{"id":14206,"date":"2017-05-27T08:28:19","date_gmt":"2017-05-27T00:28:19","guid":{"rendered":"\/\/www.gsbet888.com\/?p=14206"},"modified":"2019-08-02T18:53:11","modified_gmt":"2019-08-02T10:53:11","slug":"%e6%89%8b%e6%80%a7%e9%98%b4%e7%a6%bb%e5%ad%90%e7%9b%b8%e8%bd%ac%e7%a7%bb-%e9%92%af%e5%82%ac%e5%8c%96%e4%b8%8d%e5%af%b9%e7%a7%b011-%e4%ba%8c%e8%8a%b3%e5%9f%ba%e5%8c%96%e5%8f%8d%e5%ba%94","status":"publish","type":"post","link":"\/\/www.gsbet888.com\/%e5%8c%96%e5%ad%a6%e6%9d%82%e8%ae%b0\/2017\/05\/%e6%89%8b%e6%80%a7%e9%98%b4%e7%a6%bb%e5%ad%90%e7%9b%b8%e8%bd%ac%e7%a7%bb-%e9%92%af%e5%82%ac%e5%8c%96%e4%b8%8d%e5%af%b9%e7%a7%b011-%e4%ba%8c%e8%8a%b3%e5%9f%ba%e5%8c%96%e5%8f%8d%e5%ba%94.html","title":{"rendered":"\u624b\u6027\u9634\u79bb\u5b50\u76f8\u8f6c\u79fb-\u94af\u50ac\u5316\u4e0d\u5bf9\u79f01,1-\u4e8c\u82b3\u57fa\u5316\u53cd\u5e94"},"content":{"rendered":"

2016\u5e74\u3001\u72b9\u4ed6\u5927\u5b66\u30fbMatthew S. Sigman<\/a>\u7b49\u4eba\u3001\u6210\u529f\u5b9e\u73b0\u4e86\u7f3a\u7535\u5b50\u7684\u672b\u7aef\u70ef\u70c3\u7684\u624b\u60271,1-\u4e8c\u82b3\u57fa\u5316\u53cd\u5e94\u3002\u8be5\u53cd\u5e94\u4e2d\u4f5c\u8005\u8fd0\u7528\u4e86\u624b\u6027\u9634\u79bb\u5b50\u76f8\u8f6c\u79fb\u50ac\u5316\u5242 (chiral anion phase-transfer, CAPT)\u3001\u4f5c\u4e3aPd\u50ac\u5316\u5242\u7684\u624b\u6027\u914d\u4f53\u6210\u529f\u5b9e\u73b0\u4e86\u9ad8\u624b\u6027\u9009\u62e9\u6027\u7684\u5408\u6210\u3002\u540c\u65f6\u901a\u8fc7\u5bf9\u5206\u5b50\u7ed3\u6784\u7279\u6027\u7684\u591a\u53d8\u91cf\u5206\u6790\uff0c\u89e3\u6790\u4e86\u4e3a\u4f55\u80fd\u5f97\u5230\u751f\u6210\u9ad8\u624b\u6027\u4ea7\u7269\u7684\u4e00\u4e9b\u91cd\u8981\u8981\u7d20\u3002<\/b><\/p>\n

\u201cDevelopment and Analysis of Pd(0) Catalyzed Enantioselective 1,1-Diarylation of Acrylates Enabled by Chiral Anion Phase Transfer\u201d
\nYamamoto, E.; Hilton, M. J.; Orlandi, M.; Saini, V.; Toste, F. D.; Sigman, M. S.* J. Am. Chem. Soc.<\/i> 2016<\/b>, 138<\/i>, 15877. DOI: 10.1021\/jacs.6b11367<\/a><\/p><\/blockquote>\n

\u7814\u7a76\u7684\u96be\u70b9\uff08\u95ee\u9898\u70b9\uff09<\/h4>\n

1,1-\u4e8c\u82b3\u57fa\u70f7\u70c3\u662f\u5404\u79cd\u751f\u7269\u6d3b\u6027\u7269\u8d28\u7684\u91cd\u8981\u7ec4\u6210\u9aa8\u67b6\u5355\u4f4d\u4e4b\u4e00\u3002\u8be5\u7ed3\u6784\u53ef\u4ee5\u901a\u8fc7\u672b\u7aef\u70ef\u70c3\u4e0e2\u79cd\u82b3\u57fa\u4f9b\u4f53\u8fdb\u884c\u4e09\u7ec4\u5206\u53cd\u5e94\u8fdb\u884c\u7b80\u4fbf\u5408\u6210\u83b7\u5f97\u3002\u8fd9\u7c7b\u53cd\u5e94\u5728\u672c\u8bba\u6587\u4f5c\u8005\u4ee5\u524d\u7684\u5de5\u4f5c\u4e2d\u5df2\u7ecf\u6709\u6709\u8fc7\u62a5\u9053\uff0c\u800c\u5f53\u65f6\u7684\u624b\u6027\u53cd\u5e94\u4e00\u76f4\u6ca1\u6709\u89e3\u51b3[1]\u3002\u5f53\u65f6\u7684\u7814\u7a76\u4e2d\uff0c\u4f5c\u8005\u53d1\u73b0\u4f7f\u7528\u542bN\u6216\u8005\u542bP\u7684\u624b\u6027\u914d\u4f53\u540e\uff0c\u53cd\u5e94\u6d3b\u6027\u663e\u8457\u4e0b\u964d\uff0c\u56e0\u6b64\u5728\u5f53\u65f6\u4f5c\u8005\u6ca1\u6709\u8fdb\u4e00\u6b65\u7b5b\u9009\u914d\u4f53\u3002<\/p>\n

\u7ee7\u800c\u5728\u53bb\u5e74\uff0c\u4f5c\u8005\u7528\u4e86CAPT<\/strong>[2]\uff0c\u8fd9\u4e2a\u76f8\u8f6c\u79fb\u8bd5\u5242\u7684\u52a0\u5165\uff0c\u4f7f\u5f97\u624b\u6027\u9009\u62e9\u6027\u5b9e\u73b0\u56f0\u96be\u7684\u672c\u53cd\u5e94\uff0c\u4e5f\u80fd\u5f97\u5230\u9ad8\u9009\u62e9\u6027\u7684\u8fdb\u884c\uff0c\u5f97\u5230\u9ad8\u624b\u6027\u4ea7\u7269\u3002<\/p>\n

 <\/p>\n

\u89e3\u51b3\u624b\u6cd5<\/h4>\n

Pd\u50ac\u5316\u5242\u4e0eCAPT\u7684\u7ec4\u5408\u65e9\u57282015\u5e74Toster\u7b49\u4eba\u62a5\u9053\u76841,1-\u4e8c\u82b3\u57fa\u787c\u5316\u53cd\u5e94[3]\u4e2d\u5c31\u5df2\u7ecf\u88ab\u8bc1\u660e\u662f\u975e\u5e38\u6709\u6548\u7684\u3002\u4e0d\u6eb6\u6027\u7684\u91cd\u6c2e\u76d0\u4e0eCAPT\u78f7\u9178\u9634\u79bb\u5b50\u5f62\u6210\u7684\u79bb\u5b50pair\uff0c\u4f7f\u5f97\u91cd\u6c2e\u76d0\u6eb6\u89e3\u6027\u589e\u5f3a\uff0c\u5728\u4f53\u7cfb\u5185\u4ee5\u624b\u6027ion pair\u5b58\u5728\u3002\u7136\u540e\u7531Pd(0)\u5f97\u5230\u7684\u82b3\u57faPd(II)\u4e0e\u70ef\u70c3\u53cd\u5e94\uff0c\u7ecf\u8fc7\u91cd\u6392\u63d2\u5165\/\u03b2\u6d88\u9664\/\u5411\u03c0-\u82c4\u57fa\u6d3b\u6027\u79cd\u7684\u91cd\u6392\uff0c\u6700\u540e\u751f\u6210\u787c\u9178\u5316\u53cd\u5e94\u3002\u800c\u5f53\u65f6\u8be5\u53cd\u5e94\u662f\u5355\u82b3\u57fa\u5316\u7684\u787c\u9178\u5316\u53cd\u5e94\uff0c\u56e0\u6b64\uff0c\u8fd0\u7528\u7c7b\u4f3c\u7684\u8be5\u65b9\u6cd5\uff0c\u8fdb\u884c\u4e8c\u82b3\u57fa\u5316\u53cd\u5e94\u7684\u7814\u7a76\u5728\u5f53\u65f6\u8fd8\u662f\u5f88\u503c\u5f97\u671f\u5f85\u7684\u3002<\/p>\n

\"\"<\/p>\n

\u5177\u4f53\u5b9e\u9a8c\u65b9\u6cd5<\/h4>\n

\u2460\u6eb6\u5242\u7684\u7b5b\u9009<\/b><\/h5>\n

\u4f5c\u8005\u4ee5\u82c4\u916f\u3001\u82ef\u57fa\u91cd\u6c2e\u76d0\u30014-\u7f9f\u57fa\u82ef\u57fa\u787c\u9178\u4e3a\u5e95\u7269\u8fdb\u884c\u53cd\u5e94\u6761\u4ef6\u7684\u7b5b\u9009\u3002\u4ee5\u6b63\u5df1\u70f7\u4e3a\u6eb6\u5242\u7684\u65f6\u5019\uff0c\u53cd\u5e94\u5b8c\u5168\u6ca1\u6709\u8fdb\u884c\u3002\u800c\u6539\u7528THF\uff0c\u63d0\u9ad8\u4e86\u91cd\u6c2e\u76d0\u7684\u6eb6\u89e3\u6027\u540e\uff0c\u53cd\u5e94\u8fdb\u884c\u4e86\uff0c\u4f46\u662f\u624b\u6027\u9009\u62e9\u6027\u5f88\u5dee\u3002\u56e0\u6b64\u4f5c\u8005\u8ba4\u4e3a\uff0c\u5982\u679c\u52a0\u5165\u76f8\u8f6c\u79fb\u9634\u79bb\u5b50CAPT\u5728\u6539\u5584\u91cd\u6c2e\u76d0\u7684\u6eb6\u89e3\u6027\u7684\u540c\u65f6\uff0c\u4e5f\u80fd\u4fc3\u8fdb\u624b\u6027\u9009\u62e9\u6027\u7684\u4ea7\u751f\u3002<\/p>\n

\u2461CAPT\u7ed3\u6784\u7684\u7b5b\u9009<\/b><\/h5>\n

CAPT\u6784\u9020\u4e0eer\u7684\u5173\u8054\u6027\uff0c\u4f5c\u8005\u8fdb\u884c\u4e86\u6df1\u5165\u7814\u7a76\uff0c\u8fd9\u4e2a\u5de5\u4f5c\u91cf\u5176\u5b9e\u8fd8\u662f\u5f88\u5927\u7684\u3002\u4f5c\u8005\u5177\u4f53\u5bf93,3\u2019\u4f4d\u82b3\u9999\u73af\uff0c2-\u4f4d\u53d6\u4ee3\u6216\u80052,6-\u53d6\u4ee3\u7684\u60c5\u51b5\u8fdb\u884c\u4e86\u7b5b\u9009\uff0c\u53d1\u73b0\u53d6\u4ee3\u57fa\u4f4d\u963b\u7684\u5927\u5c0f\u5bf9ee\u7684\u9009\u62e9\u6027\u6709\u663e\u8457\u5f71\u54cd\u3002\u4f5c\u8005\u5bf9\u4e8eCAPT\u78f7\u9178\u9634\u79bb\u5b50\u7684\u6a21\u578b\u7ed3\u6784\u8fdb\u884c\u4e86\u591a\u53d8\u91cf\u8981\u7d20\u7684\u5206\u6790\uff0c\u5f97\u5230\u4e86\u4ee5\u4e0b\u4e09\u4e2a\u4e0e\u624b\u6027\u9009\u62e9\u6027\u76f8\u5173\u7684\u8981\u7d20\u3002<\/p>\n

    \n
  1. C3\u7684\u82b3\u57fa\u4e0eBINAP\u4e4b\u95f4\u7684\u4e8c\u9762\u89d2\uff08\u03b1\uff09<\/li>\n
  2. P=O\u7684\u4f38\u7f29\u9891\u7387\uff08\u03bdPOsy<\/sub>\uff09<\/li>\n
  3. C3\u82b3\u57fa\u4e0a\u7684\u95f4\u4f4d\u53d6\u4ee3\u57fa(B1meta<\/sub>)<\/li>\n<\/ol>\n

    \"\"<\/p>\n

    \u2462\u5e95\u7269\u7ed3\u6784\u6700\u4f18\u5316\u7b5b\u9009<\/b><\/h5>\n

    \u4f5c\u8005\u5728\u5f97\u5230\u6700\u4f18\u7ed3\u6784\u7684CAPT\uff08\u6807\u9898\u56fe\u4e2d\u6240\u793a\uff09\u540e\u3001\u518d\u901a\u8fc7\u7b5b\u82c4\u57fa\u4e0a\u7684\u53d6\u4ee3\u57fa\u3001\u89c2\u5bdf\u4e86\u8fd9\u4f4d\u7f6e\u4e0a\u7684\u53d6\u4ee3\u57fa\u5bf9\u624b\u6027\u9009\u62e9\u6027\u7684\u5f71\u54cd\u3002\u901a\u8fc7\u5bf9\u6bd4\u53d1\u73b0\u3001\u53d6\u4ee3\u57fa\u4e3a\u5438\u7535\u5b50\u57fa\u56e2\uff0c\u7279\u522b\u662f\u57283,5-\u53d6\u4ee3\u7684\u8bdd\u90fd\u5f97\u5230\u4e86\u975e\u5e38\u597d\u7684\u7ed3\u679c\u3002\u540c\u65f6\u7528\u2461\u4e2d\u7684\u65b9\u6cd5\uff0c\u5bf9\u591a\u53d8\u91cf\u7684\u8981\u7d20\u8fdb\u884c\u89e3\u6790\u540e\u53d1\u73b02,6\u4f4d\u6c22\u539f\u5b50\u7684\u7f3a\u7535\u6027\u4e0e\u9009\u62e9\u6027\u7684\u9ad8\u4f4e\u5177\u6709\u76f4\u63a5\u7684\u76f8\u5173\u6027\u3002<\/p>\n

    \u82c4\u57fa\u4e0e\u53cd\u5e94\u4f4d\u70b9\u8ddd\u79bb\u6bd4\u8f83\u8fdc\uff0c\u6240\u4ee5CAPT\u4e0a\u76849-\u84bd\u57fa\u4e0e\u5e95\u7269\u7684\u82c4\u57fa\u95f4\u5b58\u5728\u7684\u975e\u5171\u4ef7\u952e\u7ed3\u5408\u7684\u76f8\u4e92\u4f5c\u7528\uff0c\u4e5f\u662f\u5bf9\u624b\u6027\u9009\u62e9\u6027\u7684\u63d0\u9ad8\u5177\u6709\u91cd\u8981\u8d21\u732e\u7684\u3002<\/p>\n

    \"\"<\/p>\n

    \u2463\u5e95\u7269\u62d3\u5c55<\/b><\/h5>\n

    3,5-\u6c2f\u82ef\u4e19\u70ef\u9178\u916f\u4f5c\u4e3a\u5e95\u7269\uff0c\u8fdb\u884c\u4e86\u5404\u79cd\u4e8c\u82b3\u57fa\u5316\u53cd\u5e94\u7684\u5e95\u7269\u62d3\u5c55\uff08\u4e0b\u56fe\u6240\u793a\uff09\u3002\u4e0d\u7ba1\u662f\u5bcc\u7535\u5b50\u30fb\u7f3a\u7535\u5b50\u7684\u82b3\u9999\u73af\uff0c\u53cd\u5e94\u90fd\u80fd\u8fdb\u884c\uff0c\u7136\u800c\uff0c\u7f3a\u7535\u5b50\u7684\u82b3\u9999\u5316\u7684\u60c5\u51b5\uff0c\u5176\u624b\u6027\u9009\u62e9\u6027\u7a0d\u5fae\u6bd4\u8f83\u4f4e\u3002\u53e6\u5916\u5bf9\u4e8e\u82b3\u9999\u57fa\u787c\u9178\u53cd\u5e94\u8bd5\u5242\u6765\u8bf4\uff0c\u53ea\u6709\u542b\u6709\u5bcc\u7535\u5b50\u7684\u82b3\u9999\u73af\u7684\u624d\u80fd\u53c2\u4e0e\u53cd\u5e94\u3002\u8fd9\u662f\u56e0\u4e3a\u8be5\u4e8c\u82b3\u57fa\u5316\u4e0eHeck\u53cd\u5e94\u6709\u4e00\u4e2a\u7ade\u4e89\u6027\u7684\u7f18\u6545\u3002\u56e0\u6b64\uff0cPd\u4e0e\u787c\u9178\u95f4\u7684transmetallization\u8fd9\u4e00\u6b65\u9700\u8981\u7684\u53cd\u5e94\u5e95\u7269\u5fc5\u987b\u662f\u975e\u5e38\u5feb\u7684\u3002\u53e6\u5916\u787c\u9178\u4e0e\u78f7\u9178\u7684\u76f4\u63a5\u76f8\u4e92\u4f5c\u7528\u4e5f\u662f\u5bfc\u81f4transmetallization\u6bd4\u8f83\u96be\u53d1\u751f\u7684\u4e00\u4e2a\u539f\u56e0\u3002<\/p>\n

    \"\"<\/p>\n

    \u8fd8\u9700\u8981\u6ce8\u610f\u7684\u70b9<\/h4>\n