u539f\u50ac\u5316\u8102\u80aa\u65cf\u70ef\u70c3\u4e0ecollidine\u00b7HX\u76d0\u7684\u6c22\u5364\u5316\u53cd\u5e94\u65b9\u6cd5\u5b66\uff0c\u8fdb\u800c\u6210\u529f\u5b8c\u6210\u4e00\u7cfb\u5217\u9ad8\u5ea6\u5b98\u80fd\u56e2\u5316\u7684\u70f7\u57fa\u5364\u5206\u5b50\u7684\u6784\u5efa\u3002 A Dual Cobalt and Photoredox Catalysis for Hydrohalogenation of Alkenes S. Shibutani, K. Nagao, H. Ohmiya, J. Am. Chem. Soc. 2024, 146, 4375. doi: 10.1021\/jacs.3c10133 \u6b63\u6587\uff1a \u70f7\u57fa\u5364\u9aa8\u67b6\u662f\u4e00\u79cd\u5e38\u89c1\u7684\u5076\u8054\u8bd5\u5242\uff0c\u5e76\u5e7f\u6cdb\u5b58\u5728\u4e8e\u5404\u7c7b\u5929\u7136\u4ea7\u7269\u4ee5\u53ca\u836f\u7269\u5206\u5b50\u4e2d\u3002\u5e76\u4e14\uff0c\u5728\u8fc7\u53bb\u7684\u51e0\u5341\u5e74\u91cc\uff0c\u8bf8\u591a\u7814\u7a76\u56e2\u961f\u5df2\u7ecf\u6210\u529f\u8bbe\u8ba1\u51fa\u591a\u79cd\u5229\u7528\u70ef\u70c3\u7684\u6c22\u5364\u5316\u53cd\u5e94\u65b9\u6cd5\u5b66\u6784\u5efa\u70f7\u57fa\u5364\u5206\u5b50\u7684\u5408\u6210\u8f6c\u5316\u7b56\u7565[1] (Scheme 1A, left and middle)\u3002\u7136\u800c\uff0c\u6b64\u7c7b\u7b56\u7565\u5b58\u5728\u5b98\u80fd\u56e2\u517c\u5bb9\u6027\u5dee\u4ee5\u53ca\u539f\u5b50\u7ecf\u6d4e\u6027\u5dee\u7b49\u5f0a\u7aef\u3002\u53d7\u5230\u8fd1\u5e74\u6765\u53cc\u91cd\u94b4\/\u5149\u6c27\u5316\u8fd8\u539f\u50ac\u5316\u53cd\u5e94\u65b9\u6cd5\u5b66[2]\u4ee5\u53ca\u5149\u6c27\u5316\u8fd8\u539f\u50ac\u5316\u70ef\u70c3\u6c22\u5364\u5316\u53cd\u5e94\u65b9\u6cd5\u5b66[3]\u76f8\u5173\u7814\u7a76\u62a5\u9053\u7684\u542f\u53d1\uff0c\u8fd9\u91cc\uff0c\u65e5\u672c\u4eac\u90fd\u5927\u5b66\u7684Hirohisa Ohmiya\u4e0eKazunori Nagao\u8bfe\u9898\u7ec4\u62a5\u9053\u4e00\u79cd\u5168\u65b0\u7684\u53cc\u91cd\u94b4\/\u5149\u6c27\u5316\u8fd8\u539f\u50ac\u5316\u8102\u80aa\u65cf\u70ef\u70c3\u4e0ecollidine\u00b7HX\u76d0\u7684\u6c22\u5364\u5316\u53cd\u5e94\u65b9\u6cd5\u5b66\uff0c\u8fdb\u800c\u6210\u529f\u5b8c\u6210\u4e00\u7cfb\u5217\u9ad8\u5ea6\u5b98\u80fd\u56e2\u5316\u7684\u70f7\u57fa\u5364\u5206\u5b50\u7684\u6784\u5efa\uff0c\u6d89\u53ca\u5173\u952e\u7684\u6781\u6027\u53cd\u8f6c\u7684\u8fc7\u7a0b (Scheme 1B)\u3002 \u9996\u5148\uff0c\u4f5c\u8005\u91c7\u75284-\u82ef\u57fa-1-\u4e01\u70ef1a\u4e0ecollidine\u00b7HBr\u76d02a\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\u7528Co-1\u4f5c\u4e3a\u50ac\u5316\u5242\uff0cIr(ppy)3\u4f5c\u4e3a\u5149\u50ac\u5316\u5242\uff0c34W\u84dd\u8272LED (0.5 cm away)\u4f5c\u4e3a\u5149\u6e90\uff0c\u5728THF\u53cd\u5e94\u6eb6\u5242\u4e2d\uff0c\u6700\u7ec8\u83b7\u5f9771%\u5206\u79bb\u6536\u7387\u7684\u4ea7\u72693aa\u3002 \u540c\u65f6\uff0c\u901a\u8fc7\u53cd\u5e94\u6761\u4ef6\u7684\u7a0d\u5fae\u4fee\u6539\uff0c\u8be5\u7b56\u7565\u8fd8\u53ef\u7528\u4e8e\u5176\u4ed6\u5364\u7d20\u7684\u6c22\u5364\u5316\u53cd\u5e94\u65b9\u6cd5\u5b66(Figure 1A)\u3002\u7d27\u63a5\u7740\uff0c\u4f5c\u8005\u5bf9\u4e00\u7cfb\u5217\u70ef\u70c3\u5e95\u7269\u4e0e\u5364\u7d20\u5e95\u7269 (Figure 1B)\u7684\u5e94\u7528\u8303\u56f4\u8fdb\u884c\u6df1\u5165\u7814\u7a76\u3002 \u6b64\u5916\uff0c\u5bf9\u4e8eC\u2212X\u952e\u7684\u5f62\u6210\u53ef\u80fd\u5b58\u5728\u4e24\u79cd\u53ef\u80fd\u7684\u673a\u7406\uff0c\u5373\u70f7\u57fa\u81ea\u7531\u57fa\u6216\u70f7\u57fa\u94b4(III)\u4e0e\u5364\u5316\u94b4(III)\u7684SH2\u53cd\u5e94 (Scheme 1B)\u4ee5\u53ca\u5364\u5316\u7269\u9634\u79bb\u5b50\u4e0e\u70f7\u57fa\u94b4(IV)\u914d\u5408\u7269\u4e4b\u95f4\u7684SN2\u53cd\u5e94\u3002\u4e3a\u4e86\u533a\u5206\u4e0a\u8ff0\u7684\u53cd\u5e94\u673a\u7406\uff0c\u4f5c\u8005\u5bf9\u4e0a\u8ff0\u6c22\u5364\u5316\u8fc7\u7a0b\u7684\u53cd\u5e94\u673a\u7406\u8fdb\u884c\u8fdb\u4e00\u6b65\u7814\u7a76 \u00a0(Figure 2)\u3002 \u603b\u7ed3\uff1a \u65e5\u672c\u4eac\u90fd\u5927\u5b66\u7684Hirohisa Ohmiya\u4e0eKazunori Nagao\u8bfe\u9898\u7ec4\u62a5\u9053\u4e00\u79cd\u5168\u65b0\u7684\u53cc\u91cd\u94b4\/\u5149\u6c27\u5316\u8fd8\u539f\u50ac\u5316\u8102\u80aa\u65cf\u70ef\u70c3\u4e0ecollidine\u00b7HX\u76d0\u7684\u6c22\u5364\u5316\u53cd\u5e94\u65b9\u6cd5\u5b66\uff0c\u8fdb\u800c\u6210\u529f\u5b8c\u6210\u4e00\u7cfb\u5217\u9ad8\u5ea6\u5b98\u80fd\u56e2\u5316\u7684\u70f7\u57fa\u5364\u5206\u5b50\u7684\u6784\u5efa\u3002\u8fd9\u4e00\u5168\u65b0\u7684\u6c22\u5364\u5316\u5408\u6210\u8f6c\u5316\u7b56\u7565\u5177\u6709\u5e95\u7269\u8303\u56f4\u5e7f\u6cdb\u3001\u4f18\u826f\u7684\u5b98\u80fd\u56e2\u517c\u5bb9\u6027\u4ee5\u53ca\u4f18\u826f\u7684\u539f\u5b50\u7ecf\u6d4e\u6027\u7b49\u4f18\u52bf\u3002 \u53c2\u8003\u6587\u732e\uff1a [1] S. W. M. Crossley, C. Obradors, R. M. Martinez, R. A. Shenvi, Chem. Rev. 2016, 116, 8912. doi:10.1021\/acs.chemrev.6b00334. [2] D. J. Wilger, J. M. M. Grandjean, T. R. Lammert, D. A. Nicewicz, Nat. Chem. 2014, 6, 720. doi:10.1038\/nchem.2000. [3] J. Kim, X. Sun, B. A. 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\u8bd1\u81eaChem-Station\u7f51\u7ad9\u65e5\u672c\u7248 \u539f\u6587\u94fe\u63a5\uff1a
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2024\u5e741\u6708\uff0cACS Medicinal Chemistry Letters\u00a0\u671f\u520a\u53d1\u5e03\u4e86\u4e00\u7bc7\u4ee5”\u5929\u7136\u7269\u5168\u5408\u6210\u81f3\u4eca\u4ecd\u7136\u662f\u521b\u836f\u5316\u5b66<\/strong>(<\/strong>\u533b\u836f\u5316\u5b66<\/strong>)<\/strong>\u4e00\u4e2a\u5f88\u597d\u7684\u8bad\u7ec3\u8bfe\u7a0b<\/strong>“\u4e3a\u4e3b\u9898\u7684\u89c2\u70b9\u8bba\u6587\uff0c2024\u5e746\u6708\u8be5\u7bc7\u8bba\u6587\u5f53\u9009\u4e3aACS Medicinal Chemistry Letters<\/strong>\u7684Most Read Article\u3002<\/p>\n
10.1021\/acsmedchemlett.3c00556<\/em><\/a><\/p><\/blockquote>\nTotal Synthesis as Training for Medicinal Chemistry
\nLewis D. Pennington
\nACS Med. Chem. Lett.<\/em>\u00a02024,\u00a015<\/em>,\u00a02<\/em>, 156\u2013158, DOI:\u00a0\u8bba\u6587\u4f5c\u8005Lewis D. Pennington<\/strong>\u73b0\u62c5\u4efbMystic River Medicinal Chemistry, LLC\u7684\u987e\u95ee\uff0c\u5728\u7f8e\u56fd\u62e5\u670918\u9879\u4e13\u5229\uff0cWO\u7533\u8bf7\u4e13\u522937\u4ef6\uff0c\u53c2\u4e0e\u4e86\u4e24\u79cd\u5df2\u8fdb\u5165\u4e34\u5e8a\u8bd5\u9a8c\u836f\u7269\u7684\u7814\u53d1\u3002\u4ece2003\u5e74\u81f32015\u5e74\u5728Amgen\u5de5\u4f5c\u3002<\/p>\n
\u5168\u5408\u6210\u548c\u521b\u836f\u5316\u5b66<\/h4>\n
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\u5f53\u4eca\u7684\u836f\u7269\u5316\u5b66\u5bb6\u8981\u9762\u5bf9\u7684\u662f\u6781\u5177\u6311\u6218\u6027\u7684\u6cbb\u7597\u9776\u5411\uff0c\u8fd8\u6709\u8fc5\u901f\u4f18\u5316\u5404\u7c7b\u53c2\u6570\u4ee5\u53ca\u529f\u80fd\u4ea4\u53c9 (cross-functional)\u6027\u8d28\u7684\u9700\u8981\uff0c\u6240\u4ee5\u4ec5\u4ec5\u662f\u5408\u6210\u9886\u57df\u7684\u77e5\u8bc6\u65e0\u6cd5\u6ee1\u8db3\u73b0\u4ee3\u836f\u7269\u5316\u5b66\u5bb6\u4eec\u7684\u9700\u6c42\uff0c\u73b0\u4ee3\u836f\u7269\u5316\u5b66\u5bb6\u9700\u8981\u7684\u662f\u4ea4\u53c9\u9886\u57df\u7684\u77e5\u8bc6\u3002\u6b64\u5916\uff0c\u836f\u7269\u5316\u5b66\u4e5f\u6d89\u53ca\u6838\u9178\u3001\u80bd\u7c7b\u3001\u6297\u4f53-\u836f\u7269\u5076\u8054\u7269\uff08Antibody-drug conjugate\uff0c\u7b80\u79f0\u4e3aADC\uff09\u7b49\u65b0\u578b\u836f\u7269\u5f62\u5f0f\u7684\u5f00\u53d1\uff0c\u4f46\u53e6\u4e00\u65b9\u9762\uff0c\u6709\u4eba\u6307\u51fa\u5728\u5236\u836f\u884c\u4e1a\u76f8\u8f83\u4e8e\u5168\u5408\u6210\uff0c\u5316\u5b66\u751f\u7269\u5b66\u548c\u8ba1\u7b97\u5316\u5b66\u7684\u8bad\u7ec3\u53ef\u80fd\u66f4\u4e3a\u6709\u76ca\u3002\u5f53\u4e0bAI\u521b\u836f\u662f\u5927\u52bf\u6240\u8d8b\uff0c\u5728\u8fd9\u6837\u7684\u80cc\u666f\u4e0b\u5168\u5408\u6210\u80fd\u591f\u6301\u7eed\u4e3a\u73b0\u4ee3\u521b\u836f\u5316\u5b66\u521b\u9020\u51fa\u4ef7\u503c\u5417\uff1f<\/p>\n
\u4f5c\u4e3a\u672c\u6587\u4f5c\u8005\u7684\u6211\u5bf9\u4ee5\u4e0a\u7591\u95ee\u7684\u56de\u7b54\u662f\u300cYES<\/strong>\u300d\uff0c\u7b14\u8005\u8fd8\u76f8\u4fe1\u4f5c\u4e3a\u836f\u7269\u5316\u5b66\u5bb6\u8bad\u7ec3\u8425\u7684\u5168\u5408\u6210\u7684\u5b66\u4e60\u542b\u91d1\u91cf\u4eca\u540e\u8fd8\u4f1a\u4e0d\u65ad\u5730”\u5347\u503c”\u3002<\/p>\n
\u5728\u73b0\u4ee3\u836f\u7269\u5316\u5b66\uff0c\u7279\u522b\u662f\u5c0f\u5206\u5b50\u836f\u7269\u7814\u53d1\u4e2d\uff0c\u7ed3\u6784\u7684\u65b0\u9896\u6027\u548c\u5206\u5b50\u7684\u590d\u6742\u6027\u4e0d\u65ad\u589e\u52a0\uff0c\u800c\u4ee5\u5929\u7136\u7269\u4e3a\u57fa\u7840\u7684\u836f\u7269\u4f9d\u7136\u662f\u5c0f\u5206\u5b50\u5230\u4e2d\u5206\u5b50\u836f\u7269\u7684\u6a21\u677f\u3002\u6b64\u5916\uff0c\u6b63\u5982Fsp3<\/sub>\u8fd9\u4e00\u53c2\u6570\u6240\u4ee3\u8868\u7684\u90a3\u6837\uff0c\u7c7b\u4f3c\u5929\u7136\u7269\u7684\u4f4e\u5e73\u9762\u6027\u548c\u9ad8\u67d4\u6027\u7684\u5206\u5b50\u5728\u836f\u7269\u7814\u53d1\u4e2d\u53ef\u80fd\u5177\u6709\u8f83\u9ad8\u7684\u6210\u529f\u6982\u7387\uff0c\u56e0\u6b64\uff0c\u4ece\u5168\u5408\u6210\u4e2d\u53ef\u4ee5\u5b66\u5230\u5f88\u591a\u4e1c\u897f\u3002<\/p>\n
\u5168\u5408\u6210\u548c\u521b\u836f\u5316\u5b66\u7684\u76f8\u4f3c\u6027<\/h4>\n
<\/p>\n
\u5168\u5408\u6210\u4e5f\u8981\u836f\u7269\u5316\u5b66\u4e5f\u597d\uff0c\u7686\u4e3b\u8981\u805a\u7126\u4e8e\u5c0f\u5206\u5b50\uff0c\u901a\u8fc7\u53cd\u590d\u5730\u8bbe\u8ba1\u548c\u5408\u6210\u6765\u5f97\u5230\u76ee\u6807\u5206\u5b50\u3002\u5168\u5408\u6210\u4ece\u6613\u5f97\u7684\u539f\u6599\u5f00\u59cb\uff0c\u901a\u8fc7\u4e00\u7cfb\u5217\u5408\u6210\u6b65\u9aa4\u83b7\u5f97\u76ee\u6807\u5929\u7136\u7269\u3002\u53e6\u4e00\u65b9\u9762\uff0c\u521b\u836f\u5316\u5b66\u4ece\u7b5b\u9009\u7b49\u65b9\u6cd5\u53d1\u73b0\u7684\u6d3b\u6027\u5316\u5408\u7269\u5f00\u59cb\uff0c\u901a\u8fc7\u8bbe\u8ba1\u548c\u5408\u6210\u884d\u751f\u7269\uff0c\u4ee5\u83b7\u5f97\u4e34\u5e8a\u5019\u9009\u836f\u7269\u4e3a\u76ee\u7684\u3002\u4e24\u8005\u90fd\u5728\u5206\u5b50\u8bbe\u8ba1\u3001\u5408\u6210\u8def\u5f84\u7684\u6784\u5efa\u3001\u4e2d\u95f4\u4f53\u6216\u7c7b\u4f3c\u7269\u7684\u5206\u6790\u4ee5\u53ca\u6709\u65f6\u8fdb\u884c\u751f\u7406\u6d3b\u6027\u6d4b\u8bd5\u65b9\u9762\u5b58\u5728\u5171\u901a\u70b9\u3002\u6b64\u5916\u8bba\u6587\u8fd8\u6307\u51fa\uff0c\u8fd1\u5e74\u6765\u4e0d\u4ec5\u5728\u836f\u7269\u5316\u5b66\u9886\u57df\uff0c\u800c\u4e14\u5728\u5168\u5408\u6210\u9886\u57df\u4e2dAI\u548c\u673a\u5668\u5b66\u4e60\u3001\u9ad8\u901a\u91cf\u6d4b\u8bd5\u7b49\u6280\u672f\u7684\u5e94\u7528\u4e5f\u5728\u589e\u52a0\u3002<\/p>\n
\u5168\u5408\u6210\u548c\u521b\u836f\u7684\u7814\u7a76\u6d41\u7a0b\u5bf9\u6bd4<\/h4>\n
\u7b14\u8005\u5217\u51fa\u4e86\u5168\u5408\u6210\u548c\u521b\u836f\u5404\u81ea\u7684\u7814\u7a76\u6d41\u7a0b\u8868(\u89c1\u4e0b\uff0c\u8868\u683c\u6839\u636e
\u8bba\u6587<\/a>\u8868\u683c\u7ffb\u8bd1)\u3002\u867d\u7136\u770b\u8d77\u6765\u4e24\u8005\u7684\u6d41\u7a0b\u90fd\u5dee\u4e0d\u591a\uff0c\u8fd8\u662f\u6709\u51e0\u4e2a\u4e0d\u540c\u7684\u73af\u8282\uff0c\u4f46\u6211\u4ecd\u65e7\u8ba4\u4e3a\u7814\u7a76\u8005\u5728\u5168\u5408\u6210\u9886\u57df\u79ef\u7d2f\u7684\u5404\u5f0f\u6280\u80fd\u4ecd\u80fd\u5728\u521b\u836f\u9886\u57df\u53d1\u6325\u4f5c\u7528\u3002<\/p>\nTable, \u00a0Analogous Conceptual Frameworks of Total Synthesis and Medicinal Chemistry<\/strong><\/p>\n
\n\n\n\n\n\n\n\n\n\n\n\n\n\n\n\n\n\n\n