{"id":37557,"date":"2021-03-18T08:00:52","date_gmt":"2021-03-18T00:00:52","guid":{"rendered":"\/\/www.gsbet888.com\/?p=37557"},"modified":"2021-03-14T22:10:23","modified_gmt":"2021-03-14T14:10:23","slug":"%e6%97%a5%e6%9c%ac%e5%be%ae%e7%94%9f%e7%89%a9%e5%8c%96%e5%ad%a6%e7%a0%94%e7%a9%b6%e6%89%80masakatsu-shibasaki%e6%95%99%e6%8e%88%e8%af%be%e9%a2%98%e7%bb%84angew%ef%bc%9a-%e9%95%8d-%e5%8d%a1%e5%ae%be","status":"publish","type":"post","link":"\/\/www.gsbet888.com\/%e5%8c%96%e5%ad%a6%e6%9d%82%e8%ae%b0\/recentpaper\/2021\/03\/%e6%97%a5%e6%9c%ac%e5%be%ae%e7%94%9f%e7%89%a9%e5%8c%96%e5%ad%a6%e7%a0%94%e7%a9%b6%e6%89%80masakatsu-shibasaki%e6%95%99%e6%8e%88%e8%af%be%e9%a2%98%e7%bb%84angew%ef%bc%9a-%e9%95%8d-%e5%8d%a1%e5%ae%be.html","title":{"rendered":"\u65e5\u672c\u5fae\u751f\u7269\u5316\u5b66\u7814\u7a76\u6240Masakatsu Shibasaki\u6559\u6388\u8bfe\u9898\u7ec4Angew\uff1a \u954d-\u5361\u5bbe\u50ac\u5316\u70f7\u57fa\u8148\u548c\u919b\u7684\u4e0d\u5bf9\u79f0\u52a0\u6210\u53cd\u5e94"},"content":{"rendered":"

\u672c\u6587\u4f5c\u8005\uff1a\u6749\u6749<\/strong><\/p>\n

\u5bfc\u8bfb<\/h4>\n

\u5728\u70f7\u57fa\u8148\uff08alkylnitrile\uff09\u7684\u52a0\u6210\u53cd\u5e94\u4e2d\uff0c\u4e59\u8148\u4e0e\u919b\u7684\u50ac\u5316\u4e0d\u5bf9\u79f0\u52a0\u6210\uff08ee > 90\uff05\uff09\u4e00\u76f4\u5177\u6709\u6311\u6218\u3002\u8fd1\u65e5\uff0c\u65e5\u672c\u5fae\u751f\u7269\u5316\u5b66\u7814\u7a76\u6240Masakatsu Shibasaki\u6559\u6388\u8bfe\u9898\u7ec4\u5728Angew. Chem. Int. Ed<\/i><\/em>.\u4e0a\u53d1\u8868\u8bba\u6587\uff0c\u901a\u8fc7\u4f7f\u7528Ni(II)-\u5361\u5bbe\u914d\u5408\u7269\u6210\u529f\u5b9e\u73b0\u4e59\u8148\u4e0e\u919b\u7684\u50ac\u5316\u4e0d\u5bf9\u79f0\u52a0\u6210\u53cd\u5e94\uff0c\u4ece\u800c\u83b7\u5f97\u5bf9\u6620\u4f53\u5bcc\u96c6\u7684\u03b2<\/i><\/em>-\u7f9f\u57fa\u8148\u884d\u751f\u7269\u3002\u5176\u4e2d\uff0c\u65e5\u672c\u5fae\u751f\u7269\u5316\u5b66\u7814\u7a76\u6240Masakatsu Shibasaki\u6559\u6388\u548cNaoya Kumagai\u535a\u58eb\u4e3a\u5171\u540c\u901a\u8baf\u4f5c\u8005\u3002<\/p>\n

Direct Catalytic Asymmetric Addition of Aklylnitriles to Aldehydes\u00a0with Designed Ni-Carbene Complexes<\/p>\n

Akira Saito, Shinya Adachi, Naoya Kumagai, and Masakatsu Shibasaki<\/p>\n

Angew. Chem. Int. Ed<\/i><\/em>.\u00a0ASAP DOI:\u00a010.1002\/anie.202016690<\/u><\/a><\/p><\/blockquote>\n

\"\"<\/a><\/p>\n

\u6b63\u6587<\/h4>\n

\u9634\u79bb\u5b50\u78b3\u4eb2\u6838\u8bd5\u5242\u7684\u50ac\u5316\u4e0d\u5bf9\u79f0\u52a0\u6210\u53cd\u5e94\uff0c\u4f5c\u4e3a\u6784\u5efa\u590d\u6742\u5bf9\u6620\u4f53\u5bcc\u96c6\u5206\u5b50\u7684\u6709\u6548\u7b56\u7565\u3002\u5176\u4e2d\uff0c\u70ef\u9187\u76d0\u4f5c\u4e3a\u5e38\u89c1\u7684\u6d3b\u6027\u4eb2\u6838\u8bd5\u5242\uff0c\u4f46\u5176\u8303\u56f4\u6709\u9650\u3002\u5bf9\u4e8e\u8148\u7c7b\u5316\u5408\u7269\uff08\u4f5c\u4e3a\u03b1<\/i><\/em>-\u6c30\u57fa\u78b3\u9634\u79bb\u5b50\u7684\u76f4\u63a5\u524d\u4f53\uff09\uff0c\u7531\u4e8e\u5176\u60f0\u6027\u548c\u7a33\u5b9a\u6027\uff0c\u5df2\u88ab\u7528\u4e8e\u5404\u7c7b\u8272\u8c31\u548c\u53cd\u5e94\u7684\u6eb6\u5242\u3002\u5176\u4e2d\uff0c\u4e59\u8148\u4f5c\u4e3a\u4f7f\u7528\u6700\u5e7f\u6cdb\u7684\u6eb6\u5242\u3002\u7136\u800c\uff0c\u7531\u4e8e\u4e59\u8148\u5177\u6709\u9ad8pKa\u663e\u7740\u5f71\u54cd\u4e86\u76f8\u5e94\u7684\u03b1<\/i><\/em>-\u6c30\u57fa\u78b3\u9634\u79bb\u5b50\u7684\u751f\u6210\uff0c\u5e76\u4e14\u5728\u67d0\u4e9b\u4eb2\u7535\u8bd5\u5242\u5f62\u6210\u78b3-\u78b3\u952e\u7684\u8fc7\u7a0b\u4e2d\uff0c\u7531\u4e8e\u7a7a\u95f4\u504f\u501a\u5bfc\u81f4\u96be\u4ee5\u5b9e\u73b0\u7acb\u4f53\u9009\u62e9\u6027\u7684\u63a7\u5236\uff08Scheme 1\uff09\u3002\u76ee\u524d\u4e3a\u6b62\uff0c\u867d\u7136\u5df2\u5b9e\u73b0\u91d1\u5c5e\u914d\u5408\u7269\u50ac\u5316\u4e59\u8148\u4e0e\u5404\u79cd\u4eb2\u7535\u8bd5\u5242\u7684\u52a0\u6210\u53cd\u5e94\uff0c\u4f46\u7acb\u4f53\u9009\u62e9\u6027\u5747\u96be\u4ee5\u63a7\u5236\u3002\u6700\u8fd1\uff0c\u672c\u8bfe\u9898\u7ec4[1]<\/sup>\u00a0\u62a5\u9053\u4e86Ni(II)\u914d\u5408\u7269\u50ac\u5316\u4e59\u8148\u548cN<\/i><\/em>-\u4e8c\u82ef\u57fa\u81a6\u9170\u57fa\uff08N-Dpp\uff09\u4e9a\u80fa\u7684\u52a0\u6210\u53cd\u5e94\uff0c\u4ece\u800c\u5b9e\u73b0\u9ad8\u5ea6\u5bf9\u6620\u9009\u62e9\u6027\u3002\u7136\u800c\uff0c\u5bf9\u4e8e\u4e59\u8148\u4e0e\u919b\u7684\u76f4\u63a5\u52a0\u6210\u5408\u6210\u03b2<\/i><\/em>-\u7f9f\u57fa\u8148\u884d\u751f\u7269\uff0c\u4ecd\u5177\u6709\u6311\u6218\u3002\u5728\u672c\u6587\u4e2d\uff0c\u4f5c\u8005\u6210\u529f\u5b9e\u73b0\u919b\u548c\u70f7\u57fa\u8148\u7684\u4e0d\u5bf9\u79f0\u52a0\u6210\uff0c\u4ece\u800c\u83b7\u5f97\u4e00\u7cfb\u5217\u5bf9\u6620\u4f53\u5bcc\u96c6\u7684\u03b2<\/i><\/em>-\u7f9f\u57fa\u8148\u884d\u751f\u7269\u3002<\/p>\n

\"\"<\/a><\/p>\n

\u57fa\u4e8e\u524d\u671f\u7684\u7814\u7a76\u6210\u679c[2,3]<\/sup>\uff0c\u4f5c\u8005\u4ee5\u4e59\u8148\u4e0e2-\u8418\u919b1a<\/b><\/strong>\u4f5c\u4e3a\u6a21\u578b\u5e95\u7269\uff0c\u8fdb\u884c\u4e86\u76f8\u5173\u52a0\u6210\u53cd\u5e94\u6761\u4ef6\u7684\u7b5b\u9009\uff08Table 1\uff09\u3002\u7b5b\u9009\u7ed3\u679c\u8868\u660e\uff0c\u4ee52 mol%\u7684C1<\/b><\/strong>\u4e3a\u50ac\u5316\u5242\uff0c2 mol%\u7684t<\/i><\/em>BuOK\u4e3a\u78b1\uff0c\u53ef\u4e8eCH3<\/sub>CN\/iPrOH\u7684\u6df7\u5408\u6eb6\u5242\u4e2d-20 \u2103\u53cd\u5e94\uff0c\u83b7\u5f9799%\u6536\u7387\u548c93% ee\u7684\u76ee\u6807\u4ea7\u72692a<\/b><\/strong>\u3002<\/p>\n

\"\"\"\"<\/a><\/p>\n

\u540c\u65f6\uff0c\u6839\u636eAriafard\u7b49\u5bf9\u6b64\u7c7b\u53cd\u5e94\u76f8\u5173DFT\u7684\u7814\u7a76\u00a0[4]<\/sup>\uff0c\u4f5c\u8005\u63d0\u51fa\u4e86\u4e00\u79cd\u53ef\u80fd\u7684\u53cd\u5e94\u673a\u7406\uff08Figure 2\uff09\u3002\u9996\u5148\uff0cC1<\/b><\/strong>\u548ct<\/i><\/em>BuOK\u53cd\u5e94\u5f62\u6210C1<\/b><\/strong>\u914d\u5408\u7269I<\/b><\/strong>\uff0c\u5e76\u4e0e\u914d\u5408\u7269II<\/b><\/strong>\u5904\u4e8e\u5e73\u8861\u72b6\u6001\u3002\u968f\u540e\uff0c\u914d\u5408\u7269I<\/b><\/strong>\u4e0e\u919b\u7ecf\u52a0\u6210\u53cd\u5e94\uff0c\u751f\u6210\u4e2d\u95f4\u4f53III<\/b><\/strong>\u3002\u6700\u540e\uff0c\u518d\u4e0e\u4e59\u8148\u53cd\u5e94\uff0c\u5373\u53ef\u751f\u6210\u76ee\u6807\u4ea7\u72693<\/b><\/strong>\u3002<\/p>\n

\"\"\"\"<\/a><\/p>\n

\u5728\u83b7\u5f97\u4e0a\u8ff0\u6700\u4f73\u53cd\u5e94\u6761\u4ef6\u4e4b\u540e\uff0c\u4f5c\u8005\u5bf9\u53cd\u5e94\u8303\u56f4\u8fdb\u884c\u4e86\u6269\u5c55\uff08Table 2\uff09\u3002\u9996\u5148\uff0c\u5177\u6709\u8418\u57fa\u3001\u53d6\u4ee3\u82ef\u4e59\u70ef\u57fa\u3001\u55b9\u5549\u57fa\u3001\u5432\u54da\u57fa\u3001\u82ef\u5e76\u567b\u5429\u57fa\u7684\u919b\uff0c\u5747\u53ef\u987a\u5229\u53cd\u5e94\uff0c\u83b7\u5f97>90% ee\u7684\u76f8\u5e94\u4ea7\u72692a<\/b><\/strong>–2l<\/b><\/strong>\u3002\u540c\u65f6\uff0c\u5bf9\u4e8e\u5421\u5576\u57fa\u3001\u567b\u5429\u57fa\u3001\u544b\u5583\u57fa\u53d6\u4ee3\u7684\u919b\u4ee5\u53cap<\/i><\/em>-MeO\u3001-Cl\u3001-Br\u6216m<\/i><\/em>-MeO\u53d6\u4ee3\u82ef\u7532\u919b\uff0c\u83b7\u5f9780-90%ee\u7684\u76f8\u5e94\u4ea7\u72692j<\/b><\/strong>–2s<\/b><\/strong>\u3002\u6b64\u5916\uff0c\u5bf9\u4e8e\u65e0\u53d6\u4ee3\u3001p<\/i><\/em>-F\u3001m<\/i><\/em>-Cl\u3001\u80e1\u6912\u57fa\u53d6\u4ee3\u7684\u82ef\u7532\u919b\uff0c\u5747\u83b7\u5f97\u4e2d\u7b49\u4ee5\u4e0aee\u7684\u76ee\u6807\u4ea7\u72692t<\/b><\/strong>–2w<\/b><\/strong>\u3002<\/p>\n

\"\"\"\"<\/a><\/p>\n

\u4e3a\u4e86\u8fdb\u4e00\u6b65\u8bc1\u660e\u53cd\u5e94\u7684\u5b9e\u7528\u6027\uff0c\u4f5c\u8005\u5bf9\u4ea7\u7269\u8fdb\u884c\u4e86\u76f8\u5173\u7684\u540e\u671f\u884d\u751f\u5316\uff08Scheme 3\uff09\u3002\u82e5\u4f7f\u7528BH3<\/sub>\u2022SMe2<\/sub>\u5728THF\u4e2d\u56de\u6d41\u53cd\u5e94\u5219\u751f\u6210\u6c28\u57fa\u91874<\/b><\/strong>\u3002\u82e5\u5728\u5f3a\u78b1\u6027\u6761\u4ef6\u4e0b\u4f7f\u7528H2<\/sub>O2<\/sub>\u6c34\u6eb6\u6db2\u6c34\u89e3\uff0c\u5219\u751f\u6210\u7fa7\u91785<\/b><\/strong>\u3002\u82e5\u5728\u5f31\u78b1\u6027\u6761\u4ef6\u4e0b\u4f7f\u7528H2<\/sub>O2<\/sub>\u6c34\u6eb6\u6db2\u6c34\u89e3\uff0c\u5219\u751f\u6210\u9170\u80fa6<\/b><\/strong>\u3002<\/p>\n

\"\"\"\"<\/a><\/p>\n

\u603b\u7ed3<\/h4>\n

\u65e5\u672c\u5fae\u751f\u7269\u5316\u5b66\u7814\u7a76\u6240Masakatsu Shibasaki\u6559\u6388\u8bfe\u9898\u7ec4\u62a5\u9053\u4e86\u4e00\u79cd\u901a\u8fc7\u4f7f\u7528Ni(II)-\u5361\u5bbe\u914d\u5408\u7269\u4e3a\u50ac\u5316\u5242\uff0c\u6210\u529f\u5b9e\u73b0\u4e59\u8148\u4e0e\u919b\u7684\u9ad8\u5ea6\u5bf9\u6620\u9009\u62e9\u6027\u52a0\u6210\u53cd\u5e94\uff0c\u4ece\u800c\u83b7\u5f97\u5bf9\u6620\u4f53\u5bcc\u96c6\u7684\u03b2<\/i><\/em>-\u7f9f\u57fa\u8148\u884d\u751f\u7269\u3002\u540c\u65f6\uff0c\u8be5\u53cd\u5e94\u5177\u6709\u5e7f\u6cdb\u7684\u5e95\u7269\u8303\u56f4\uff0c\u60f0\u6027\u7684\u4e59\u8148\u4ee5\u53ca\u5404\u7c7b\u919b\uff08\u82b3\u919b\uff09\u5747\u4e0e\u4f53\u7cfb\u517c\u5bb9\u3002\u6b64\u5916\uff0c\u901a\u8fc7\u5bf9\u4ea7\u7269\u7684\u540e\u671f\u4fee\u9970\uff0c\u8fdb\u4e00\u6b65\u8bc1\u660e\u4e86\u53cd\u5e94\u7684\u5b9e\u7528\u6027\u3002<\/p>\n

\u53c2\u8003\u6587\u732e<\/h4>\n[1]\u00a0S. M. Weinreb, R. K. Orr, Synthesis <\/i><\/em>2005<\/b><\/strong>, 1205-1227.<\/p>\n[2] The use of biscarbene of C1 <\/b><\/strong>as a NHC catalyst: Y. Ma, S. Wei, J. Wu, F.\u00a0Yang, B. Liu, J. Lan, S. Yang, J. You, Adv. Synth. Catal. <\/i><\/em>2008<\/b><\/strong>, 350<\/i><\/em>, 2645-2651.<\/p>\n[3] The use of biscarbene of C1 <\/b><\/strong>for the construction of supramolecular metal\u00a0complexes, see: S. Wei, X. Li, Z. Yang, J. Lan, G. Gao, Y. Xue, J. You,\u00a0Chem. Sci. <\/i><\/em>2012<\/b><\/strong>, 3<\/i><\/em>, 359-363.<\/p>\n[4] a) B. A. D\u2019Sa, P. Kisanga, J. G. Verkade, J. Org. Chem. <\/i><\/em>1998<\/b><\/strong>, 63<\/i><\/em>, 3961-3967; b) P. Kisanga, D. McLeod, B. D\u2019Sa, J. Verkade, J. Org. Chem.<\/i><\/em>\u00a01999<\/b><\/strong>, 64<\/i><\/em>, 3090-3094; c) P. B. Kisanga, J. G. Verkade, J. Org. Chem.<\/i><\/em>\u00a02000<\/b><\/strong>, 65<\/i><\/em>, 5431-5432; d) J. G. Verkade, P. B. Kisanga, Tetrahedron <\/i><\/em>2003<\/b><\/strong>,\u00a059<\/i><\/em>, 7819-7858; e) N. Kumagai, S. Matsunaga, M. Shibasaki, J. Am.<\/i><\/em>\u00a0Chem. Soc. <\/i><\/em>2004<\/b><\/strong>, 126<\/i><\/em>, 13632-13633; f) L. Fan, O. V. Ozerov, Chem.<\/i><\/em>\u00a0Commun. <\/i><\/em>2005<\/b><\/strong>, 4450-4452; g) N. Kumagai, S. Matsunaga, M. Shibasaki,\u00a0Chem. Commun. <\/i><\/em>2005<\/b><\/strong>, 3600-3602; h) N. Kumagai, S. Matsunaga, M.\u00a0Shibasaki, Tetrahedron <\/i><\/em>2007<\/b><\/strong>, 63<\/i><\/em>, 8598-8608; i) A. Goto, K. Endo, Y. Ukai,\u00a0S. Irle, S. Saito, Chem. Commun. <\/i><\/em>2008<\/b><\/strong>, 2212-2214; j) A. Goto, H. Naka,\u00a0R. Noyori, S. Saito, Chem. Asian J <\/i><\/em>2011<\/b><\/strong>, 6<\/i><\/em>, 1740-1743; k) S. Chakraborty,\u00a0Y. J. Patel, J. A. Krause, H. Guan, Angew. Chem. Int. Ed. <\/i><\/em>2013<\/b><\/strong>, 52<\/i><\/em>, 7523-7526; l) A. Ariafard, H. Ghari, Y. Khaledi, A. Hossein Bagi, T. S. Wierenga,\u00a0M. G. Gardiner, A. J. Canty, ACS Catal. <\/i><\/em>2016<\/b><\/strong>, 6<\/i><\/em>, 60-68.<\/p>\n","protected":false},"excerpt":{"rendered":"\u672c\u6587\u4f5c\u8005\uff1a\u6749\u6749 \u5bfc\u8bfb \u5728\u70f7\u57fa\u8148\uff08alkylnitrile\uff09\u7684\u52a0\u6210\u53cd\u5e94\u4e2d\uff0c\u4e59\u8148\u4e0e\u919b\u7684\u50ac\u5316\u4e0d\u5bf9\u79f0\u52a0\u6210\uff08ee > 90\uff05\uff09\u4e00\u76f4\u5177\u6709\u6311\u6218\u3002\u8fd1\u65e5\uff0c\u65e5\u672c\u5fae\u751f\u7269\u5316\u5b66\u7814\u7a76\u6240Masakatsu Shibasaki\u6559\u6388\u8bfe\u9898\u7ec4\u5728Angew. Chem. Int. Ed.\u4e0a\u53d1\u8868\u8bba\u6587\uff0c\u901a\u8fc7\u4f7f\u7528Ni(II)-\u5361\u5bbe\u914d\u5408\u7269\u6210\u529f\u5b9e\u73b0\u4e59\u8148\u4e0e\u919b\u7684\u50ac\u5316\u4e0d\u5bf9\u79f0\u52a0\u6210\u53cd\u5e94\uff0c\u4ece\u800c\u83b7\u5f97\u5bf9\u6620\u4f53\u5bcc\u96c6\u7684\u03b2-\u7f9f\u57fa\u8148\u884d\u751f\u7269\u3002\u5176\u4e2d\uff0c\u65e5\u672c\u5fae\u751f\u7269\u5316\u5b66\u7814\u7a76\u6240Masakatsu Shibasaki\u6559\u6388\u548cNaoya Kumagai\u535a\u58eb\u4e3a\u5171\u540c\u901a\u8baf\u4f5c\u8005\u3002 Direct Catalytic Asymmetric Addition of Aklylnitriles to Aldehydes\u00a0with Designed Ni-Carbene Complexes Akira Saito, Shinya Adachi, Naoya Kumagai, and Masakatsu Shibasaki Angew. Chem. Int. Ed.\u00a0ASAP DOI:\u00a010.1002\/anie.202016690 \u6b63\u6587 \u9634\u79bb\u5b50\u78b3\u4eb2\u6838\u8bd5\u5242\u7684\u50ac\u5316\u4e0d\u5bf9\u79f0\u52a0\u6210\u53cd\u5e94\uff0c\u4f5c\u4e3a\u6784\u5efa\u590d\u6742\u5bf9\u6620\u4f53\u5bcc\u96c6\u5206\u5b50\u7684\u6709\u6548\u7b56\u7565\u3002\u5176\u4e2d\uff0c\u70ef\u9187\u76d0\u4f5c\u4e3a\u5e38\u89c1\u7684\u6d3b\u6027\u4eb2\u6838\u8bd5\u5242\uff0c\u4f46\u5176\u8303\u56f4\u6709\u9650\u3002\u5bf9\u4e8e\u8148\u7c7b\u5316\u5408\u7269\uff08\u4f5c\u4e3a\u03b1-\u6c30\u57fa\u78b3\u9634\u79bb\u5b50\u7684\u76f4\u63a5\u524d\u4f53\uff09\uff0c\u7531\u4e8e\u5176\u60f0\u6027\u548c\u7a33\u5b9a\u6027\uff0c\u5df2\u88ab\u7528\u4e8e\u5404\u7c7b\u8272\u8c31\u548c\u53cd\u5e94\u7684\u6eb6\u5242\u3002\u5176\u4e2d\uff0c\u4e59\u8148\u4f5c\u4e3a\u4f7f\u7528\u6700\u5e7f\u6cdb\u7684\u6eb6\u5242\u3002\u7136\u800c\uff0c\u7531\u4e8e\u4e59\u8148\u5177\u6709\u9ad8pKa\u663e\u7740\u5f71\u54cd\u4e86\u76f8\u5e94\u7684\u03b1-\u6c30\u57fa\u78b3\u9634\u79bb\u5b50\u7684\u751f\u6210\uff0c\u5e76\u4e14\u5728\u67d0\u4e9b\u4eb2\u7535\u8bd5\u5242\u5f62\u6210\u78b3-\u78b3\u952e\u7684\u8fc7\u7a0b\u4e2d\uff0c\u7531\u4e8e\u7a7a\u95f4\u504f\u501a\u5bfc\u81f4\u96be\u4ee5\u5b9e\u73b0\u7acb\u4f53\u9009\u62e9\u6027\u7684\u63a7\u5236\uff08Scheme 1\uff09\u3002\u76ee\u524d\u4e3a\u6b62\uff0c\u867d\u7136\u5df2\u5b9e\u73b0\u91d1\u5c5e\u914d\u5408\u7269\u50ac\u5316\u4e59\u8148\u4e0e\u5404\u79cd\u4eb2\u7535\u8bd5\u5242\u7684\u52a0\u6210\u53cd\u5e94\uff0c\u4f46\u7acb\u4f53\u9009\u62e9\u6027\u5747\u96be\u4ee5\u63a7\u5236\u3002\u6700\u8fd1\uff0c\u672c\u8bfe\u9898\u7ec4[1]\u00a0\u62a5\u9053\u4e86Ni(II)\u914d\u5408\u7269\u50ac\u5316\u4e59\u8148\u548cN-\u4e8c\u82ef\u57fa\u81a6\u9170\u57fa\uff08N-Dpp\uff09\u4e9a\u80fa\u7684\u52a0\u6210\u53cd\u5e94\uff0c\u4ece\u800c\u5b9e\u73b0\u9ad8\u5ea6\u5bf9\u6620\u9009\u62e9\u6027\u3002\u7136\u800c\uff0c\u5bf9\u4e8e\u4e59\u8148\u4e0e\u919b\u7684\u76f4\u63a5\u52a0\u6210\u5408\u6210\u03b2-\u7f9f\u57fa\u8148\u884d\u751f\u7269\uff0c\u4ecd\u5177\u6709\u6311\u6218\u3002\u5728\u672c\u6587\u4e2d\uff0c\u4f5c\u8005\u6210\u529f\u5b9e\u73b0\u919b\u548c\u70f7\u57fa\u8148\u7684\u4e0d\u5bf9\u79f0\u52a0\u6210\uff0c\u4ece\u800c\u83b7\u5f97\u4e00\u7cfb\u5217\u5bf9\u6620\u4f53\u5bcc\u96c6\u7684\u03b2-\u7f9f\u57fa\u8148\u884d\u751f\u7269\u3002 \u57fa\u4e8e\u524d\u671f\u7684\u7814\u7a76\u6210\u679c[2,3]\uff0c\u4f5c\u8005\u4ee5\u4e59\u8148\u4e0e2-\u8418\u919b1a\u4f5c\u4e3a\u6a21\u578b\u5e95\u7269\uff0c\u8fdb\u884c\u4e86\u76f8\u5173\u52a0\u6210\u53cd\u5e94\u6761\u4ef6\u7684\u7b5b\u9009\uff08Table 1\uff09\u3002\u7b5b\u9009\u7ed3\u679c\u8868\u660e\uff0c\u4ee52 mol%\u7684C1\u4e3a\u50ac\u5316\u5242\uff0c2 mol%\u7684tBuOK\u4e3a\u78b1\uff0c\u53ef\u4e8eCH3CN\/iPrOH\u7684\u6df7\u5408\u6eb6\u5242\u4e2d-20 \u2103\u53cd\u5e94\uff0c\u83b7\u5f9799%\u6536\u7387\u548c93% ee\u7684\u76ee\u6807\u4ea7\u72692a\u3002 \u540c\u65f6\uff0c\u6839\u636eAriafard\u7b49\u5bf9\u6b64\u7c7b\u53cd\u5e94\u76f8\u5173DFT\u7684\u7814\u7a76\u00a0[4]\uff0c\u4f5c\u8005\u63d0\u51fa\u4e86\u4e00\u79cd\u53ef\u80fd\u7684\u53cd\u5e94\u673a\u7406\uff08Figure 2\uff09\u3002\u9996\u5148\uff0cC1\u548ctBuOK\u53cd\u5e94\u5f62\u6210C1\u914d\u5408\u7269I\uff0c\u5e76\u4e0e\u914d\u5408\u7269II\u5904\u4e8e\u5e73\u8861\u72b6\u6001\u3002\u968f\u540e\uff0c\u914d\u5408\u7269I\u4e0e\u919b\u7ecf\u52a0\u6210\u53cd\u5e94\uff0c\u751f\u6210\u4e2d\u95f4\u4f53III\u3002\u6700\u540e\uff0c\u518d\u4e0e\u4e59\u8148\u53cd\u5e94\uff0c\u5373\u53ef\u751f\u6210\u76ee\u6807\u4ea7\u72693\u3002 \u5728\u83b7\u5f97\u4e0a\u8ff0\u6700\u4f73\u53cd\u5e94\u6761\u4ef6\u4e4b\u540e\uff0c\u4f5c\u8005\u5bf9\u53cd\u5e94\u8303\u56f4\u8fdb\u884c\u4e86\u6269\u5c55\uff08Table 2\uff09\u3002\u9996\u5148\uff0c\u5177\u6709\u8418\u57fa\u3001\u53d6\u4ee3\u82ef\u4e59\u70ef\u57fa\u3001\u55b9\u5549\u57fa\u3001\u5432\u54da\u57fa\u3001\u82ef\u5e76\u567b\u5429\u57fa\u7684\u919b\uff0c\u5747\u53ef\u987a\u5229\u53cd\u5e94\uff0c\u83b7\u5f97>90% ee\u7684\u76f8\u5e94\u4ea7\u72692a–2l\u3002\u540c\u65f6\uff0c\u5bf9\u4e8e\u5421\u5576\u57fa\u3001\u567b\u5429\u57fa\u3001\u544b\u5583\u57fa\u53d6\u4ee3\u7684\u919b\u4ee5\u53cap-MeO\u3001-Cl\u3001-Br\u6216m-MeO\u53d6\u4ee3\u82ef\u7532\u919b\uff0c\u83b7\u5f9780-90%ee\u7684\u76f8\u5e94\u4ea7\u72692j–2s\u3002\u6b64\u5916\uff0c\u5bf9\u4e8e\u65e0\u53d6\u4ee3\u3001p-F\u3001m-Cl\u3001\u80e1\u6912\u57fa\u53d6\u4ee3\u7684\u82ef\u7532\u919b\uff0c\u5747\u83b7\u5f97\u4e2d\u7b49\u4ee5\u4e0aee\u7684\u76ee\u6807\u4ea7\u72692t–2w\u3002 \u4e3a\u4e86\u8fdb\u4e00\u6b65\u8bc1\u660e\u53cd\u5e94\u7684\u5b9e\u7528\u6027\uff0c\u4f5c\u8005\u5bf9\u4ea7\u7269\u8fdb\u884c\u4e86\u76f8\u5173\u7684\u540e\u671f\u884d\u751f\u5316\uff08Scheme 3\uff09\u3002\u82e5\u4f7f\u7528BH3\u2022SMe2\u5728THF\u4e2d\u56de\u6d41\u53cd\u5e94\u5219\u751f\u6210\u6c28\u57fa\u91874\u3002\u82e5\u5728\u5f3a\u78b1\u6027\u6761\u4ef6\u4e0b\u4f7f\u7528H2O2\u6c34\u6eb6\u6db2\u6c34\u89e3\uff0c\u5219\u751f\u6210\u7fa7\u91785\u3002\u82e5\u5728\u5f31\u78b1\u6027\u6761\u4ef6\u4e0b\u4f7f\u7528H2O2\u6c34\u6eb6\u6db2\u6c34\u89e3\uff0c\u5219\u751f\u6210\u9170\u80fa6\u3002 \u603b\u7ed3 \u65e5\u672c\u5fae\u751f\u7269\u5316\u5b66\u7814\u7a76\u6240Masakatsu Shibasaki\u6559\u6388\u8bfe\u9898\u7ec4\u62a5\u9053\u4e86\u4e00\u79cd\u901a\u8fc7\u4f7f\u7528Ni(II)-\u5361\u5bbe\u914d\u5408\u7269\u4e3a\u50ac\u5316\u5242\uff0c\u6210\u529f\u5b9e\u73b0\u4e59\u8148\u4e0e\u919b\u7684\u9ad8\u5ea6\u5bf9\u6620\u9009\u62e9\u6027\u52a0\u6210\u53cd\u5e94\uff0c\u4ece\u800c\u83b7\u5f97\u5bf9\u6620\u4f53\u5bcc\u96c6\u7684\u03b2-\u7f9f\u57fa\u8148\u884d\u751f\u7269\u3002\u540c\u65f6\uff0c\u8be5\u53cd\u5e94\u5177\u6709\u5e7f\u6cdb\u7684\u5e95\u7269\u8303\u56f4\uff0c\u60f0\u6027\u7684\u4e59\u8148\u4ee5\u53ca\u5404\u7c7b\u919b\uff08\u82b3\u919b\uff09\u5747\u4e0e\u4f53\u7cfb\u517c\u5bb9\u3002\u6b64\u5916\uff0c\u901a\u8fc7\u5bf9\u4ea7\u7269\u7684\u540e\u671f\u4fee\u9970\uff0c\u8fdb\u4e00\u6b65\u8bc1\u660e\u4e86\u53cd\u5e94\u7684\u5b9e\u7528\u6027\u3002 \u53c2\u8003\u6587\u732e [1]\u00a0S. M. Weinreb, R. K. Orr, Synthesis 2005, 1205-1227. [2] The use of biscarbene of C1 as a NHC catalyst: Y. Ma, S. Wei, J. Wu, F.\u00a0Yang, B. Liu, J. Lan, S. Yang, J. You, Adv. Synth. Catal. 2008, 350, 2645-2651. [3] The use of biscarbene of C1 for the construction of supramolecular metal\u00a0complexes, […]","protected":false},"author":26,"featured_media":37546,"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":[3383,3384,3382],"jetpack_publicize_connections":[],"jetpack_featured_media_url":"https:\/\/assets.www.gsbet888.com\/uploads\/2021\/03\/1-25.png","jetpack_shortlink":"https:\/\/wp.me\/p96op1-9LL","jetpack_sharing_enabled":true,"_links":{"self":[{"href":"\/\/www.gsbet888.com\/wp-json\/wp\/v2\/posts\/37557"}],"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=37557"}],"version-history":[{"count":1,"href":"\/\/www.gsbet888.com\/wp-json\/wp\/v2\/posts\/37557\/revisions"}],"predecessor-version":[{"id":37558,"href":"\/\/www.gsbet888.com\/wp-json\/wp\/v2\/posts\/37557\/revisions\/37558"}],"wp:featuredmedia":[{"embeddable":true,"href":"\/\/www.gsbet888.com\/wp-json\/wp\/v2\/media\/37546"}],"wp:attachment":[{"href":"\/\/www.gsbet888.com\/wp-json\/wp\/v2\/media?parent=37557"}],"wp:term":[{"taxonomy":"category","embeddable":true,"href":"\/\/www.gsbet888.com\/wp-json\/wp\/v2\/categories?post=37557"},{"taxonomy":"post_tag","embeddable":true,"href":"\/\/www.gsbet888.com\/wp-json\/wp\/v2\/tags?post=37557"}],"curies":[{"name":"wp","href":"https:\/\/api.w.org\/{rel}","templated":true}]}}