{"id":30215,"date":"2020-02-14T08:00:02","date_gmt":"2020-02-14T00:00:02","guid":{"rendered":"\/\/www.gsbet888.com\/?p=30215"},"modified":"2020-02-12T20:31:25","modified_gmt":"2020-02-12T12:31:25","slug":"%e4%b8%8a%e6%b5%b7%e4%ba%a4%e9%80%9a%e5%a4%a7%e5%ad%a6%e5%bc%a0%e4%b8%87%e6%96%8c%e6%95%99%e6%8e%88%e8%af%be%e9%a2%98%e7%bb%84angew%ef%bc%9a%e9%95%8d%e5%82%ac%e5%8c%962-%e9%85%b0%e8%83%ba%e5%9f%ba","status":"publish","type":"post","link":"\/\/www.gsbet888.com\/%e5%8c%96%e5%ad%a6%e6%9d%82%e8%ae%b0\/recentpaper\/2020\/02\/%e4%b8%8a%e6%b5%b7%e4%ba%a4%e9%80%9a%e5%a4%a7%e5%ad%a6%e5%bc%a0%e4%b8%87%e6%96%8c%e6%95%99%e6%8e%88%e8%af%be%e9%a2%98%e7%bb%84angew%ef%bc%9a%e9%95%8d%e5%82%ac%e5%8c%962-%e9%85%b0%e8%83%ba%e5%9f%ba.html","title":{"rendered":"\u4e0a\u6d77\u4ea4\u901a\u5927\u5b66\u5f20\u4e07\u658c\u6559\u6388\u8bfe\u9898\u7ec4Angew\uff1a\u954d\u50ac\u53162-\u9170\u80fa\u57fa\u4e19\u70ef\u9178\u916f\u7684\u4e0d\u5bf9\u79f0\u6c22\u5316\u53cd\u5e94"},"content":{"rendered":"

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

\u5bfc\u8bfb<\/h4>\n

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

\uff08\u56fe\u7247\u6765\u6e90\uff1aAngew. Chem. Int. Ed<\/em>.\uff09<\/p>\n

\u6b63\u6587<\/h4>\n

\u624b\u6027\u03b1<\/em>-\u6c28\u57fa\u9178\u4f5c\u4e3a\u5316\u5b66\u548c\u751f\u7269\u5b66\u4e2d\u6700\u91cd\u8981\u7684\u9aa8\u67b6\u4e4b\u4e00\uff08Figure 1\uff09\u3002\u56e0\u6b64\uff0c\u624b\u6027\u03b1<\/em>-\u6c28\u57fa\u9178\u53ca\u5176\u884d\u751f\u7269\u7684\u4e0d\u5bf9\u79f0\u5408\u6210\u53d7\u5230\u5e7f\u6cdb\u7684\u5173\u6ce8\uff0c\u6570\u4ee5\u4e07\u8ba1\u7684\u6587\u732e\u5df2\u62a5\u9053\u4e86\u6570\u5341\u79cd\u65b9\u6cd5\uff0c\u800c\u8fc7\u6e21\u91d1\u5c5e\u50ac\u53162-\u9170\u80fa\u57fa\u4e19\u70ef\u9178\u916f\u7684\u4e0d\u5bf9\u79f0\u6c22\u5316\u53cd\u5e94\u662f\u5176\u4e2d\u6700\u9ad8\u6548\u7684\u65b9\u6cd5\u3002\u5728\u8fc7\u53bb\u6570\u5341\u5e74\u4e2d\uff0c\u63d0\u9ad8\u8be5\u65b9\u6cd5\u7684\u6548\u7387\u548c\u5b9e\u7528\u6027\u4e00\u76f4\u662f\u8be5\u9886\u57df\u7814\u7a76\u7684\u91cd\u70b9\uff0c\u4e00\u4e9b\u7531Rh\u3001Ru\u548cIr\u7ec4\u6210\u7684\u50ac\u5316\u5242\u5df2\u88ab\u62a5\u9053\uff08Figure 2\uff09\u30022001\u5e74\uff0c\u5f53Knowles\u901a\u8fc7Rh\u50ac\u5316\u4e0d\u5bf9\u79f0\u6c22\u5316\u53cd\u5e94\u5b9e\u73b0L-DOPA\u7684\u5de5\u4e1a\u5408\u6210\uff0c\u4ece\u800c\u83b7\u5f97\u8bfa\u8d1d\u5c14\u5316\u5b66\u5956\uff0c\u4f7f\u8be5\u9886\u57df\u53d8\u5f97\u66f4\u4e3a\u91cd\u8981\u3002\u7136\u800c\uff0c\u8d35\u91d1\u5c5e\u50ac\u5316\u5242\u7684\u9ad8\u6210\u672c\u548c\u9ad8\u6bd2\u6027\u963b\u788d\u4e86\u8be5\u6280\u672f\u7684\u5e7f\u6cdb\u5e94\u7528\u3002<\/p>\n

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

\uff08\u56fe\u7247\u6765\u6e90\uff1aAngew. Chem. Int. Ed<\/em>.\uff09<\/p>\n

\u4e0e\u8d35\u91d1\u5c5e\u50ac\u5316\u5242\u76f8\u6bd4\uff0c\u4e00\u4e9bMn\u3001Fe\u3001Co\u3001Ni\u3001Cu\u7b49\u8fc7\u6e21\u91d1\u5c5e\u50ac\u5316\u5242\u4e5f\u53ef\u5b9e\u73b0\u4e0d\u5bf9\u79f0\u6c22\u5316\u53cd\u5e94\uff0c\u540c\u65f6\u5177\u6709\u6210\u672c\u4f4e\u3001\u6bd2\u6027\u4f4e\u7b49\u4f18\u70b9\u3002\u76ee\u524d\u4e3a\u6b62\uff0c\u53ea\u6709\u94b4\u914d\u5408\u7269\u5b9e\u73b02-\u9170\u80fa\u57fa\u4e19\u70ef\u9178\u916f\u7684\u4e0d\u5bf9\u79f0\u6c22\u5316\u53cd\u5e94\uff0c\u5408\u6210\u624b\u6027\u03b1<\/em>-\u6c28\u57fa\u9178\u6216\u9170\u80fa\u884d\u751f\u7269\uff08Figure 2\uff09\u3002\u4f46\u662f\uff0c\u5176\u4ed6\u8fc7\u6e21\u91d1\u5c5e\u5177\u6709\u5404\u81ea\u7684\u914d\u4f4d\u6a21\u5f0f\uff0c\u65e0\u6cd5\u5229\u7528\u9170\u80fa\u57fa\u56e2\u7684\u6d3b\u5316\u7b56\u7565\uff0c\u4ece\u800c\u963b\u788d\u4e862-\u9170\u80fa\u57fa\u4e19\u70ef\u9178\u916f\u4e0d\u5bf9\u79f0\u6c22\u5316\u53cd\u5e94\u7684\u5c1d\u8bd5\u3002\u6700\u8fd1\uff0cChirik\u548cZhang\u8bfe\u9898\u7ec4\u62a5\u9053\u4e86Ni\u50ac\u5316\u70ef\u70c3\u7684\u4e0d\u5bf9\u79f0\u52a0\u6c22\u53cd\u5e94\uff0c\u540c\u65f6\u8fd8\u5f00\u53d1\u4e86\u4e00\u4e2aNi\u50ac\u5316\u4e9a\u80fa\u7684\u4e0d\u5bf9\u79f0\u6c22\u5316\u53cd\u5e94\u3002\u5728\u6b64\u5b9e\u9a8c\u4e2d\uff0c\u4f5c\u8005\u53d1\u73b0\uff0c\u5e95\u7269\u548c\u50ac\u5316\u5242\u4e4b\u95f4\u5b58\u5728\u4e00\u5b9a\u7684\u76f8\u4e92\u4f5c\u7528\u53ef\u63d0\u9ad8\u50ac\u5316\u6d3b\u6027\uff08\u9002\u5f53\u7684\u91d1\u5c5e\/\u914d\u4f53\u6bd4\u53ef\u63d0\u9ad8\u50ac\u5316\u6548\u7387\uff09\u3002\u56e0\u6b64\uff0c\u4f5c\u8005\u8bbe\u60f3\uff0c\u662f\u5426\u53ef\u4ee5\u901a\u8fc7\u4e0a\u8ff0\u7c7b\u4f3c\u7684\u7b56\u7565\uff0c\u5b9e\u73b0\u7b2c\u4e00\u4e2aNi\u50ac\u53162-\u9170\u80fa\u57fa\u4e19\u70ef\u9178\u916f\u7684\u4e0d\u5bf9\u79f0\u6c22\u5316\u53cd\u5e94\uff0c\u5408\u6210\u624b\u6027\u03b1<\/em>-\u6c28\u57fa\u9178\u884d\u751f\u7269\uff08Figure 2\uff09\u3002<\/p>\n

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

\uff08\u56fe\u7247\u6765\u6e90\uff1aAngew. Chem. Int. Ed<\/em>.\uff09<\/p>\n

\u9996\u5148\uff0c\u4f5c\u8005\u5bf9\u4e0d\u540c\u53d6\u4ee3\u7684\u5e95\u72691<\/strong>\u8fdb\u884c\u4e86\u5927\u91cf\u7684\u53cd\u5e94\u7814\u7a76\uff08Table 1\uff09\u3002\u5f53\u4ee51a<\/strong>\u4f5c\u4e3a\u5e95\u7269\uff0c\u4ee5Ni(OAc)2<\/sub>\u00b74H2<\/sub>O\u4f5c\u4e3a\u50ac\u5316\u5242\uff0c(S<\/em>)-BINAP\u4e3a\u914d\u4f53\uff0c\u4ec5\u83b7\u5f9723\uff05\u8f6c\u5316\u7387\u548c40\uff05ee\u7684\u4ea7\u72692a<\/strong>\uff08entry 1\uff09\u3002\u968f\u540e\uff0c\u4f5c\u8005\u7814\u7a76\u4e86\u4e0d\u540c\u53d6\u4ee3\u7684R1<\/sup>\u548cR2<\/sup>\u57fa\u56e2\u770b\u662f\u5426\u53ef\u4ee5\u83b7\u5f97\u66f4\u597d\u7684\u7ed3\u679c\uff0c\u53cd\u5e94\u7ed3\u679c\u8868\u660e\uff0c\u4e0d\u540c\u53d6\u4ee3\u7684R1<\/sup>\u548cR2<\/sup>\u57fa\u56e2\u5bf9\u53cd\u5e94\u5177\u6709\u4e00\u5b9a\u7684\u5f71\u54cd\uff08entries 2-12\uff09\uff0c\u5f53R2<\/sup>\u57fa\u56e2\u4e3ao<\/em>-MeO-C6<\/sub>H4<\/sub>\u65f6\uff0c\u53ef\u83b7\u5f97\u6700\u4f73\u7ed3\u679c\uff08\u4ea7\u738774\uff05\u300196\uff05ee\uff09\u3002\u63a5\u4e0b\u6765\uff0c\u4f5c\u8005\u4e5f\u5bf9\u5404\u7c7bNi\u50ac\u5316\u5242\u548c\u6eb6\u5242\u8fdb\u884c\u4e86\u7b5b\u9009\uff0c\u53cd\u5e94\u7ed3\u679c\u8868\u660e\uff0cNi(OAc)2<\/sub>\u00b74H2<\/sub>O\u4f5c\u4e3a\u6700\u4f73\u50ac\u5316\u5242\uff0cTFE\u4f5c\u4e3a\u6700\u4f73\u6eb6\u5242\u3002\u6b64\u5916\uff0c\u4f5c\u8005\u4e5f\u5bf9\u591a\u79cd\u624b\u6027\u53cc\u81a6\u914d\u4f53\u8fdb\u884c\u4e86\u7b5b\u9009\uff0c\u5176\u4e2d\u8f74\u5411\u624b\u6027\u914d\u4f53\u8868\u73b0\u51fa\u8f83\u597d\u7684\u7ed3\u679c\u3002\u4f7f\u7528(S<\/em>)-MeO-BIPHEP\u3001(S<\/em>)-H8-BINAP\u3001(S<\/em>)-GarPhos\u65f6\u53ef\u4ee5\u83b7\u5f97\u8f83\u597d\u7684\u7ed3\u679c\uff0c\u540c\u65f6\u4f5c\u8005\u53d1\u73b0\uff0c\u7a7a\u95f4\u6548\u5e94\u662f\u5f71\u54cd\u4e0d\u540c\u914d\u4f53\u6027\u80fd\u7684\u5173\u952e\u56e0\u7d20\u3002\u56e0\u6b64\uff0c\u4f5c\u8005\u7814\u7a76\u4e86\u5176\u4ed6\u4e09\u4e2a\u5177\u6709\u4e2d\u7b49\u4e8c\u9762\u89d2\u7684\u8f74\u5411\u624b\u6027\u914d\u4f53\uff0c(S<\/em>)-DM-BINAP\uff0c(S<\/em>)-DM-MeO-BIPHEP\u548c(S<\/em>)-DM-SegPhos\uff0c\u5f53(S<\/em>)-DM-MeO-BIPHEP\u7528\u4f5c\u914d\u4f53\uff0c\u53ef\u5c06\u53cd\u5e94\u65f6\u95f4\u53ef\u4ee5\u7f29\u77ed\u523024h\uff0c\u5e76\u83b7\u5f9795\uff05\u8f6c\u6362\u7387\u548c95-96\uff05ee\u7684\u76f8\u5e94\u4ea7\u7269\u3002<\/p>\n

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

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

\uff08\u56fe\u7247\u6765\u6e90\uff1aAngew. Chem. Int. Ed<\/em>.\uff09<\/p>\n

\u5728\u83b7\u5f97\u4e0a\u8ff0\u6700\u4f73\u53cd\u5e94\u6761\u4ef6\u540e\uff0c\u4f5c\u8005\u5f00\u59cb\u5bf9\u5e95\u7269\u8fdb\u884c\u4e86\u6269\u5c55\uff08Scheme 1\uff09\u3002\u5728\u82b3\u57fa\u76842,3,4\u4f4d\u4e0a\u5177\u6709\u4f9b\u7535\u5b50\u548c\u5438\u7535\u5b50\u53d6\u4ee3\u57fa\u65f6\u5747\u53ef\u83b7\u5f97\u76f8\u5e94\u7684\u76ee\u6807\u4ea7\u72692l<\/strong>–2ad<\/strong>\uff08\u6536\u738793-99%\uff0c90-96\uff05ee\uff09\u3002\u540c\u65f6\uff0c\u4e8c\u53d6\u4ee3\uff081ae<\/strong>–1af<\/strong>\uff09\u3001\u8418\u57fa\uff081ag<\/strong>–1ah<\/strong>\uff09\u548c\u567b\u5429\u57fa\u5e95\u7269\uff081ai<\/strong>\uff09\u540c\u6837\u83b7\u5f97\u8f83\u597d\u7684\u7ed3\u679c\u3002\u6b64\u5916\uff0c\u5f53\u82b3\u57fa\u6539\u53d8\u4e3a\u73af\u5df1\u57fa\u65f6\uff0c\u6c22\u5316\u53cd\u5e94\u4e5f\u80fd\u591f\u987a\u5229\u8fdb\u884c\uff0c\u83b7\u5f9793\uff05ee\u7684\u76f8\u5e94\u4ea7\u72692aj<\/strong>\uff0c\u4f46\u50ac\u5316\u5242\u91cf\u9700\u589e\u52a0\u3002<\/p>\n

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

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

\uff08\u56fe\u7247\u6765\u6e90\uff1aAngew. Chem. Int. Ed<\/em>.\uff09<\/p>\n

\u968f\u540e\uff0c\u4f5c\u8005\u8fdb\u4e00\u6b65\u5bf9\u50ac\u5316\u6548\u7387\u7ee7\u7eed\u8fdb\u884c\u7814\u7a76\u3002\u8d77\u521d\uff0c\u5f53S\/C=500\u65f6\uff0c\u5373\u4f7f\u957f\u65f6\u95f4\u53cd\u5e94\u4e5f\u672a\u80fd\u5b8c\u5168\u8f6c\u5316\uff0c\u4e3a\u4e86\u8fdb\u4e00\u6b65\u63d0\u9ad8\u6548\u7387\uff0c\u4f5c\u8005\u8bd5\u56fe\u5728\u53cd\u5e94\u4f53\u7cfb\u4e2d\u589e\u52a0\u6dfb\u52a0\u5242\u3002\u53cd\u5e94\u7ed3\u679c\u8868\u660e\uff0c\u5c3d\u7ba1\u4ea7\u7269\u7684\u5bf9\u6620\u9009\u62e9\u6027\u4ece96\uff05\u7565\u964d\u81f393\uff05\uff0c\u4f46\u52a0\u5165AcOH\u540e\u53ef\u5927\u5927\u63d0\u9ad8\u53cd\u5e94\u901f\u5ea6\uff0c\u53ef\u80fd\u662f\u7531\u4e8e\u5bf9\u8d28\u5b50\u5206\u89e3\u6b65\u9aa4\u4fc3\u8fdb\u4f5c\u7528\u4ee5\u53ca\u4fc3\u8fdb\u914d\u4f53\u6eb6\u89e3\u5bfc\u81f4\u3002\u53e6\u4e00\u65b9\u9762\uff0c\u63d0\u9ad8\u91d1\u5c5e\/\u914d\u4f53\u7684\u6bd4\u4f8b\u53ef\u8fdb\u4e00\u6b65\u63d0\u9ad8\u50ac\u5316\u5242\u6548\u7387\u3002\u4f5c\u8005\u901a\u8fc71<\/sup>H NMR\u5149\u8c31\u5206\u6790\uff0c\u7814\u7a76\u4e86(S<\/em>)-DM-MeO-BIPHEP\u4e0eNi(OAc)2<\/sub>\u00b74H2<\/sub>O\u5728\u4e0d\u540c\u914d\u6bd4\u548c\u6e29\u5ea6\u4e0b\u7684\u76f8\u5173\u914d\u4f4d\u5173\u7cfb\uff08Figure 3\uff09\u3002\u5f53L\/M\u4e3a1\/1\u65f6\uff0cComplex-1\u7684\u542b\u91cf\u7ea6\u4e3a50\uff05\uff0c\u800c\u5f53L\/M\u6bd4\u4e3a2\/1\u62161\/2\u65f6\uff0cComplex-1\u7684\u542b\u91cf\u5206\u522b\u589e\u52a0\u81f365\uff05\u548c68\uff05\u3002\u56e0\u6b64\uff0c\u8fc7\u91cf\u7684\u954d\u76d0\u6216\u914d\u4f53\u53ef\u4ee5\u4fc3\u8fdb\u6d3b\u6027Complex-1\u7684\u5f62\u6210\uff0c\u4ece\u800c\u63d0\u9ad8\u6c22\u5316\u6548\u7387\u3002\u6b64\u5916\uff0c NMR\u53d8\u6e29\u5b9e\u9a8c\u7684\u7ed3\u679c\u8868\u660e\uff0c\u5728Complex-1\u548c(S<\/em>)-DM-MeO-BIPHEP\/Ni(OAc)2<\/sub>\u4e4b\u95f4\u5b58\u5728\u914d\u4f4d\u548c\u89e3\u79bb\u5e73\u8861\u5173\u7cfb\u3002<\/p>\n

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

\uff08\u56fe\u7247\u6765\u6e90\uff1aAngew. Chem. Int. Ed<\/em>.\uff09<\/p>\n

\u7d27\u63a5\u7740\uff0c\u4f5c\u8005\u5bf9\u53cd\u5e94\u7684\u5b9e\u7528\u6027\u4e5f\u8fdb\u884c\u4e86\u76f8\u5173\u7684\u7814\u7a76\uff08Scheme 2\uff09\u3002\u5f53\u4f7f\u75285\u5f53\u91cf\u7684AcOH\u548cL\/S=2\/1\uff0c\u5373\u4f7f\u5728S\/C=2000\u4e0b\u4e5f\u53ef\u5b8c\u6210\u6c22\u5316\u53cd\u5e94\uff0c\u8be5\u7ed3\u679c\u4ee3\u8868\u4e86Ni\u50ac\u5316C=C\u952e\u4e0d\u5bf9\u79f0\u6c22\u5316\u7684\u6700\u9ad8\u6548\u7387\u3002\u6b64\u5916\uff0c\u5c06\u83b7\u5f97\u7684\u4ea7\u7269\u8fdb\u4e00\u6b65\u4fee\u9970\u53ef\u83b7\u5f97\u66f4\u5177\u6709\u4ef7\u503c\u7684\u4ea7\u54c1\u3002\u5f531l<\/strong>\u4e0e\u914d\u4f53(R<\/em>)-DM-MeO-BIPHEP\u53d1\u751f\u6c22\u5316\u53cd\u5e94\u65f6\uff0c\u53ef\u83b7\u5f9792\uff05ee\u7684\u5bf9\u6620\u4f53\u4ea7\u7269(S<\/em>)-2l<\/strong>\u3002\u901a\u8fc7\u7528Schwartz\u8bd5\u5242\u5904\u7406\uff0c\u7136\u540e\u6c34\u89e3(S<\/em>)-3l<\/strong>\uff0c\u53ef\u83b7\u5f97\u624b\u6027\u03b1<\/em>-\u6c28\u57fa\u9178(S<\/em>)-4l<\/strong>\u3002(S<\/em>)-2l<\/strong>\u7ecf\u8fd8\u539f\u4e0eBoc\u57fa\u56e2\u7684\u4ea4\u6362\uff0c\u53ef\u83b7\u5f9791\uff05ee\u7684(S<\/em>)-6l<\/strong>\u3002(S<\/em>)-4l<\/strong>\u548c (R<\/em>)-5l<\/strong>\u8fd8\u53ef\u4ee5\u7ee7\u7eed\u8f6c\u5316\u4e3a(S<\/em>)-7l<\/strong>\u548c(R<\/em>)-8l<\/strong>\uff08\u5b83\u4eec\u5206\u522b\u662f\u86cb\u767d\u9176\u4f53\u6291\u5236\u5242\u548c\u591a\u5df4\u80fa\/\u53bb\u7532\u80be\u4e0a\u817a\u7d20\u518d\u6444\u53d6\u6291\u5236\u5242\u7684\u524d\u4f53\uff09\u3002<\/p>\n

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

\uff08\u56fe\u7247\u6765\u6e90\uff1aAngew. Chem. Int. Ed<\/em>.\uff09<\/p>\n

\u4e3a\u4e86\u8fdb\u4e00\u6b65\u4e86\u89e3\u53cd\u5e94\u7684\u673a\u7406\uff0c\u4f5c\u8005\u8fdb\u884c\u4e86\u76f8\u5173\u7684\u6c18\u4ee3\u5b9e\u9a8c\uff08Scheme 3\uff09\u3002\u5728D2<\/sub>\u6c14\u4f53\u4e0b\uff0c\u6c18\u4e3b\u8981\u4f4d\u4e8e\u03b2-<\/em>\u4f4d\u7f6e\uff08Scheme 3-I\uff09\u3002\u800c\u5728CF3<\/sub>CH2<\/sub>OD\u7684H2<\/sub>\u6c14\u4f53\u4e0b\u53cd\u5e94\uff0c\u83b7\u5f97\u03b1<\/em>-\u548c\u03b2<\/em>-\u4f4d\u90fd\u63ba\u6709\u6c18\u7684\u4ea7\u7269\uff08Scheme 3-II\uff09\u3002\u5f53\u540c\u65f6\u4f7f\u7528D2<\/sub>\u548cCF3<\/sub>CH2<\/sub>OD\u53cd\u5e94\u65f6\uff0c\u03b2<\/em>-\u4f4d\u7f6e\u5b8c\u5168\u6c18\u5316\u800c\u03b1<\/em>-\u4f4d\u7f6e\u90e8\u5206\u6c18\u5316\uff08Scheme 3-III\uff09\u3002\u800c\u4f7f\u7528\u65e0\u6c34Ni(OAc)2<\/sub>\u53cd\u5e94\u65f6\uff0c\u7ed3\u679c\u4e0eNi(OAc)2<\/sub>\u00b74H2<\/sub>O\u76f8\u540c\uff08Scheme 3-IV\uff09\u3002\u4f7f\u7528CF3<\/sub>CD2<\/sub>OD\u548cD2<\/sub>\u5c06\u03b2<\/em>-\u4f4d\u7f6e\u6c18\u5316\u81f31.16 D\uff0c\u8fd8\u5c06\u03b1<\/em>-\u4f4d\u7f6e\u90e8\u5206\u6c18\u5316\uff080.86 D\uff09\uff08Scheme 3-V\uff09\u3002\u5982\u679c\u4e0d\u5b58\u5728H2<\/sub>\u6216D2<\/sub>\u6761\u4ef6\u4e0b\u53cd\u5e94\uff0c\u5219\u4e0d\u4f1a\u68c0\u6d4b\u5230\u4efb\u4f55\u4ea7\u7269\uff0c\u8fd9\u8868\u660e\u8be5\u8fd8\u539f\u53cd\u5e94\u662f\u6c22\u5316\u53cd\u5e94\uff0c\u800c\u4e0d\u662f\u8f6c\u79fb\u6c22\u5316\u53cd\u5e94\u3002\u6839\u636e\u6c18\u6807\u8bb0\u5b9e\u9a8c\uff0c\u53ef\u4ee5\u63a8\u65ad\u51fa\u03b2<\/em>-H\/D\u4e3b\u8981\u6e90\u81eaH2<\/sub>\/D2<\/sub>\uff0c\u800c\u03b1<\/em>-H\/D\u6765\u81ea\u4e2d\u95f4\u4f53\u4e2d\u7684H+<\/sup>\/D+<\/sup>\u3002<\/p>\n

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

\uff08\u56fe\u7247\u6765\u6e90\uff1aAngew. Chem. Int. Ed<\/em>.\uff09<\/p>\n

\u6839\u636e\u4e0a\u8ff0\u7684\u5b9e\u9a8c\u548c\u76f8\u5173\u6587\u732e\u7684\u67e5\u9605\uff0c\u4f5c\u8005\u63d0\u51fa\u4e86\u4e00\u79cd\u53ef\u80fd\u7684\u53cd\u5e94\u673a\u7406\uff08Scheme 4\uff09\u3002\u9996\u5148\uff0cH2<\/sub>\u4e0eA<\/strong>\u8fdb\u884c\u5f02\u8d28\u88c2\u89e3\u5f62\u6210Ni(II)-H\u7edc\u5408\u7269B<\/strong>\uff0cB<\/strong>\u518d\u4e0e\u5e95\u72691l<\/strong>\u914d\u4f4d\uff0c\u6d3b\u5316\u4e59\u70ef\u57fa\uff0c\u5f62\u6210\u4e2d\u95f4\u4f53C<\/strong>\u3002\u7136\u540e\uff0cNi-H\u63d2\u5165\u4e59\u70ef\u57fa\u7684\u03b2<\/em>-\u4f4d\uff0c\u751f\u6210C-Ni\u4e2d\u95f4\u4f53D<\/strong>\u3002\u6700\u540e\uff0cD<\/strong>\u7ecf\u8d28\u5b50\u5206\u89e3\u540e\u91ca\u653e\u83b7\u5f97\u76ee\u6807\u4ea7\u72692l<\/strong>\u3002<\/p>\n

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

\uff08\u56fe\u7247\u6765\u6e90\uff1aAngew. Chem. Int. Ed<\/em>.\uff09<\/p>\n

\u603b\u7ed3<\/h4>\n

\u4e0a\u6d77\u4ea4\u901a\u5927\u5b66\u5f20\u4e07\u658c\u6559\u6388\u8bfe\u9898\u62a5\u9053\uff0c\u901a\u8fc7\u954d\u4e0e\u624b\u6027\u53cc\u81a6\u914d\u4f53\u7684\u7ed3\u5408\uff0c\u5b9e\u73b02-\u9170\u80fa\u57fa\u4e19\u70ef\u9178\u916f\u4e0d\u5bf9\u79f0\u6c22\u5316\u53cd\u5e94\uff0c\u4ee5\u9ad8\u6536\u7387\uff08\u9ad8\u8fbe99%\uff09\u548c\u9ad8\u5bf9\u6620\u9009\u62e9\u6027\uff08\u9ad8\u8fbe96\uff05ee\uff09\u83b7\u5f97\u624b\u6027\u03b1<\/em>-\u6c28\u57fa\u9178\u916f\u884d\u751f\u7269\u3002\u6b64\u5916\uff0c\u53ef\u5c06\u50ac\u5316\u5242\u8f7d\u91cf\u964d\u81f3S\/C=2000\uff0c\u4ece\u800c\u5b9e\u73b0\u9ad8\u50ac\u5316\u6548\u7387\uff0c\u8fd9\u4e5f\u4ee3\u8868\u4e86Ni\u50ac\u5316\u70ef\u70c3\u7684\u4e0d\u5bf9\u79f0\u6c22\u5316\u7684\u6700\u9ad8\u50ac\u5316\u6548\u7387\u3002\u540c\u65f6\uff0c\u83b7\u5f97\u7684\u76ee\u6807\u4ea7\u7269\u53ef\u8fdb\u4e00\u6b65\u8f6c\u5316\u4e3a\u624b\u6027\u03b1<\/em>-\u6c28\u57fa\u9178\uff0c\u03b2<\/em>-\u6c28\u57fa\u9187\u53ca\u5176\u751f\u7269\u6d3b\u6027\u884d\u751f\u7269\u3002<\/p>\n

\u672c\u6587\u7248\u6743\u5c5e\u4e8e\u00a0Chem-Station\u5316\u5b66\u7a7a\u95f4<\/a>\uff0c<\/strong>\u00a0\u6b22\u8fce\u70b9\u51fb\u6309\u94ae\u5206\u4eab\uff0c\u672a\u7ecf\u8bb8\u53ef\uff0c\u8c22\u7edd\u8f6c\u8f7d\uff01<\/p>\n","protected":false},"excerpt":{"rendered":"\u672c\u6587\u4f5c\u8005\uff1a\u6749\u6749 \u5bfc\u8bfb \u8fd1\u65e5\uff0c\u4e0a\u6d77\u4ea4\u901a\u5927\u5b66\u5f20\u4e07\u658c\u6559\u6388\u8bfe\u9898\u5728Angew\u53d1\u8868\u8bba\u6587\uff0c\u62a5\u9053\u4e86\u901a\u8fc7\u954d\u4e0e\u624b\u6027\u53cc\u81a6\u914d\u4f53\u7684\u7ed3\u5408\uff0c\u5b9e\u73b02-\u9170\u80fa\u57fa\u4e19\u70ef\u9178\u916f\u4e0d\u5bf9\u79f0\u6c22\u5316\u53cd\u5e94\uff0c\u4ee5\u9ad8\u6536\u7387\u548c\u9ad8\u5bf9\u6620\u9009\u62e9\u6027\u83b7\u5f97\u624b\u6027\u03b1-\u6c28\u57fa\u9178\u916f\u884d\u751f\u7269\u3002\u6b64\u5916\uff0c\u53ef\u5c06\u50ac\u5316\u5242\u8f7d\u91cf\u964d\u81f3S\/C=2000\uff0c\u4ece\u800c\u5b9e\u73b0\u9ad8\u6548\u7684\u50ac\u5316\u6548\u7387\u3002\u540c\u65f6\uff0c\u83b7\u5f97\u7684\u76ee\u6807\u4ea7\u7269\u53ef\u8fdb\u4e00\u6b65\u8f6c\u5316\u4e3a\u624b\u6027\u03b1-\u6c28\u57fa\u9178\uff0c\u03b2-\u6c28\u57fa\u9187\u7b49\u4e00\u4e9b\u751f\u7269\u6d3b\u6027\u884d\u751f\u7269\u3002\u6587\u7ae0\u94fe\u63a5DOI\uff1a10.1002\/anie.201916534 \uff08\u56fe\u7247\u6765\u6e90\uff1aAngew. Chem. Int. Ed.\uff09 \u6b63\u6587 \u624b\u6027\u03b1-\u6c28\u57fa\u9178\u4f5c\u4e3a\u5316\u5b66\u548c\u751f\u7269\u5b66\u4e2d\u6700\u91cd\u8981\u7684\u9aa8\u67b6\u4e4b\u4e00\uff08Figure 1\uff09\u3002\u56e0\u6b64\uff0c\u624b\u6027\u03b1-\u6c28\u57fa\u9178\u53ca\u5176\u884d\u751f\u7269\u7684\u4e0d\u5bf9\u79f0\u5408\u6210\u53d7\u5230\u5e7f\u6cdb\u7684\u5173\u6ce8\uff0c\u6570\u4ee5\u4e07\u8ba1\u7684\u6587\u732e\u5df2\u62a5\u9053\u4e86\u6570\u5341\u79cd\u65b9\u6cd5\uff0c\u800c\u8fc7\u6e21\u91d1\u5c5e\u50ac\u53162-\u9170\u80fa\u57fa\u4e19\u70ef\u9178\u916f\u7684\u4e0d\u5bf9\u79f0\u6c22\u5316\u53cd\u5e94\u662f\u5176\u4e2d\u6700\u9ad8\u6548\u7684\u65b9\u6cd5\u3002\u5728\u8fc7\u53bb\u6570\u5341\u5e74\u4e2d\uff0c\u63d0\u9ad8\u8be5\u65b9\u6cd5\u7684\u6548\u7387\u548c\u5b9e\u7528\u6027\u4e00\u76f4\u662f\u8be5\u9886\u57df\u7814\u7a76\u7684\u91cd\u70b9\uff0c\u4e00\u4e9b\u7531Rh\u3001Ru\u548cIr\u7ec4\u6210\u7684\u50ac\u5316\u5242\u5df2\u88ab\u62a5\u9053\uff08Figure 2\uff09\u30022001\u5e74\uff0c\u5f53Knowles\u901a\u8fc7Rh\u50ac\u5316\u4e0d\u5bf9\u79f0\u6c22\u5316\u53cd\u5e94\u5b9e\u73b0L-DOPA\u7684\u5de5\u4e1a\u5408\u6210\uff0c\u4ece\u800c\u83b7\u5f97\u8bfa\u8d1d\u5c14\u5316\u5b66\u5956\uff0c\u4f7f\u8be5\u9886\u57df\u53d8\u5f97\u66f4\u4e3a\u91cd\u8981\u3002\u7136\u800c\uff0c\u8d35\u91d1\u5c5e\u50ac\u5316\u5242\u7684\u9ad8\u6210\u672c\u548c\u9ad8\u6bd2\u6027\u963b\u788d\u4e86\u8be5\u6280\u672f\u7684\u5e7f\u6cdb\u5e94\u7528\u3002 \uff08\u56fe\u7247\u6765\u6e90\uff1aAngew. Chem. Int. Ed.\uff09 \u4e0e\u8d35\u91d1\u5c5e\u50ac\u5316\u5242\u76f8\u6bd4\uff0c\u4e00\u4e9bMn\u3001Fe\u3001Co\u3001Ni\u3001Cu\u7b49\u8fc7\u6e21\u91d1\u5c5e\u50ac\u5316\u5242\u4e5f\u53ef\u5b9e\u73b0\u4e0d\u5bf9\u79f0\u6c22\u5316\u53cd\u5e94\uff0c\u540c\u65f6\u5177\u6709\u6210\u672c\u4f4e\u3001\u6bd2\u6027\u4f4e\u7b49\u4f18\u70b9\u3002\u76ee\u524d\u4e3a\u6b62\uff0c\u53ea\u6709\u94b4\u914d\u5408\u7269\u5b9e\u73b02-\u9170\u80fa\u57fa\u4e19\u70ef\u9178\u916f\u7684\u4e0d\u5bf9\u79f0\u6c22\u5316\u53cd\u5e94\uff0c\u5408\u6210\u624b\u6027\u03b1-\u6c28\u57fa\u9178\u6216\u9170\u80fa\u884d\u751f\u7269\uff08Figure 2\uff09\u3002\u4f46\u662f\uff0c\u5176\u4ed6\u8fc7\u6e21\u91d1\u5c5e\u5177\u6709\u5404\u81ea\u7684\u914d\u4f4d\u6a21\u5f0f\uff0c\u65e0\u6cd5\u5229\u7528\u9170\u80fa\u57fa\u56e2\u7684\u6d3b\u5316\u7b56\u7565\uff0c\u4ece\u800c\u963b\u788d\u4e862-\u9170\u80fa\u57fa\u4e19\u70ef\u9178\u916f\u4e0d\u5bf9\u79f0\u6c22\u5316\u53cd\u5e94\u7684\u5c1d\u8bd5\u3002\u6700\u8fd1\uff0cChirik\u548cZhang\u8bfe\u9898\u7ec4\u62a5\u9053\u4e86Ni\u50ac\u5316\u70ef\u70c3\u7684\u4e0d\u5bf9\u79f0\u52a0\u6c22\u53cd\u5e94\uff0c\u540c\u65f6\u8fd8\u5f00\u53d1\u4e86\u4e00\u4e2aNi\u50ac\u5316\u4e9a\u80fa\u7684\u4e0d\u5bf9\u79f0\u6c22\u5316\u53cd\u5e94\u3002\u5728\u6b64\u5b9e\u9a8c\u4e2d\uff0c\u4f5c\u8005\u53d1\u73b0\uff0c\u5e95\u7269\u548c\u50ac\u5316\u5242\u4e4b\u95f4\u5b58\u5728\u4e00\u5b9a\u7684\u76f8\u4e92\u4f5c\u7528\u53ef\u63d0\u9ad8\u50ac\u5316\u6d3b\u6027\uff08\u9002\u5f53\u7684\u91d1\u5c5e\/\u914d\u4f53\u6bd4\u53ef\u63d0\u9ad8\u50ac\u5316\u6548\u7387\uff09\u3002\u56e0\u6b64\uff0c\u4f5c\u8005\u8bbe\u60f3\uff0c\u662f\u5426\u53ef\u4ee5\u901a\u8fc7\u4e0a\u8ff0\u7c7b\u4f3c\u7684\u7b56\u7565\uff0c\u5b9e\u73b0\u7b2c\u4e00\u4e2aNi\u50ac\u53162-\u9170\u80fa\u57fa\u4e19\u70ef\u9178\u916f\u7684\u4e0d\u5bf9\u79f0\u6c22\u5316\u53cd\u5e94\uff0c\u5408\u6210\u624b\u6027\u03b1-\u6c28\u57fa\u9178\u884d\u751f\u7269\uff08Figure 2\uff09\u3002 \uff08\u56fe\u7247\u6765\u6e90\uff1aAngew. Chem. Int. Ed.\uff09 \u9996\u5148\uff0c\u4f5c\u8005\u5bf9\u4e0d\u540c\u53d6\u4ee3\u7684\u5e95\u72691\u8fdb\u884c\u4e86\u5927\u91cf\u7684\u53cd\u5e94\u7814\u7a76\uff08Table 1\uff09\u3002\u5f53\u4ee51a\u4f5c\u4e3a\u5e95\u7269\uff0c\u4ee5Ni(OAc)2\u00b74H2O\u4f5c\u4e3a\u50ac\u5316\u5242\uff0c(S)-BINAP\u4e3a\u914d\u4f53\uff0c\u4ec5\u83b7\u5f9723\uff05\u8f6c\u5316\u7387\u548c40\uff05ee\u7684\u4ea7\u72692a\uff08entry 1\uff09\u3002\u968f\u540e\uff0c\u4f5c\u8005\u7814\u7a76\u4e86\u4e0d\u540c\u53d6\u4ee3\u7684R1\u548cR2\u57fa\u56e2\u770b\u662f\u5426\u53ef\u4ee5\u83b7\u5f97\u66f4\u597d\u7684\u7ed3\u679c\uff0c\u53cd\u5e94\u7ed3\u679c\u8868\u660e\uff0c\u4e0d\u540c\u53d6\u4ee3\u7684R1\u548cR2\u57fa\u56e2\u5bf9\u53cd\u5e94\u5177\u6709\u4e00\u5b9a\u7684\u5f71\u54cd\uff08entries 2-12\uff09\uff0c\u5f53R2\u57fa\u56e2\u4e3ao-MeO-C6H4\u65f6\uff0c\u53ef\u83b7\u5f97\u6700\u4f73\u7ed3\u679c\uff08\u4ea7\u738774\uff05\u300196\uff05ee\uff09\u3002\u63a5\u4e0b\u6765\uff0c\u4f5c\u8005\u4e5f\u5bf9\u5404\u7c7bNi\u50ac\u5316\u5242\u548c\u6eb6\u5242\u8fdb\u884c\u4e86\u7b5b\u9009\uff0c\u53cd\u5e94\u7ed3\u679c\u8868\u660e\uff0cNi(OAc)2\u00b74H2O\u4f5c\u4e3a\u6700\u4f73\u50ac\u5316\u5242\uff0cTFE\u4f5c\u4e3a\u6700\u4f73\u6eb6\u5242\u3002\u6b64\u5916\uff0c\u4f5c\u8005\u4e5f\u5bf9\u591a\u79cd\u624b\u6027\u53cc\u81a6\u914d\u4f53\u8fdb\u884c\u4e86\u7b5b\u9009\uff0c\u5176\u4e2d\u8f74\u5411\u624b\u6027\u914d\u4f53\u8868\u73b0\u51fa\u8f83\u597d\u7684\u7ed3\u679c\u3002\u4f7f\u7528(S)-MeO-BIPHEP\u3001(S)-H8-BINAP\u3001(S)-GarPhos\u65f6\u53ef\u4ee5\u83b7\u5f97\u8f83\u597d\u7684\u7ed3\u679c\uff0c\u540c\u65f6\u4f5c\u8005\u53d1\u73b0\uff0c\u7a7a\u95f4\u6548\u5e94\u662f\u5f71\u54cd\u4e0d\u540c\u914d\u4f53\u6027\u80fd\u7684\u5173\u952e\u56e0\u7d20\u3002\u56e0\u6b64\uff0c\u4f5c\u8005\u7814\u7a76\u4e86\u5176\u4ed6\u4e09\u4e2a\u5177\u6709\u4e2d\u7b49\u4e8c\u9762\u89d2\u7684\u8f74\u5411\u624b\u6027\u914d\u4f53\uff0c(S)-DM-BINAP\uff0c(S)-DM-MeO-BIPHEP\u548c(S)-DM-SegPhos\uff0c\u5f53(S)-DM-MeO-BIPHEP\u7528\u4f5c\u914d\u4f53\uff0c\u53ef\u5c06\u53cd\u5e94\u65f6\u95f4\u53ef\u4ee5\u7f29\u77ed\u523024h\uff0c\u5e76\u83b7\u5f9795\uff05\u8f6c\u6362\u7387\u548c95-96\uff05ee\u7684\u76f8\u5e94\u4ea7\u7269\u3002 \uff08\u56fe\u7247\u6765\u6e90\uff1aAngew. Chem. Int. Ed.\uff09 \u5728\u83b7\u5f97\u4e0a\u8ff0\u6700\u4f73\u53cd\u5e94\u6761\u4ef6\u540e\uff0c\u4f5c\u8005\u5f00\u59cb\u5bf9\u5e95\u7269\u8fdb\u884c\u4e86\u6269\u5c55\uff08Scheme 1\uff09\u3002\u5728\u82b3\u57fa\u76842,3,4\u4f4d\u4e0a\u5177\u6709\u4f9b\u7535\u5b50\u548c\u5438\u7535\u5b50\u53d6\u4ee3\u57fa\u65f6\u5747\u53ef\u83b7\u5f97\u76f8\u5e94\u7684\u76ee\u6807\u4ea7\u72692l–2ad\uff08\u6536\u738793-99%\uff0c90-96\uff05ee\uff09\u3002\u540c\u65f6\uff0c\u4e8c\u53d6\u4ee3\uff081ae–1af\uff09\u3001\u8418\u57fa\uff081ag–1ah\uff09\u548c\u567b\u5429\u57fa\u5e95\u7269\uff081ai\uff09\u540c\u6837\u83b7\u5f97\u8f83\u597d\u7684\u7ed3\u679c\u3002\u6b64\u5916\uff0c\u5f53\u82b3\u57fa\u6539\u53d8\u4e3a\u73af\u5df1\u57fa\u65f6\uff0c\u6c22\u5316\u53cd\u5e94\u4e5f\u80fd\u591f\u987a\u5229\u8fdb\u884c\uff0c\u83b7\u5f9793\uff05ee\u7684\u76f8\u5e94\u4ea7\u72692aj\uff0c\u4f46\u50ac\u5316\u5242\u91cf\u9700\u589e\u52a0\u3002 \uff08\u56fe\u7247\u6765\u6e90\uff1aAngew. Chem. Int. Ed.\uff09 \u968f\u540e\uff0c\u4f5c\u8005\u8fdb\u4e00\u6b65\u5bf9\u50ac\u5316\u6548\u7387\u7ee7\u7eed\u8fdb\u884c\u7814\u7a76\u3002\u8d77\u521d\uff0c\u5f53S\/C=500\u65f6\uff0c\u5373\u4f7f\u957f\u65f6\u95f4\u53cd\u5e94\u4e5f\u672a\u80fd\u5b8c\u5168\u8f6c\u5316\uff0c\u4e3a\u4e86\u8fdb\u4e00\u6b65\u63d0\u9ad8\u6548\u7387\uff0c\u4f5c\u8005\u8bd5\u56fe\u5728\u53cd\u5e94\u4f53\u7cfb\u4e2d\u589e\u52a0\u6dfb\u52a0\u5242\u3002\u53cd\u5e94\u7ed3\u679c\u8868\u660e\uff0c\u5c3d\u7ba1\u4ea7\u7269\u7684\u5bf9\u6620\u9009\u62e9\u6027\u4ece96\uff05\u7565\u964d\u81f393\uff05\uff0c\u4f46\u52a0\u5165AcOH\u540e\u53ef\u5927\u5927\u63d0\u9ad8\u53cd\u5e94\u901f\u5ea6\uff0c\u53ef\u80fd\u662f\u7531\u4e8e\u5bf9\u8d28\u5b50\u5206\u89e3\u6b65\u9aa4\u4fc3\u8fdb\u4f5c\u7528\u4ee5\u53ca\u4fc3\u8fdb\u914d\u4f53\u6eb6\u89e3\u5bfc\u81f4\u3002\u53e6\u4e00\u65b9\u9762\uff0c\u63d0\u9ad8\u91d1\u5c5e\/\u914d\u4f53\u7684\u6bd4\u4f8b\u53ef\u8fdb\u4e00\u6b65\u63d0\u9ad8\u50ac\u5316\u5242\u6548\u7387\u3002\u4f5c\u8005\u901a\u8fc71H NMR\u5149\u8c31\u5206\u6790\uff0c\u7814\u7a76\u4e86(S)-DM-MeO-BIPHEP\u4e0eNi(OAc)2\u00b74H2O\u5728\u4e0d\u540c\u914d\u6bd4\u548c\u6e29\u5ea6\u4e0b\u7684\u76f8\u5173\u914d\u4f4d\u5173\u7cfb\uff08Figure 3\uff09\u3002\u5f53L\/M\u4e3a1\/1\u65f6\uff0cComplex-1\u7684\u542b\u91cf\u7ea6\u4e3a50\uff05\uff0c\u800c\u5f53L\/M\u6bd4\u4e3a2\/1\u62161\/2\u65f6\uff0cComplex-1\u7684\u542b\u91cf\u5206\u522b\u589e\u52a0\u81f365\uff05\u548c68\uff05\u3002\u56e0\u6b64\uff0c\u8fc7\u91cf\u7684\u954d\u76d0\u6216\u914d\u4f53\u53ef\u4ee5\u4fc3\u8fdb\u6d3b\u6027Complex-1\u7684\u5f62\u6210\uff0c\u4ece\u800c\u63d0\u9ad8\u6c22\u5316\u6548\u7387\u3002\u6b64\u5916\uff0c NMR\u53d8\u6e29\u5b9e\u9a8c\u7684\u7ed3\u679c\u8868\u660e\uff0c\u5728Complex-1\u548c(S)-DM-MeO-BIPHEP\/Ni(OAc)2\u4e4b\u95f4\u5b58\u5728\u914d\u4f4d\u548c\u89e3\u79bb\u5e73\u8861\u5173\u7cfb\u3002 \uff08\u56fe\u7247\u6765\u6e90\uff1aAngew. Chem. Int. Ed.\uff09 \u7d27\u63a5\u7740\uff0c\u4f5c\u8005\u5bf9\u53cd\u5e94\u7684\u5b9e\u7528\u6027\u4e5f\u8fdb\u884c\u4e86\u76f8\u5173\u7684\u7814\u7a76\uff08Scheme 2\uff09\u3002\u5f53\u4f7f\u75285\u5f53\u91cf\u7684AcOH\u548cL\/S=2\/1\uff0c\u5373\u4f7f\u5728S\/C=2000\u4e0b\u4e5f\u53ef\u5b8c\u6210\u6c22\u5316\u53cd\u5e94\uff0c\u8be5\u7ed3\u679c\u4ee3\u8868\u4e86Ni\u50ac\u5316C=C\u952e\u4e0d\u5bf9\u79f0\u6c22\u5316\u7684\u6700\u9ad8\u6548\u7387\u3002\u6b64\u5916\uff0c\u5c06\u83b7\u5f97\u7684\u4ea7\u7269\u8fdb\u4e00\u6b65\u4fee\u9970\u53ef\u83b7\u5f97\u66f4\u5177\u6709\u4ef7\u503c\u7684\u4ea7\u54c1\u3002\u5f531l\u4e0e\u914d\u4f53(R)-DM-MeO-BIPHEP\u53d1\u751f\u6c22\u5316\u53cd\u5e94\u65f6\uff0c\u53ef\u83b7\u5f9792\uff05ee\u7684\u5bf9\u6620\u4f53\u4ea7\u7269(S)-2l\u3002\u901a\u8fc7\u7528Schwartz\u8bd5\u5242\u5904\u7406\uff0c\u7136\u540e\u6c34\u89e3(S)-3l\uff0c\u53ef\u83b7\u5f97\u624b\u6027\u03b1-\u6c28\u57fa\u9178(S)-4l\u3002(S)-2l\u7ecf\u8fd8\u539f\u4e0eBoc\u57fa\u56e2\u7684\u4ea4\u6362\uff0c\u53ef\u83b7\u5f9791\uff05ee\u7684(S)-6l\u3002(S)-4l\u548c (R)-5l\u8fd8\u53ef\u4ee5\u7ee7\u7eed\u8f6c\u5316\u4e3a(S)-7l\u548c(R)-8l\uff08\u5b83\u4eec\u5206\u522b\u662f\u86cb\u767d\u9176\u4f53\u6291\u5236\u5242\u548c\u591a\u5df4\u80fa\/\u53bb\u7532\u80be\u4e0a\u817a\u7d20\u518d\u6444\u53d6\u6291\u5236\u5242\u7684\u524d\u4f53\uff09\u3002 \uff08\u56fe\u7247\u6765\u6e90\uff1aAngew. Chem. Int. Ed.\uff09 \u4e3a\u4e86\u8fdb\u4e00\u6b65\u4e86\u89e3\u53cd\u5e94\u7684\u673a\u7406\uff0c\u4f5c\u8005\u8fdb\u884c\u4e86\u76f8\u5173\u7684\u6c18\u4ee3\u5b9e\u9a8c\uff08Scheme 3\uff09\u3002\u5728D2\u6c14\u4f53\u4e0b\uff0c\u6c18\u4e3b\u8981\u4f4d\u4e8e\u03b2-\u4f4d\u7f6e\uff08Scheme 3-I\uff09\u3002\u800c\u5728CF3CH2OD\u7684H2\u6c14\u4f53\u4e0b\u53cd\u5e94\uff0c\u83b7\u5f97\u03b1-\u548c\u03b2-\u4f4d\u90fd\u63ba\u6709\u6c18\u7684\u4ea7\u7269\uff08Scheme 3-II\uff09\u3002\u5f53\u540c\u65f6\u4f7f\u7528D2\u548cCF3CH2OD\u53cd\u5e94\u65f6\uff0c\u03b2-\u4f4d\u7f6e\u5b8c\u5168\u6c18\u5316\u800c\u03b1-\u4f4d\u7f6e\u90e8\u5206\u6c18\u5316\uff08Scheme 3-III\uff09\u3002\u800c\u4f7f\u7528\u65e0\u6c34Ni(OAc)2\u53cd\u5e94\u65f6\uff0c\u7ed3\u679c\u4e0eNi(OAc)2\u00b74H2O\u76f8\u540c\uff08Scheme 3-IV\uff09\u3002\u4f7f\u7528CF3CD2OD\u548cD2\u5c06\u03b2-\u4f4d\u7f6e\u6c18\u5316\u81f31.16 D\uff0c\u8fd8\u5c06\u03b1-\u4f4d\u7f6e\u90e8\u5206\u6c18\u5316\uff080.86 D\uff09\uff08Scheme 3-V\uff09\u3002\u5982\u679c\u4e0d\u5b58\u5728H2\u6216D2\u6761\u4ef6\u4e0b\u53cd\u5e94\uff0c\u5219\u4e0d\u4f1a\u68c0\u6d4b\u5230\u4efb\u4f55\u4ea7\u7269\uff0c\u8fd9\u8868\u660e\u8be5\u8fd8\u539f\u53cd\u5e94\u662f\u6c22\u5316\u53cd\u5e94\uff0c\u800c\u4e0d\u662f\u8f6c\u79fb\u6c22\u5316\u53cd\u5e94\u3002\u6839\u636e\u6c18\u6807\u8bb0\u5b9e\u9a8c\uff0c\u53ef\u4ee5\u63a8\u65ad\u51fa\u03b2-H\/D\u4e3b\u8981\u6e90\u81eaH2\/D2\uff0c\u800c\u03b1-H\/D\u6765\u81ea\u4e2d\u95f4\u4f53\u4e2d\u7684H+\/D+\u3002 \uff08\u56fe\u7247\u6765\u6e90\uff1aAngew. Chem. Int. Ed.\uff09 \u6839\u636e\u4e0a\u8ff0\u7684\u5b9e\u9a8c\u548c\u76f8\u5173\u6587\u732e\u7684\u67e5\u9605\uff0c\u4f5c\u8005\u63d0\u51fa\u4e86\u4e00\u79cd\u53ef\u80fd\u7684\u53cd\u5e94\u673a\u7406\uff08Scheme 4\uff09\u3002\u9996\u5148\uff0cH2\u4e0eA\u8fdb\u884c\u5f02\u8d28\u88c2\u89e3\u5f62\u6210Ni(II)-H\u7edc\u5408\u7269B\uff0cB\u518d\u4e0e\u5e95\u72691l\u914d\u4f4d\uff0c\u6d3b\u5316\u4e59\u70ef\u57fa\uff0c\u5f62\u6210\u4e2d\u95f4\u4f53C\u3002\u7136\u540e\uff0cNi-H\u63d2\u5165\u4e59\u70ef\u57fa\u7684\u03b2-\u4f4d\uff0c\u751f\u6210C-Ni\u4e2d\u95f4\u4f53D\u3002\u6700\u540e\uff0cD\u7ecf\u8d28\u5b50\u5206\u89e3\u540e\u91ca\u653e\u83b7\u5f97\u76ee\u6807\u4ea7\u72692l\u3002 \uff08\u56fe\u7247\u6765\u6e90\uff1aAngew. Chem. Int. 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