新利18网址|新利官方网站

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\u4f5c\u8005 \u77f3\u6cb9\u919a<\/p>\n

\u5bfc\u8bfb<\/h4>\n
\u8fd1\u65e5\uff0c\u65b0\u52a0\u5761\u56fd\u7acb\u5927\u5b66\u5434\u6770<\/strong>\u8bfe\u9898\u7ec4\u4e0e\u5929\u6d25\u5927\u5b66\u9a6c\u519b\u5b89<\/strong>\uff0c\u5f20\u53d1\u5149<\/strong>\u8bfe\u9898\u7ec4\u5229\u7528\u5ec9\u4ef7\u7684\u5de5\u4e1a\u5316\u5b66\u54c1\u6c2f\u4e8c\u6c1f\u7532\u70f7\uff08<\/strong>ClCF_{2<\/sub>H, Freon-22<\/strong>\uff09\u4f5c\u4e3a\u6c1f\u6e90<\/strong>\uff0c\u5c06\u80fa\u787c\u70f7\u81ea\u7531\u57fa\u8bf1\u5bfc\u7684\u5364\u7d20\u539f\u5b50\u8f6c\u79fb\uff08<\/strong>XAT<\/strong>\uff09\u4e0e\u6709\u673a\u5149\u6c27\u5316\u8fd8\u539f\u50ac\u5316\u76f8\u7ed3\u5408<\/strong>\uff0c\u5b9e\u73b0\u4e86\u672a\u6d3b\u5316\u70ef\u70c3\u7684\u81ea\u7531\u57fa\u4e8c\u6c1f\u7532\u57fa\u5316\u53cd\u5e94<\/strong>\u3002\u8be5\u53cd\u5e94\u5177\u6709\u4f18\u5f02\u7684\u5b98\u80fd\u56e2\u517c\u5bb9\u6027\uff0c\u5e76\u4e14\u53ef\u4ee5\u5bf9\u836f\u7269\u5206\u5b50\u548c\u5929\u7136\u4ea7\u7269\u4ee5\u826f\u597d\u7684\u6548\u7387\u8fdb\u884c\u540e\u671f\u5b98\u80fd\u56e2\u4fee\u9970\uff08<\/strong>LSF<\/strong>\uff09<\/strong>\u3002\u5b9e\u9a8c\u548c\u8ba1\u7b97\u7ed3\u5408\u7814\u7a76\u8868\u660e\uff0c\u7531\u4e8e\u53cd\u5e94\u7269\u7684\u78b3-\u6c2f\u952e\u53cd\u952e\u8f68\u9053\u80fd\u91cf\u4f4e\uff0c\u4ea7\u7269\u787c-\u6c2f\u952e\u952e\u80fd\u9ad8\uff0cClCF_{2<\/sub>H\u7684\u5364\u7d20\u539f\u5b50\u8f6c\u79fb\u8fc7\u7a0b\uff08XAT\uff09\u5728\u52a8\u529b\u5b66\u548c\u70ed\u529b\u5b66\u4e0a\u5747\u4f18\u4e8e\u6c22\u539f\u5b50\u8f6c\u79fb\u9014\u5f84\uff08HAT\uff09\u3002\u76f8\u5173\u7814\u7a76\u6210\u679c\u53d1\u8868\u5728J. Am. Chem. Soc. <\/em><\/strong>\u6742\u5fd7\u3002<\/p>\n}}

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Difluoromethylation of Unactivated Alkenes Using Freon-22 through Tertiary Amine-Borane-Triggered Halogen Atom Transfer<\/p>\n
Zhi-Qi Zhang,# Yue-Qian Sang,# Cheng-Qiang Wang, Peng Dai, Xiao-Song Xue, Jared L. Piper,\u00a0Zhi-Hui Peng, Jun-An Ma,* Fa-Guang Zhang,* and Jie Wu<\/p>\n
J.<\/em>\u00a0Am. Chem. Soc. ASAP. \u00a0<\/em>DOI: 10.1021\/jacs.2c05356<\/a><\/p>\n<\/blockquote>\n*
\u6b63\u6587<\/h4>\n
\u4e0e C(sp^{3<\/sup>) \u539f\u5b50\u76f8\u8fde\u7684\u4e8c\u6c1f\u7532\u57fa\uff08CF_{2<\/sub>H\uff09\u56e0\u5176\u72ec\u7279\u7684\u6027\u8d28\u5728\u5236\u836f\u548c\u519c\u4e1a\u5316\u5b66\u79d1\u5b66\u4e2d\u5f15\u8d77\u4e86\u6781\u5927\u7684\u5174\u8da3\uff0c\u5b58\u5728\u4e8e\u8bb8\u591a\u751f\u7269\u6d3b\u6027\u5316\u5408\u7269\u4e2d\uff08\u56fe 1A\uff09\uff0c\u5e76\u4e14\u53ef\u4ee5\u4f5c\u4e3a\u4eb2\u8102\u6027\u6c22\u952e\u4f9b\u4f53\u548c\u7f9f\u57fa\u3001\u786b\u9187\u548c\u80fa\u57fa\u7684\u751f\u7269\u7b49\u6392\u4f53\u3002\u56e0\u6b64\uff0c\u4e8c\u6c1f\u7532\u57fa\u5316\u5df2\u6210\u4e3a\u6539\u53d8\u5148\u5bfc\u5316\u5408\u7269\u751f\u7269\u6d3b\u6027\u7684\u6709\u529b\u7b56\u7565\uff0c\u5c24\u5176\u662f\u901a\u8fc7\u540e\u671f\u5b98\u80fd\u56e2\u4fee\u9970\u3002\u5c3d\u7ba1C(sp^{3<\/sup>)-CF_{2<\/sub>H \u952e\u7684\u5f62\u6210\u662f\u901a\u8fc7\u4eb2\u6838\u3001\u4eb2\u7535\u548c\u81ea\u7531\u57fa\u4e8c\u6c1f\u7532\u57fa\u5316\u5b9e\u73b0\u7684\uff0c\u4f46\u5927\u591a\u6570\u65b9\u6cd5\u90fd\u4f9d\u8d56\u4e8e\u9700\u8981\u591a\u4e2a\u6b65\u9aa4\u6765\u5236\u5907\u7684\u6602\u8d35\u8bd5\u5242\u6216\u7ed3\u6784\u5355\u5143\u3002<\/p>\n}}}}
\u6c2f\u4e8c\u6c1f\u7532\u70f7\uff08ClCF_{2<\/sub>H\uff0c\u4e5f\u79f0\u4e3aFreon-22\uff09\u662f\u4e00\u79cd\u7406\u60f3\u7684\u6c1f\u6e90\uff0c\u662f\u751f\u4ea7\u5404\u79cd\u542b\u6c1f\u805a\u5408\u7269\uff08\u5982\u805a\u56db\u6c1f\u4e59\u70ef\u548c\u805a\u504f\u4e8c\u6c1f\u4e59\u70ef\uff09\u7684\u4e30\u5bcc\u5de5\u4e1a\u539f\u6599\u3002\u7531\u4e8eClCF_{2<\/sub>H \u7684\u4f4e\u53cd\u5e94\u6d3b\u6027\uff0c\u5176\u8f6c\u5316\u76f8\u5f53\u6709\u9650\uff0c\u4e3b\u8981\u6d89\u53ca\u4e8c\u6c1f\u5361\u5bbe\u4e2d\u95f4\u4f53\u3002\u53e6\u5916\uff0cC-H (~100 kcal\/mol) \u548c C-Cl (\u223c87 kcal\/mol) \u952e\u7684\u89e3\u79bb\u80fd (BDE) \u90fd\u5f88\u9ad8\uff0c\u56e0\u6b64\u901a\u8fc7HAT\u6216XAT\u8fc7\u7a0b\u6d3b\u5316 ClCF_{2<\/sub>H\u4e5f\u90fd\u5177\u6709\u6311\u6218\u6027\uff08\u56fe 1B\uff09\u3002\u5728\u6b64\u80cc\u666f\u4e0b\uff0c\u7531 Roberts \u7b49\u4eba\u53d1\u5c55\u7684\u914d\u4f4d\u787c\u57fa\u81ea\u7531\u57fa\uff08\u901a\u5f0f\uff1aLB^{+<\/sup>-R_{2<\/sub>B^{\u2022-<\/sup>\uff09\uff0c\u5177\u6709\u4eb2\u6838\u6027\u5e76\u53ef\u4ee5\u901a\u8fc7\u914d\u4f53\u8c03\u63a7B-H\u952e\u7684\u952e\u80fd\u3002Curran\u548cRyu\u4f7f\u7528NHC-\u787c\u70f7\u8fdb\u884c\u8131\u7898\u548c\u7f9f\u7532\u57fa\u5316\u53cd\u5e94\u8fdb\u4e00\u6b65\u8bc1\u660e\u4e86XAT\u53cd\u5e94\u6027\uff0c\u4f46\u4ec5\u9650\u4e8e\u70f7\u57fa\u7898\u548c\u6eb4\u7684\u6d3b\u5316\u3002\u6700\u8fd1\uff0c\u4e0a\u6d77\u4ea4\u901a\u5927\u5b66\u53f6\u4fca\u6d9b\u5c0f\u7ec4\u5728\u5149\u6c27\u5316\u8fd8\u539f\u50ac\u5316\u4e0b\uff0c\u4f7f\u7528\u80fa\u787c\u70f7\u4f5c\u4e3aHAT\u8bd5\u5242\uff0c\u5b9e\u73b0\u4e86\u5bf9\u672a\u6d3b\u5316\u70ef\u70c3\u7684\u6c22\u70f7\u57fa\u5316\u3002\u7531\u4e8e\u5bf9\u6c14\u4f53\u4f5c\u4e3a\u539f\u6599\u7684\u8f6c\u5316\u548c\u6c1f\u70f7\u57fa\u5316\u53cd\u5e94\u7684\u5174\u8da3\uff0c\u4f5c\u8005\u53d1\u5c55\u4e86\u80fa\u787c\u70f7\u4f5c\u4e3aXAT\u8bd5\u5242\u6d3b\u5316ClCF_{2<\/sub>H\uff0c\u4ee5\u65e0\u91d1\u5c5e\u53c2\u4e0e\u7684\u7b56\u7565\u5bf9\u672a\u6d3b\u5316\u70ef\u70c3\u8fdb\u884c\u4e8c\u6c1f\u7532\u57fa\u5316\uff0c\u540c\u65f6\u8be5\u7b56\u7565\u53ef\u5e94\u7528\u4e8e\u836f\u7269\u5206\u5b50\u548c\u5929\u7136\u4ea7\u7269\u7684\u540e\u671f\u5b98\u80fd\u56e2\u4fee\u9970\uff08\u56fe 1D\uff09\u3002<\/p>\n}}}}}}}
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\u673a\u7406\u7814\u7a76<\/strong>\uff1a\u4f5c\u8005\u8fdb\u884c\u4e86\u4e00\u7cfb\u5217\u5b9e\u9a8c\u548c\u8ba1\u7b97\u7814\u7a76\u4ee5\u63a2\u7d22\u8be5\u53cd\u5e94\u7684\u673a\u7406\u3002\u9996\u5148\uff0c\u6a21\u677f\u53cd\u5e94\u7684\u8d28\u91cf\u5e73\u8861\u8bc1\u5b9e\u4e86Me_{3<\/sub>N-BH_{2<\/sub>Cl\u548cMe_{3<\/sub>N-BHCl_{2<\/sub>\u4f5c\u4e3a\u76f8\u5e94\u526f\u4ea7\u7269\u7684\u751f\u6210\uff08\u56fe 4A\uff09\uff0c\u4e0e\u6700\u521d\u63d0\u51fa\u7684XAT\u8fc7\u7a0b\u4e00\u81f4\u3002TEMPO\u7684\u81ea\u7531\u57fa\u6355\u83b7\u5b9e\u9a8c\u5b8c\u5168\u6291\u5236\u4e86\u4e8c\u6c1f\u7532\u57fa\u5316\u4ea7\u7269\u7684\u5f62\u6210\uff0c\u5e76\u68c0\u6d4b\u5230\u52a0\u6210\u4ea7\u7269TEMPO-CF_{2<\/sub>H\uff08\u56fe4B\uff09\u3002\u5728\u6807\u51c6\u6761\u4ef6\u4e0b\u7528\u53cc\u73af\u841c\u70ef\u03b2-\u848e\u70ef\u8fdb\u884c\u7684\u81ea\u7531\u57fa\u949f\u5b9e\u9a8c\u4ee550%\u7684\u6536\u7387\u5f97\u5230\u4e86\u5f00\u73af\u4ea7\u7269\uff08\u56fe4C\uff09\u3002\u8fd9\u4e24\u4e2a\u5b9e\u9a8c\u7ed3\u679c\u8868\u660eCF_{2<\/sub>H\u81ea\u7531\u57fa\u7684\u53c2\u4e0e\u3002\u91cd\u8981\u7684\u662f\uff0c\u8be5\u53cd\u5e94\u53ef\u4ee5\u6709\u6548\u5730\u6269\u5c55\u5230\u5176\u4ed6\u7f3a\u7535\u5b50\u7684\u5364\u4ee3\u70f7\uff0c\u800c\u6ca1\u6709\u5438\u7535\u5b50\u53d6\u4ee3\u57fa\u7684\u5364\u4ee3\u70f7\u4e0d\u53d1\u751f\u53cd\u5e94\uff0c\u4e3b\u8981\u662f\u7531\u4e8e\u5438\u7535\u5b50\u53d6\u4ee3\u57fa\u5b58\u5728\u4e0b\u7684XAT\u8fc7\u6e21\u6001\u4e2d\u7a33\u5b9a\u7684\u90e8\u5206\u8d1f\u7535\u8377\u3002\u6b64\u5916\uff0c\u4f7f\u7528Me_{3<\/sub>N-BH_{3<\/sub>\u548cMe_{3<\/sub>N-BD_{3<\/sub>\u8fdb\u884c\u4e86\u4e24\u4e2a\u5e73\u884c\u53cd\u5e94\uff0c\u5728\u540e\u4e00\u79cd\u60c5\u51b5\u4e0b\uff0c\u5c11\u91cf\u6c18\u539f\u5b50\u5f15\u5165\u4ea7\u7269(16%D)\uff0c\u52a8\u529b\u5b66\u540c\u4f4d\u7d20\u6548\u5e94 (KIE) \u503c\u6d4b\u91cf\u4e3a1.2\uff0c\u8fd9\u610f\u5473\u7740\u787c\u57fa\u81ea\u7531\u57fa\u7684\u4ea7\u751f\u53ef\u80fd\u4e0d\u53c2\u4e0e\u51b3\u901f\u6b65 (\u56fe 4E)\u3002\u6dfb\u52a0\u6c18\u4ee3\u6c34\u7684\u5bf9\u7167\u5b9e\u9a8c\u7684\u4ea7\u7269\u5177\u670980%\u7684\u6c18\u4ee3\u7387\uff0c\u8868\u660e\u5728\u53cd\u5e94\u8fc7\u7a0b\u4e2d\u53ef\u80fd\u8fdb\u884c\u8d28\u5b50\u4ea4\u6362\u3002\u4f7f\u7528Me_{3<\/sub>N-BH_{3<\/sub>\u548cPhSSPh\u8fdb\u884c\u7684Stern-Volmer\u731d\u706d\u5b9e\u9a8c\u8868\u660e\uff0cPhSSPh\u6bd4Me_{3<\/sub>N-BH_{3<\/sub>\u53ef\u4ee5\u66f4\u6709\u6548\u5730\u731d\u706d\u6fc0\u53d1\u7684\u5149\u50ac\u5316\u5242\uff08\u56fe 4F\uff09\u3002<\/p>\n}}}}}}}}}}}}}}
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\u6b64\u5916\uff0c\u4f5c\u8005\u548c\u4e0a\u6d77\u6709\u673a\u6240\u859b\u5c0f\u677e\u8bfe\u9898\u7ec4<\/strong>\u5408\u4f5c\uff0c\u901a\u8fc7\u5bc6\u5ea6\u6cdb\u51fd\u7406\u8bba\uff08DFT\uff09\u8ba1\u7b97\u53d1\u73b0XAT\u8fc7\u7a0b\u901f\u7387\u9ad8\u4e14\u4e0d\u53ef\u9006\uff0c\u81ea\u7531\u80fd\u80fd\u5792\u4e3a10.2 kcal\/mol\uff0c\u4ea7\u7269\u91ca\u653e\u80fd\u91cf31.7 kcal\/mol\uff08\u56fe 5A-1\uff09\u3002\u7136\u800c\uff0cHAT\u8fc7\u7a0b\u7684\u80fd\u5792\u6bd4XAT\u8fc7\u7a0b\u9ad82.0 kcal\/mol\uff0c\u4ea7\u7269\u5438\u6536\u80fd\u91cf2.1 kcal\/mol\u3002\u4e8c\u8005\u80fd\u5792\u5dee\u5f02\u53ef\u5f52\u56e0\u4e8eClCF_{2<\/sub>H\u7684\u5206\u5b50\u8f68\u9053\uff0c\u5176\u4e2dC-Cl\u952e\u53cd\u952e\u8f68\u9053 (\u03c3_{C-Cl<\/sub>, LUMO) \u7684\u80fd\u91cf\u4f4e\u4e8eC-H\u952e\u53cd\u952e\u8f68\u9053 (\u03c3_{C-H<\/sub>, LUMO+1) (\u56fe 5A-2)\u3002\u4e0e\u539f\u59cb\u7684C-Cl \u952e\uff08cal. BDE = 86 kcal\/mol\uff09\u76f8\u6bd4\uff0cXAT\u8fc7\u7a0b\u7684\u70ed\u529b\u5b66\u9a71\u52a8\u529b\u662f\u5f62\u6210\u66f4\u7a33\u5b9a\u7684B-Cl\u952e\uff08cal. BDE = 117 kcal\/mol\uff09\u3002\u80fa-\u787c\u57fa\u81ea\u7531\u57fa\u7684\u4eb2\u6838\u7279\u6027\u5141\u8bb8\u5728\u787c\u539f\u5b50\u4e0a\u79ef\u7d2f\u90e8\u5206\u6b63\u7535\u8377\uff0c\u4ece\u800c\u901a\u8fc7\u6781\u6027\u6548\u5e94\u964d\u4f4eXAT\u8fc7\u7a0b\u80fd\u5792\uff08\u56fe5A-3\uff09\u3002\u56e0\u6b64\uff0c\u5355\u6c2f\u787c\u57fa\u548c\u4e8c\u6c2f\u787c\u57fa\u81ea\u7531\u57fa\u7684\u4eb2\u6838\u6027\u4e0d\u8db3\u4ee5\u52a0\u901f\u53cd\u5e94\u3002XAT\u8fc7\u7a0b\u7684\u8fc7\u6e21\u6001\u7ed3\u6784\u66f4\u63a5\u8fd1\u53cd\u5e94\u7269\uff0c\u5176\u4e2dC-Cl\u952e\u7565\u5fae\u62c9\u957f0.16 \u00c5\uff08\u4ece1.78 \u00c5\u53d8\u4e3a1.94 \u00c5\uff09\u3002\u76f8\u5e94\u5185\u7980\u53cd\u5e94\u5750\u6807\u8ba1\u7b97\uff08IRC\uff09\u53d1\u73b0\u80fa\u787c\u57fa\u81ea\u7531\u57fa\u7684\u81ea\u65cb\u5bc6\u5ea6\u4ece1.000\uff08\u81ea\u7531\u57fa\uff09\u964d\u4f4e\u52300.621\uff08\u8fc7\u6e21\u6001\uff09\uff0c\u8bf4\u660e\u90e8\u5206\u81ea\u65cb\u8f6c\u79fb\u5148\u4e8eC-Cl\u952e\u65ad\u88c2\u53d1\u751f\u3002<\/p>\n}}}
<\/a><\/p>\n
\u603b\u7ed3<\/strong><\/h4>\n
\u65b0\u52a0\u5761\u56fd\u7acb\u5927\u5b66\u5434\u6770\u8bfe\u9898\u7ec4\u4e0e\u5929\u6d25\u5927\u5b66\u9a6c\u519b\u5b89\uff0c\u5f20\u53d1\u5149\u8bfe\u9898\u7ec4\u62a5\u9053\u4e86\u901a\u8fc7\u4f7f\u7528\u5ec9\u4ef7\u4e14\u4e30\u5bcc\u7684ClCF_{2<\/sub>H\u4f5c\u4e3a\u6c1f\u6e90\uff0c1\u5728\u6e29\u548c\u4e14\u65e0\u91d1\u5c5e\u7684\u6761\u4ef6\u4e0b\u6210\u529f\u5730\u5b9e\u73b0\u4e86\u672a\u6d3b\u5316\u70ef\u70c3\u7684\u4e8c\u6c1f\u7532\u57fa\u5316\u53cd\u5e94\u3002\u8be5\u65b9\u6cd5\u5177\u6709\u975e\u5e38\u5e7f\u6cdb\u7684\u5e95\u7269\u8303\u56f4\uff0c\u5e76\u6210\u529f\u5e94\u7528\u4e8e\u590d\u6742\u751f\u7269\u6d3b\u6027\u5206\u5b50\u7684\u540e\u671f\u5b98\u80fd\u56e2\u5316\u4fee\u9970\u3002\u5149\u6c27\u5316\u8fd8\u539f\u50ac\u5316\u4e0e\u53d4\u80fa\u787c\u70f7\u7684\u7ed3\u5408\u88ab\u8bc1\u660e\u662f\u9009\u62e9\u6027XAT\u8fc7\u7a0b\u6d3b\u5316ClCF_{2<\/sub>H\u7684\u6709\u529b\u7b56\u7565\uff0c\u4ece\u800c\u4e3a\u6c1f\u5229\u6602\u5316\u5b66\u539f\u6599\u5728\u5b9e\u9645\u5408\u6210\u5316\u5b66\u4e2d\u7684\u5229\u7528\u5f00\u8f9f\u4e86\u65b0\u65b9\u5411\u3002\u5929\u6d25\u5927\u5b66-\u65b0\u52a0\u5761\u56fd\u7acb\u5927\u5b66\u798f\u5dde\u8054\u5408\u5b66\u9662\u535a\u58eb\u751f\u5f20\u5fd7\u5947<\/strong>\u548c\u4e0a\u6d77\u6709\u673a\u6240\u535a\u58eb\u751f\u6851\u5cb3\u5343<\/strong>\u4e3a\u5171\u540c\u7b2c\u4e00\u4f5c\u8005\u3002<\/p>\n}}
<\/p>\n
\u8bfe\u9898\u7ec4\u4e3b\u9875<\/strong>\uff1a<\/p>\n

\n
\u5434\u6770\u8bfe\u9898\u7ec4\uff1a https:\/\/www.wujiegroupnus.com\/<\/a><\/li>\n
\u9a6c\u519b\u5b89\u8bfe\u9898\u7ec4\uff1a http:\/\/tjmos.tju.edu.cn\/majunan\/<\/a><\/li>\n<\/ul>\n
<\/p>\n","protected":false},"excerpt":{"rendered":"\u4f5c\u8005 \u77f3\u6cb9\u919a \u5bfc\u8bfb \u8fd1\u65e5\uff0c\u65b0\u52a0\u5761\u56fd\u7acb\u5927\u5b66\u5434\u6770\u8bfe\u9898\u7ec4\u4e0e\u5929\u6d25\u5927\u5b66\u9a6c\u519b\u5b89\uff0c\u5f20\u53d1\u5149\u8bfe\u9898\u7ec4\u5229\u7528\u5ec9\u4ef7\u7684\u5de5\u4e1a\u5316\u5b66\u54c1\u6c2f\u4e8c\u6c1f\u7532\u70f7\uff08ClCF2H, Freon-22\uff09\u4f5c\u4e3a\u6c1f\u6e90\uff0c\u5c06\u80fa\u787c\u70f7\u81ea\u7531\u57fa\u8bf1\u5bfc\u7684\u5364\u7d20\u539f\u5b50\u8f6c\u79fb\uff08XAT\uff09\u4e0e\u6709\u673a\u5149\u6c27\u5316\u8fd8\u539f\u50ac\u5316\u76f8\u7ed3\u5408\uff0c\u5b9e\u73b0\u4e86\u672a\u6d3b\u5316\u70ef\u70c3\u7684\u81ea\u7531\u57fa\u4e8c\u6c1f\u7532\u57fa\u5316\u53cd\u5e94\u3002\u8be5\u53cd\u5e94\u5177\u6709\u4f18\u5f02\u7684\u5b98\u80fd\u56e2\u517c\u5bb9\u6027\uff0c\u5e76\u4e14\u53ef\u4ee5\u5bf9\u836f\u7269\u5206\u5b50\u548c\u5929\u7136\u4ea7\u7269\u4ee5\u826f\u597d\u7684\u6548\u7387\u8fdb\u884c\u540e\u671f\u5b98\u80fd\u56e2\u4fee\u9970\uff08LSF\uff09\u3002\u5b9e\u9a8c\u548c\u8ba1\u7b97\u7ed3\u5408\u7814\u7a76\u8868\u660e\uff0c\u7531\u4e8e\u53cd\u5e94\u7269\u7684\u78b3-\u6c2f\u952e\u53cd\u952e\u8f68\u9053\u80fd\u91cf\u4f4e\uff0c\u4ea7\u7269\u787c-\u6c2f\u952e\u952e\u80fd\u9ad8\uff0cClCF2H\u7684\u5364\u7d20\u539f\u5b50\u8f6c\u79fb\u8fc7\u7a0b\uff08XAT\uff09\u5728\u52a8\u529b\u5b66\u548c\u70ed\u529b\u5b66\u4e0a\u5747\u4f18\u4e8e\u6c22\u539f\u5b50\u8f6c\u79fb\u9014\u5f84\uff08HAT\uff09\u3002\u76f8\u5173\u7814\u7a76\u6210\u679c\u53d1\u8868\u5728J. Am. Chem. Soc. \u6742\u5fd7\u3002 Difluoromethylation of Unactivated Alkenes Using Freon-22 through Tertiary Amine-Borane-Triggered Halogen Atom Transfer Zhi-Qi Zhang,# Yue-Qian Sang,# Cheng-Qiang Wang, Peng Dai, Xiao-Song Xue, Jared L. Piper,\u00a0Zhi-Hui Peng, Jun-An Ma,* Fa-Guang Zhang,* and Jie Wu* J.\u00a0Am. Chem. Soc. ASAP. \u00a0DOI: 10.1021\/jacs.2c05356 \u6b63\u6587 \u4e0e C(sp3) \u539f\u5b50\u76f8\u8fde\u7684\u4e8c\u6c1f\u7532\u57fa\uff08CF2H\uff09\u56e0\u5176\u72ec\u7279\u7684\u6027\u8d28\u5728\u5236\u836f\u548c\u519c\u4e1a\u5316\u5b66\u79d1\u5b66\u4e2d\u5f15\u8d77\u4e86\u6781\u5927\u7684\u5174\u8da3\uff0c\u5b58\u5728\u4e8e\u8bb8\u591a\u751f\u7269\u6d3b\u6027\u5316\u5408\u7269\u4e2d\uff08\u56fe 1A\uff09\uff0c\u5e76\u4e14\u53ef\u4ee5\u4f5c\u4e3a\u4eb2\u8102\u6027\u6c22\u952e\u4f9b\u4f53\u548c\u7f9f\u57fa\u3001\u786b\u9187\u548c\u80fa\u57fa\u7684\u751f\u7269\u7b49\u6392\u4f53\u3002\u56e0\u6b64\uff0c\u4e8c\u6c1f\u7532\u57fa\u5316\u5df2\u6210\u4e3a\u6539\u53d8\u5148\u5bfc\u5316\u5408\u7269\u751f\u7269\u6d3b\u6027\u7684\u6709\u529b\u7b56\u7565\uff0c\u5c24\u5176\u662f\u901a\u8fc7\u540e\u671f\u5b98\u80fd\u56e2\u4fee\u9970\u3002\u5c3d\u7ba1C(sp3)-CF2H \u952e\u7684\u5f62\u6210\u662f\u901a\u8fc7\u4eb2\u6838\u3001\u4eb2\u7535\u548c\u81ea\u7531\u57fa\u4e8c\u6c1f\u7532\u57fa\u5316\u5b9e\u73b0\u7684\uff0c\u4f46\u5927\u591a\u6570\u65b9\u6cd5\u90fd\u4f9d\u8d56\u4e8e\u9700\u8981\u591a\u4e2a\u6b65\u9aa4\u6765\u5236\u5907\u7684\u6602\u8d35\u8bd5\u5242\u6216\u7ed3\u6784\u5355\u5143\u3002 \u6c2f\u4e8c\u6c1f\u7532\u70f7\uff08ClCF2H\uff0c\u4e5f\u79f0\u4e3aFreon-22\uff09\u662f\u4e00\u79cd\u7406\u60f3\u7684\u6c1f\u6e90\uff0c\u662f\u751f\u4ea7\u5404\u79cd\u542b\u6c1f\u805a\u5408\u7269\uff08\u5982\u805a\u56db\u6c1f\u4e59\u70ef\u548c\u805a\u504f\u4e8c\u6c1f\u4e59\u70ef\uff09\u7684\u4e30\u5bcc\u5de5\u4e1a\u539f\u6599\u3002\u7531\u4e8eClCF2H \u7684\u4f4e\u53cd\u5e94\u6d3b\u6027\uff0c\u5176\u8f6c\u5316\u76f8\u5f53\u6709\u9650\uff0c\u4e3b\u8981\u6d89\u53ca\u4e8c\u6c1f\u5361\u5bbe\u4e2d\u95f4\u4f53\u3002\u53e6\u5916\uff0cC-H (~100 kcal\/mol) \u548c C-Cl (\u223c87 kcal\/mol) \u952e\u7684\u89e3\u79bb\u80fd (BDE) \u90fd\u5f88\u9ad8\uff0c\u56e0\u6b64\u901a\u8fc7HAT\u6216XAT\u8fc7\u7a0b\u6d3b\u5316 ClCF2H\u4e5f\u90fd\u5177\u6709\u6311\u6218\u6027\uff08\u56fe 1B\uff09\u3002\u5728\u6b64\u80cc\u666f\u4e0b\uff0c\u7531 Roberts \u7b49\u4eba\u53d1\u5c55\u7684\u914d\u4f4d\u787c\u57fa\u81ea\u7531\u57fa\uff08\u901a\u5f0f\uff1aLB+-R2B\u2022-\uff09\uff0c\u5177\u6709\u4eb2\u6838\u6027\u5e76\u53ef\u4ee5\u901a\u8fc7\u914d\u4f53\u8c03\u63a7B-H\u952e\u7684\u952e\u80fd\u3002Curran\u548cRyu\u4f7f\u7528NHC-\u787c\u70f7\u8fdb\u884c\u8131\u7898\u548c\u7f9f\u7532\u57fa\u5316\u53cd\u5e94\u8fdb\u4e00\u6b65\u8bc1\u660e\u4e86XAT\u53cd\u5e94\u6027\uff0c\u4f46\u4ec5\u9650\u4e8e\u70f7\u57fa\u7898\u548c\u6eb4\u7684\u6d3b\u5316\u3002\u6700\u8fd1\uff0c\u4e0a\u6d77\u4ea4\u901a\u5927\u5b66\u53f6\u4fca\u6d9b\u5c0f\u7ec4\u5728\u5149\u6c27\u5316\u8fd8\u539f\u50ac\u5316\u4e0b\uff0c\u4f7f\u7528\u80fa\u787c\u70f7\u4f5c\u4e3aHAT\u8bd5\u5242\uff0c\u5b9e\u73b0\u4e86\u5bf9\u672a\u6d3b\u5316\u70ef\u70c3\u7684\u6c22\u70f7\u57fa\u5316\u3002\u7531\u4e8e\u5bf9\u6c14\u4f53\u4f5c\u4e3a\u539f\u6599\u7684\u8f6c\u5316\u548c\u6c1f\u70f7\u57fa\u5316\u53cd\u5e94\u7684\u5174\u8da3\uff0c\u4f5c\u8005\u53d1\u5c55\u4e86\u80fa\u787c\u70f7\u4f5c\u4e3aXAT\u8bd5\u5242\u6d3b\u5316ClCF2H\uff0c\u4ee5\u65e0\u91d1\u5c5e\u53c2\u4e0e\u7684\u7b56\u7565\u5bf9\u672a\u6d3b\u5316\u70ef\u70c3\u8fdb\u884c\u4e8c\u6c1f\u7532\u57fa\u5316\uff0c\u540c\u65f6\u8be5\u7b56\u7565\u53ef\u5e94\u7528\u4e8e\u836f\u7269\u5206\u5b50\u548c\u5929\u7136\u4ea7\u7269\u7684\u540e\u671f\u5b98\u80fd\u56e2\u4fee\u9970\uff08\u56fe 1D\uff09\u3002 \u5e95\u7269\u6269\u5c55\uff1a\u5728\u6700\u4f18\u53cd\u5e94\u6761\u4ef6\u4e0b\uff0c\u4f5c\u8005\u5bf9\u672a\u6d3b\u5316\u70ef\u70c3\u7684\u5e95\u7269\u8303\u56f4\u8fdb\u884c\u4e86\u6269\u5c55\uff08\u56fe 2\uff09\u3002\u542b\u6709\u5404\u79cd\u5b98\u80fd\u56e2\uff08\u5305\u62ec\u7f9f\u57fa\u3001\u7532\u82ef\u78fa\u9178\u916f\u3001\u6c2f\u5316\u7269\u3001\u7fa7\u9178\u916f\u3001\u7fa7\u9178\u548c\u9170\u80fa\u57fa\u56e2\uff09\u53ca\u4e0d\u540c\u82b3\u65cf\u9aa8\u67b6\uff08\u53d6\u4ee3\u7684\u82ef\u57fa\u3001\u5494\u5511\u3001\u544b\u5583\u548c\u567b\u5429\uff09\u7684\u70ef\u70c3\uff0c\u90fd\u5177\u6709\u826f\u597d\u7684\u8010\u53d7\u6027\u3002\u540c\u65f6\uff0c\u5bf9\u4e8e\u5355\u53d6\u4ee3\uff0c\u53cc\u53d6\u4ee3\uff0c\u4e09\u53d6\u4ee3\u7684\u70ef\u70c3\u90fd\u80fd\u90fd\u53ef\u4ee5\u987a\u5229\u7684\u53d1\u751f\u4e8c\u6c1f\u7532\u57fa\u5316\u53cd\u5e94\u3002 \u590d\u6742\u751f\u7269\u6d3b\u6027\u5206\u5b50\u7684\u540e\u671f\u5b98\u80fd\u56e2\u5316\u4fee\u9970\uff1a\u4e8c\u6c1f\u7532\u57fa\u5316\u7684\u5e7f\u6cdb\u9002\u5e94\u6027\u542f\u53d1\u4f5c\u8005\u63a2\u7d22\u5176\u5e94\u7528\u4e8e\u590d\u6742\u836f\u7269\u5206\u5b50\u548c\u5929\u7136\u4ea7\u7269\u7684\u540e\u671f\u5b98\u80fd\u56e2\u4fee\u9970\u7684\u53ef\u884c\u6027\u3002\u7814\u7a76\u53d1\u73b0\uff0c\u8be5\u7b56\u7565\u5bf9\u5927\u91cf\u7684\u76f4\u63a5\u6765\u81ea\u6216\u884d\u751f\u81ea\u5929\u7136\u4ea7\u7269\u3001\u836f\u7269\u5206\u5b50\u548c\u529f\u80fd\u6750\u6599\u5206\u5b50\u7684\u590d\u6742\u70ef\u70c3\u5177\u6709\u5f88\u597d\u7684\u9002\u7528\u6027\uff08\u56fe 3\uff09\u3002 \u673a\u7406\u7814\u7a76\uff1a\u4f5c\u8005\u8fdb\u884c\u4e86\u4e00\u7cfb\u5217\u5b9e\u9a8c\u548c\u8ba1\u7b97\u7814\u7a76\u4ee5\u63a2\u7d22\u8be5\u53cd\u5e94\u7684\u673a\u7406\u3002\u9996\u5148\uff0c\u6a21\u677f\u53cd\u5e94\u7684\u8d28\u91cf\u5e73\u8861\u8bc1\u5b9e\u4e86Me3N-BH2Cl\u548cMe3N-BHCl2\u4f5c\u4e3a\u76f8\u5e94\u526f\u4ea7\u7269\u7684\u751f\u6210\uff08\u56fe 4A\uff09\uff0c\u4e0e\u6700\u521d\u63d0\u51fa\u7684XAT\u8fc7\u7a0b\u4e00\u81f4\u3002TEMPO\u7684\u81ea\u7531\u57fa\u6355\u83b7\u5b9e\u9a8c\u5b8c\u5168\u6291\u5236\u4e86\u4e8c\u6c1f\u7532\u57fa\u5316\u4ea7\u7269\u7684\u5f62\u6210\uff0c\u5e76\u68c0\u6d4b\u5230\u52a0\u6210\u4ea7\u7269TEMPO-CF2H\uff08\u56fe4B\uff09\u3002\u5728\u6807\u51c6\u6761\u4ef6\u4e0b\u7528\u53cc\u73af\u841c\u70ef\u03b2-\u848e\u70ef\u8fdb\u884c\u7684\u81ea\u7531\u57fa\u949f\u5b9e\u9a8c\u4ee550%\u7684\u6536\u7387\u5f97\u5230\u4e86\u5f00\u73af\u4ea7\u7269\uff08\u56fe4C\uff09\u3002\u8fd9\u4e24\u4e2a\u5b9e\u9a8c\u7ed3\u679c\u8868\u660eCF2H\u81ea\u7531\u57fa\u7684\u53c2\u4e0e\u3002\u91cd\u8981\u7684\u662f\uff0c\u8be5\u53cd\u5e94\u53ef\u4ee5\u6709\u6548\u5730\u6269\u5c55\u5230\u5176\u4ed6\u7f3a\u7535\u5b50\u7684\u5364\u4ee3\u70f7\uff0c\u800c\u6ca1\u6709\u5438\u7535\u5b50\u53d6\u4ee3\u57fa\u7684\u5364\u4ee3\u70f7\u4e0d\u53d1\u751f\u53cd\u5e94\uff0c\u4e3b\u8981\u662f\u7531\u4e8e\u5438\u7535\u5b50\u53d6\u4ee3\u57fa\u5b58\u5728\u4e0b\u7684XAT\u8fc7\u6e21\u6001\u4e2d\u7a33\u5b9a\u7684\u90e8\u5206\u8d1f\u7535\u8377\u3002\u6b64\u5916\uff0c\u4f7f\u7528Me3N-BH3\u548cMe3N-BD3\u8fdb\u884c\u4e86\u4e24\u4e2a\u5e73\u884c\u53cd\u5e94\uff0c\u5728\u540e\u4e00\u79cd\u60c5\u51b5\u4e0b\uff0c\u5c11\u91cf\u6c18\u539f\u5b50\u5f15\u5165\u4ea7\u7269(16%D)\uff0c\u52a8\u529b\u5b66\u540c\u4f4d\u7d20\u6548\u5e94 (KIE) \u503c\u6d4b\u91cf\u4e3a1.2\uff0c\u8fd9\u610f\u5473\u7740\u787c\u57fa\u81ea\u7531\u57fa\u7684\u4ea7\u751f\u53ef\u80fd\u4e0d\u53c2\u4e0e\u51b3\u901f\u6b65 (\u56fe 4E)\u3002\u6dfb\u52a0\u6c18\u4ee3\u6c34\u7684\u5bf9\u7167\u5b9e\u9a8c\u7684\u4ea7\u7269\u5177\u670980%\u7684\u6c18\u4ee3\u7387\uff0c\u8868\u660e\u5728\u53cd\u5e94\u8fc7\u7a0b\u4e2d\u53ef\u80fd\u8fdb\u884c\u8d28\u5b50\u4ea4\u6362\u3002\u4f7f\u7528Me3N-BH3\u548cPhSSPh\u8fdb\u884c\u7684Stern-Volmer\u731d\u706d\u5b9e\u9a8c\u8868\u660e\uff0cPhSSPh\u6bd4Me3N-BH3\u53ef\u4ee5\u66f4\u6709\u6548\u5730\u731d\u706d\u6fc0\u53d1\u7684\u5149\u50ac\u5316\u5242\uff08\u56fe 4F\uff09\u3002 \u6b64\u5916\uff0c\u4f5c\u8005\u548c\u4e0a\u6d77\u6709\u673a\u6240\u859b\u5c0f\u677e\u8bfe\u9898\u7ec4\u5408\u4f5c\uff0c\u901a\u8fc7\u5bc6\u5ea6\u6cdb\u51fd\u7406\u8bba\uff08DFT\uff09\u8ba1\u7b97\u53d1\u73b0XAT\u8fc7\u7a0b\u901f\u7387\u9ad8\u4e14\u4e0d\u53ef\u9006\uff0c\u81ea\u7531\u80fd\u80fd\u5792\u4e3a10.2 kcal\/mol\uff0c\u4ea7\u7269\u91ca\u653e\u80fd\u91cf31.7 kcal\/mol\uff08\u56fe 5A-1\uff09\u3002\u7136\u800c\uff0cHAT\u8fc7\u7a0b\u7684\u80fd\u5792\u6bd4XAT\u8fc7\u7a0b\u9ad82.0 kcal\/mol\uff0c\u4ea7\u7269\u5438\u6536\u80fd\u91cf2.1 kcal\/mol\u3002\u4e8c\u8005\u80fd\u5792\u5dee\u5f02\u53ef\u5f52\u56e0\u4e8eClCF2H\u7684\u5206\u5b50\u8f68\u9053\uff0c\u5176\u4e2dC-Cl\u952e\u53cd\u952e\u8f68\u9053 (\u03c3C-Cl, LUMO) \u7684\u80fd\u91cf\u4f4e\u4e8eC-H\u952e\u53cd\u952e\u8f68\u9053 (\u03c3C-H, LUMO+1) (\u56fe 5A-2)\u3002\u4e0e\u539f\u59cb\u7684C-Cl \u952e\uff08cal. BDE = 86 kcal\/mol\uff09\u76f8\u6bd4\uff0cXAT\u8fc7\u7a0b\u7684\u70ed\u529b\u5b66\u9a71\u52a8\u529b\u662f\u5f62\u6210\u66f4\u7a33\u5b9a\u7684B-Cl\u952e\uff08cal. BDE = 117 kcal\/mol\uff09\u3002\u80fa-\u787c\u57fa\u81ea\u7531\u57fa\u7684\u4eb2\u6838\u7279\u6027\u5141\u8bb8\u5728\u787c\u539f\u5b50\u4e0a\u79ef\u7d2f\u90e8\u5206\u6b63\u7535\u8377\uff0c\u4ece\u800c\u901a\u8fc7\u6781\u6027\u6548\u5e94\u964d\u4f4eXAT\u8fc7\u7a0b\u80fd\u5792\uff08\u56fe5A-3\uff09\u3002\u56e0\u6b64\uff0c\u5355\u6c2f\u787c\u57fa\u548c\u4e8c\u6c2f\u787c\u57fa\u81ea\u7531\u57fa\u7684\u4eb2\u6838\u6027\u4e0d\u8db3\u4ee5\u52a0\u901f\u53cd\u5e94\u3002XAT\u8fc7\u7a0b\u7684\u8fc7\u6e21\u6001\u7ed3\u6784\u66f4\u63a5\u8fd1\u53cd\u5e94\u7269\uff0c\u5176\u4e2dC-Cl\u952e\u7565\u5fae\u62c9\u957f0.16 \u00c5\uff08\u4ece1.78 \u00c5\u53d8\u4e3a1.94 \u00c5\uff09\u3002\u76f8\u5e94\u5185\u7980\u53cd\u5e94\u5750\u6807\u8ba1\u7b97\uff08IRC\uff09\u53d1\u73b0\u80fa\u787c\u57fa\u81ea\u7531\u57fa\u7684\u81ea\u65cb\u5bc6\u5ea6\u4ece1.000\uff08\u81ea\u7531\u57fa\uff09\u964d\u4f4e\u52300.621\uff08\u8fc7\u6e21\u6001\uff09\uff0c\u8bf4\u660e\u90e8\u5206\u81ea\u65cb\u8f6c\u79fb\u5148\u4e8eC-Cl\u952e\u65ad\u88c2\u53d1\u751f\u3002 \u603b\u7ed3 \u65b0\u52a0\u5761\u56fd\u7acb\u5927\u5b66\u5434\u6770\u8bfe\u9898\u7ec4\u4e0e\u5929\u6d25\u5927\u5b66\u9a6c\u519b\u5b89\uff0c\u5f20\u53d1\u5149\u8bfe\u9898\u7ec4\u62a5\u9053\u4e86\u901a\u8fc7\u4f7f\u7528\u5ec9\u4ef7\u4e14\u4e30\u5bcc\u7684ClCF2H\u4f5c\u4e3a\u6c1f\u6e90\uff0c1\u5728\u6e29\u548c\u4e14\u65e0\u91d1\u5c5e\u7684\u6761\u4ef6\u4e0b\u6210\u529f\u5730\u5b9e\u73b0\u4e86\u672a\u6d3b\u5316\u70ef\u70c3\u7684\u4e8c\u6c1f\u7532\u57fa\u5316\u53cd\u5e94\u3002\u8be5\u65b9\u6cd5\u5177\u6709\u975e\u5e38\u5e7f\u6cdb\u7684\u5e95\u7269\u8303\u56f4\uff0c\u5e76\u6210\u529f\u5e94\u7528\u4e8e\u590d\u6742\u751f\u7269\u6d3b\u6027\u5206\u5b50\u7684\u540e\u671f\u5b98\u80fd\u56e2\u5316\u4fee\u9970\u3002\u5149\u6c27\u5316\u8fd8\u539f\u50ac\u5316\u4e0e\u53d4\u80fa\u787c\u70f7\u7684\u7ed3\u5408\u88ab\u8bc1\u660e\u662f\u9009\u62e9\u6027XAT\u8fc7\u7a0b\u6d3b\u5316ClCF2H\u7684\u6709\u529b\u7b56\u7565\uff0c\u4ece\u800c\u4e3a\u6c1f\u5229\u6602\u5316\u5b66\u539f\u6599\u5728\u5b9e\u9645\u5408\u6210\u5316\u5b66\u4e2d\u7684\u5229\u7528\u5f00\u8f9f\u4e86\u65b0\u65b9\u5411\u3002\u5929\u6d25\u5927\u5b66-\u65b0\u52a0\u5761\u56fd\u7acb\u5927\u5b66\u798f\u5dde\u8054\u5408\u5b66\u9662\u535a\u58eb\u751f\u5f20\u5fd7\u5947\u548c\u4e0a\u6d77\u6709\u673a\u6240\u535a\u58eb\u751f\u6851\u5cb3\u5343\u4e3a\u5171\u540c\u7b2c\u4e00\u4f5c\u8005\u3002 \u8bfe\u9898\u7ec4\u4e3b\u9875\uff1a […]","protected":false},"author":3,"featured_media":42491,"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":[414,1271],"tags":[3850,3849,3851],"jetpack_publicize_connections":[],"jetpack_featured_media_url":"https:\/\/assets.www.gsbet888.com\/uploads\/2022\/07\/JACS-cover.jpg","jetpack_shortlink":"https:\/\/wp.me\/p96op1-b33","jetpack_sharing_enabled":true,"_links":{"self":[{"href":"\/\/www.gsbet888.com\/wp-json\/wp\/v2\/posts\/42473"}],"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\/3"}],"replies":[{"embeddable":true,"href":"\/\/www.gsbet888.com\/wp-json\/wp\/v2\/comments?post=42473"}],"version-history":[{"count":4,"href":"\/\/www.gsbet888.com\/wp-json\/wp\/v2\/posts\/42473\/revisions"}],"predecessor-version":[{"id":42494,"href":"\/\/www.gsbet888.com\/wp-json\/wp\/v2\/posts\/42473\/revisions\/42494"}],"wp:featuredmedia":[{"embeddable":true,"href":"\/\/www.gsbet888.com\/wp-json\/wp\/v2\/media\/42491"}],"wp:attachment":[{"href":"\/\/www.gsbet888.com\/wp-json\/wp\/v2\/media?parent=42473"}],"wp:term":[{"taxonomy":"category","embeddable":true,"href":"\/\/www.gsbet888.com\/wp-json\/wp\/v2\/categories?post=42473"},{"taxonomy":"post_tag","embeddable":true,"href":"\/\/www.gsbet888.com\/wp-json\/wp\/v2\/tags?post=42473"}],"curies":[{"name":"wp","href":"https:\/\/api.w.org\/{rel}","templated":true}]}}

map