\u201c\u787c\u201d\u6709\u201c\u9502\u201d<\/strong><\/a>\uff0c\u624b\u6027\u4e8c\u7ea7\u70f7\u57fa\u950c\u8bd5\u5242\u7684\u5408\u6210\u53ca\u5e94\u7528<\/p>\n\u5bf9\u6620\u4f53\u5bcc\u96c6\u7684\u70f7\u57fa\u787c\u9178\u916f\u662f\u6709\u673a\u5408\u6210\u4e2d\u4e00\u79cd\u5177\u6709\u4ef7\u503c\u7684\u780c\u5757\u3002\u5b83\u4eec\u901a\u5e38\u5728\u5316\u5b66\u548c\u6784\u578b\u4e0a\u662f\u7a33\u5b9a\u7684\uff0c\u5e76\u53ef\u901a\u8fc7\u5404\u79cd\u50ac\u5316\u548c\u975e\u50ac\u5316\u65b9\u6cd5\u8fdb\u884c\u5236\u5907\u3002\u6b64\u5916\uff0c\u70f7\u57fa\u787c\u9178\u916f\u7ecf\u7acb\u4f53\u4e13\u4e00\u6027\u8f6c\u5316\uff0c\u53ef\u7528\u4e8e\u6784\u5efa\u4e00\u7cfb\u5217\u975e\u5916\u6d88\u65cb\u7684\u624b\u6027\u5316\u5408\u7269\u3002\u7136\u800c\uff0c\u4e0e\u5176\u5b83\u6709\u673a\u91d1\u5c5e\u5316\u5408\u7269\u76f8\u6bd4\uff0c\u70f7\u57fa\u787c\u9178\u916f\u662f\u5f31\u4eb2\u6838\u8bd5\u5242\uff0c\u5176\u53c2\u4e0e\u8f6c\u91d1\u5c5e\u5316\u65f6\u7684\u53cd\u5e94\u6027\u8f83\u4f4e\u3002\u76f8\u5bf9\u4e8e\u70f7\u57fa\u787c\u9178\u916f\uff0c\u6709\u673a\u950c\u8bd5\u5242\u66f4\u5177\u4eb2\u6838\u6027\uff0c\u5e76\u5728\u6784\u578b\u4e0a\u7a33\u5b9a\u30022000\u5e74\uff0cKnochel\u8bfe\u9898\u7ec4\uff08Angew. Chem., Int. Ed. 2000, 39, 4414.\uff09\u9996\u6b21\u62a5\u9053\u4e86\u4e8c\u7ea7\u70f7\u57fa\u950c\u8bd5\u5242\u53ef\u4e0e\u94dc\u548c\u94af\u8fdb\u884c\u7acb\u4f53\u4e13\u4e00\u6027\u8f6c\u91d1\u5c5e\u5316\uff08stereospecific transmetalation\uff09\u540e\uff0c\u518d\u4e0e\u4eb2\u7535\u8bd5\u5242\u8fdb\u884c\u5076\u8054\u53cd\u5e94\u3002\u76ee\u524d\uff0c\u867d\u7136\u5316\u5b66\u5bb6\u4eec\u5df2\u5f00\u53d1\u4e00\u7cfb\u5217\u5bf9\u6620\u9009\u62e9\u6027\u5408\u6210\u03b1-\u6c28\u57fa\u3001\u03b1-\u787c\u57fa\u548c\u73af\u4e19\u57fa\u53d6\u4ee3\u7684\u6709\u673a\u950c\u8bd5\u5242\u7684\u6709\u6548\u7b56\u7565\uff0c\u4f46\u5bf9\u4e8e\u5bf9\u6620\u4f53\u5bcc\u96c6\u7684\u4e8c\u7ea7\u70f7\u57fa\u950c\u5316\u5408\u7269\u7684\u5408\u6210\u4ecd\u5177\u6709\u6311\u6218\u3002\u4e0b\u8f7d\u5316\u5b66\u52a0APP\u5230\u4f60\u624b\u673a\uff0c\u66f4\u52a0\u65b9\u4fbf\uff0c\u66f4\u591a\u6536\u83b7\u3002<\/p>\n
1998\u5e74\uff0cKnochel\u8bfe\u9898\u7ec4\uff08Synlett 1998, 1998, 1438.\uff09\u62a5\u9053\u4e86\u4e00\u79cd\u7531\u70ef\u70c3\u787c\u6c22\u5316\u751f\u6210\u7684\u4e8c\u7ea7\u6709\u673a\u787c\u70f7\u53ef\u4e0e\u4e8c\u5f02\u4e19\u57fa\u950c\u8fdb\u884c\u7acb\u4f53\u4e13\u4e00\u6027\u8f6c\u91d1\u5c5e\u5316\uff0c\u8fdb\u800c\u5408\u6210\u4e86\u03b1-\u624b\u6027\u6709\u673a\u950c\u8bd5\u5242\uff08Scheme 1a\uff09\u30022020\u5e74\uff0cKnochel\u8bfe\u9898\u7ec4\uff08Angew. Chem., Int. Ed. 2020, 59, 320.\uff09\u62a5\u9053\u4e86\u4e00\u79cd\u7acb\u4f53\u4e13\u4e00\u6027\u9502\u2212\u7898\u4ea4\u6362\u53cd\u5e94\uff0c\u968f\u540e\u4f7f\u7528TMSCH2ZnCl\u00b7LiBr\u5904\u7406\uff0c\u751f\u6210\u76f8\u5e94\u7684\u6709\u673a\u950c\u8bd5\u5242\uff08Scheme 1b\uff09\u30022017\u5e74\uff0cIngleson\u8bfe\u9898\u7ec4\uff08Chem. Eur. J. 2017, 23, 15889.\uff09\u62a5\u9053\u4e86\u4e00\u79cd\u5229\u7528PhB(pin)\u00b7t-BuLi\u52a0\u5408\u7269\u4e0e\u6eb4\u5316\u950c\u751f\u6210\u4e8c\u82ef\u57fa\u950c\u7684\u7b56\u7565\uff08Scheme 1c\uff09\u3002\u8fd1\u65e5\uff0c\u7f8e\u56fd\u6ce2\u58eb\u987f\u5b66\u9662James P. Morken\u8bfe\u9898\u7ec4\u62a5\u9053\u4e86\u4e00\u79cd\u5229\u7528tBuLi\u5b9e\u73b0\u624b\u6027\u4e8c\u7ea7\u6709\u673a\u787c\u9178\u916f\u7684\u6d3b\u5316\uff0c\u8fdb\u800c\u53ef\u4e0e\u4e59\u9178\u950c\u6216\u6c2f\u5316\u950c\u8fdb\u884c\u7acb\u4f53\u4fdd\u7559\u7684\u8f6c\u91d1\u5c5e\u5316\u53cd\u5e94\uff0c\u5408\u6210\u4e86\u4e00\u7cfb\u5217\u624b\u6027\u4e8c\u7ea7\u70f7\u57fa\u950c\u8bd5\u5242\uff08Scheme 1d\uff09\u3002<\/p>\n
\u9996\u5148\uff0c\u4f5c\u8005\u4ee5\u787c\u9178\u916f\u884d\u751f\u72691\u4f5c\u4e3a\u6a21\u578b\u5e95\u7269\uff0c\u8fdb\u884c\u4e86\u76f8\u5173\u53cd\u5e94\u6761\u4ef6\u7684\u7b5b\u9009\uff08Table 1\uff09\u3002\u5f53\u4f7f\u7528tBuLi\uff081.0 eq.\uff09\u5bf9\u624b\u6027\u4e8c\u7ea7\u6709\u673a\u787c\u9178\u916f\u8fdb\u884c\u6d3b\u5316\u540e\uff0c\u518d\u4e0eZn(OAc)2\uff081.05 eq.\uff09\u8fdb\u884c\u7acb\u4f53\u4e13\u4e00\u6027\u8f6c\u91d1\u5c5e\u5316\u53cd\u5e94\uff0c\u53ef\u751f\u6210\u624b\u6027\u4e8c\u7ea7\u70f7\u57fa\u950c\u8bd5\u5242\u3002\u968f\u540e\uff0c\u5f53\u4ee5[Pd-G3]\uff080.5 mol%\uff09\u4f5c\u4e3a\u50ac\u5316\u5242\uff0cCPhos\uff082.0 mol%\uff09\u4f5c\u4e3a\u914d\u4f53\uff0cLiCl\uff081.05 eq.\uff09\u4f5c\u4e3a\u6dfb\u52a0\u5242\uff0c\u70f7\u57fa\u950c\u8bd5\u5242\u53ef\u4e0eArBr\uff081.20 eq.\uff09\u5728THF\/\u7532\u82ef\u6df7\u5408\u6eb6\u5242\u4e2d\u5ba4\u6e29\u53cd\u5e9412 h\uff0c\u53ef\u4ee582%\u7684\u6536\u7387\u5f97\u5230\u4ea7\u72692\uff0cer\u4e3a95:5\uff0ces\u4e3a98%\u3002<\/p>\n
<\/p>\n
\u5176\u6b21\uff0c\u4f5c\u8005\u901a\u8fc7\u539f\u4f4d11B\u548c13C NMR\u5bf9B-to-Zn\u8f6c\u91d1\u5c5e\u5316\u7684\u53cd\u5e94\u6027\u548c\u7acb\u4f53\u4e13\u4e00\u6027\u8fdb\u884c\u4e86\u7814\u7a76\uff08Figure 1\uff09\u3002\u7814\u7a76\u7ed3\u679c\u8868\u660e\uff0c\u4f7f\u7528\u4e59\u9178\u950c\u6216\u6c2f\u5316\u950c\u65f6\uff0c\u53cd\u5e94\u5177\u6709\u7acb\u4f53\u4e13\u4e00\u6027\u3002\u540c\u65f6\uff0c\u5916\u6d88\u65cb\u4f5c\u7528\u53ef\u80fd\u53d1\u751f\u5728\u950c\u5230\u94af\u7684\u8f6c\u91d1\u5c5e\u5316\u8fc7\u7a0b\u4e2d\u3002\u5e76\u4e14\uff0c\u70f7\u57fa\u950c\u914d\u5408\u7269\u672c\u8eab\u5728\u6784\u578b\u4e0a\u662f\u7a33\u5b9a\u7684\u3002<\/p>\n
\u5728\u83b7\u5f97\u4e0a\u8ff0\u6700\u4f73\u53cd\u5e94\u6761\u4ef6\u540e\uff0c\u4f5c\u8005\u5bf9\u4eb2\u7535\u8bd5\u5242\u7684\u5e95\u7269\u8303\u56f4\u8fdb\u884c\u4e86\u6269\u5c55\uff08Figure 2\uff09\u3002\u7814\u7a76\u8868\u660e\uff0c\u4e00\u7cfb\u5217\u82b3\u57fa\u5364\u3001\u6742\u82b3\u57fa\u5364\u4ee5\u53ca\u70ef\u57fa\u5364\uff0c\u5747\u53ef\u987a\u5229\u8fdb\u884c\u53cd\u5e94\uff0c\u83b7\u5f97\u76f8\u5e94\u7684\u4ea7\u72692-16\uff0c\u6536\u7387\u4e3a40-78%\uff0cer\u4e3a91:9-96:4\uff0ces\u4e3a91->98%\u3002<\/p>\n
\u540c\u65f6\uff0c\u901a\u8fc7\u5bf9\u53cd\u5e94\u6761\u4ef6\u7684\u4f18\u5316\u540e\uff0c\u6709\u673a\u950c\u8bd5\u5242\u53ef\u5148\u4e0e\u4e8c\u6c1f\u5361\u5bbe\u53cd\u5e94\uff0c\u968f\u540e\u7ecf\u8fdb\u4e00\u6b65\u7684\u7898\u89e3\u540e\uff0c\u53ef\u83b7\u5f97\u4e8c\u6c1f\u7898\u7532\u57fa\u884d\u751f\u7269\uff08Figure 3\uff09\u3002\u5e95\u7269\u7b5b\u9009\u7ed3\u679c\u8868\u660e\uff0c\u4e00\u7cfb\u5217\u4e8c\u7ea7\u6709\u673a\u787c\u9178\u916f\uff0c\u5747\u53ef\u987a\u5229\u8fdb\u884c\u53cd\u5e94\uff0c\u83b7\u5f97\u76f8\u5e94\u7684\u4ea7\u726917-26\uff0c\u6536\u7387\u4e3a38-93%\uff0cer\u4e3a92:8-97:3\uff0ces\u4e3a93->98%\u3002\u5176\u6b21\uff0cNBS\u6216HOAc\u4e5f\u53ef\u4f5c\u4e3a\u6355\u83b7\u8bd5\u5242\uff0c\u83b7\u5f97\u76f8\u5e94\u7684\u4ea7\u726927\u548c29-32\uff0c\u6536\u7387\u4e3a37-63%\uff0cer\u4e3a92:8-97:3\uff0ces\u4e3a93->98%\u3002\u6b64\u5916\uff0c\u4e8c\u6c1f\u7532\u57fa\u950c\u4e2d\u95f4\u4f53\u4e5f\u53ef\u4ee5\u8fdb\u884c\u94dc\u50ac\u5316\u7684\u70ef\u4e19\u57fa\u5316\u53cd\u5e94\uff0c\u53ef\u4ee538%\u7684\u6536\u7387\u5f97\u5230\u4ea7\u726928\uff0cer\u4e3a92:8\uff0ces\u4e3a93%\u3002<\/p>\n
\u6b64\u5916\uff0c\u6709\u673a\u950c\u8bd5\u5242\u8fd8\u53ef\u4e0ePyCu(CF3)3\u8fdb\u884c\u4e09\u6c1f\u7532\u57fa\u5316\u53cd\u5e94\uff0c\u83b7\u5f97\u4e00\u7cfb\u5217\u5bf9\u6620\u4f53\u5bcc\u96c6\u4e14\u542b\u6709\u4e09\u6c1f\u7532\u57fa\u5355\u5143\u7684\u4ea7\u726933-36\uff0c\u6536\u7387\u4e3a28-70%\u3002\u540c\u65f6\uff0c\u53cd\u5e94\u4ee5\u7acb\u4f53\u4fdd\u7559\u7684\u65b9\u5f0f\u8fdb\u884c\uff08Figure 4\uff09\u3002<\/p>\n
\u7d27\u63a5\u7740\uff0c\u4f5c\u8005\u63d0\u51fa\u4e86\u51e0\u79cd\u53ef\u80fd\u6d89\u53ca\u53c2\u4e0eR-B(pin)\u00b7t-BuLi\u548cZn(OAc)2\u8f6c\u91d1\u5c5e\u5316\u8fc7\u7a0b\u4e2d\u7684\u5408\u7406\u914d\u5408\u7269\uff0c\u5373A-C\uff08Figure 5\uff09\u3002<\/p>\n
<\/p>\n
\u6700\u540e\uff0c\u4f5c\u8005\u5bf9\u787c-\u950c\u8f6c\u91d1\u5c5e\u5316\u8fc7\u7a0b\u4e2d\u53ef\u80fd\u7684\u4e2d\u95f4\u4f53\u8fdb\u884c\u4e86\u7814\u7a76\uff08Figure 6\uff09\u3002\u7814\u7a76\u7ed3\u679c\u8868\u660e\uff0c\u4e09\u914d\u4f4d\u787c\u9178\u916f\u5728\u8f6c\u91d1\u5c5e\u5316\u8fc7\u7a0b\u4e2d\u662f\u53ef\u80fd\u7684\u4e2d\u95f4\u4f53\uff0c\u4f46\u5e76\u6ca1\u6709\u4e25\u683c\u786e\u5b9a\u8fd9\u4e9b\u914d\u5408\u7269\u672c\u8eab\u662f\u5426\u53c2\u4e0e\u4e86\u8f6c\u5316\u672c\u8eab\uff0c\u6216\u8005\u5b83\u4eec\u662f\u5426\u662f\u53cd\u5e94\u6027\u56db\u914d\u4f4d\u787c\u9178\u916f\u7684\u975e\u5faa\u73af\u524d\u4f53\uff08progenitors\uff09\u3002<\/p>\n
<\/p>\n
\u4e3a\u4e86\u4e86\u89e3\u56db\u914d\u4f4d\u6216\u4e09\u914d\u4f4d\u6709\u673a\u787c\u5316\u5408\u7269\u662f\u5426\u66f4\u6709\u53ef\u80fd\u53d1\u751f\u8f6c\u91d1\u5c5e\u5316\uff0c\u4f5c\u8005\u5bf9\u7fa7\u9178\u950c\u548c\u6c2f\u5316\u950c\u7684\u8fc7\u7a0b\u8fdb\u884c\u4e86DFT\u8ba1\u7b97\uff08Figure 7\uff09\u3002\u867d\u7136\u4e09\u914d\u4f4d\u787c\u914d\u5408\u7269\u7684\u8f6c\u91d1\u5c5e\u5316\u7684\u80fd\u91cf\u66f4\u9ad8\uff0c\u4f46\u56db\u914d\u4f4d\u787c\u9178\u916f\u7684\u8f6c\u91d1\u5c5e\u5316\u4f3c\u4e4e\u5f88\u5bb9\u6613\u83b7\u5f97\uff0c\u4ece\u800c\u8868\u660e\u8fd9\u53ef\u80fd\u662f\u6709\u6548\u7684\u9014\u5f84\u3002<\/p>\n
\u603b\u7ed3<\/p>\n
\u7f8e\u56fd\u6ce2\u58eb\u987f\u5b66\u9662James P. Morken\u8bfe\u9898\u7ec4\u5229\u7528tBuLi\u5b9e\u73b0\u4e86\u624b\u6027\u4e8c\u7ea7\u6709\u673a\u787c\u9178\u916f\u7684\u6d3b\u5316\uff0c\u8fdb\u800c\u53ef\u4e0e\u4e59\u9178\u950c\u6216\u6c2f\u5316\u950c\u8fdb\u884c\u7acb\u4f53\u4fdd\u7559\u7684\u8f6c\u91d1\u5c5e\u5316\u53cd\u5e94\uff0c\u53ef\u9ad8\u6548\u5408\u6210\u4e00\u7cfb\u5217\u6784\u578b\u7a33\u5b9a\u7684\u624b\u6027\u4e8c\u7ea7\u70f7\u57fa\u950c\u8bd5\u5242\u3002\u540c\u65f6\uff0c\u6709\u673a\u950c\u8bd5\u5242\u53ef\u5206\u522b\u4e0e\u4e8c\u6c1f\u5361\u5bbe\u8fdb\u884c\u7acb\u4f53\u4e13\u4e00\u6027\u53cd\u5e94\uff0c\u4e0e\u94af\u57fa\u50ac\u5316\u5242\u8fdb\u884c\u50ac\u5316\u4ea4\u53c9\u5076\u8054\u53cd\u5e94\uff0c\u5e76\u4e0e\u94dc(III)\u914d\u5408\u7269\u8fdb\u884c\u4e09\u6c1f\u7532\u57fa\u5316\u53cd\u5e94\u3002\u503c\u5f97\u6ce8\u610f\u7684\u662f\uff0c\u4e0a\u8ff0\u7ed3\u679c\u8868\u660e\uff0c\u6709\u673a\u950c\u8bd5\u5242\u53ef\u6709\u6548\u7684\u8fdb\u884c\u7acb\u4f53\u4e13\u4e00\u6027\u8f6c\u5316\u3002\u521d\u6b65\u7684\u673a\u7406\u7814\u7a76\u8868\u660e\uff0c\u70f7\u57fa\u5411\u950c\u7684\u7acb\u4f53\u4e13\u4e00\u6027\u8f6c\u79fb\u53d1\u751f\u5728\u56db\u914d\u4f4d\u787c\u9178\u916f\u914d\u5408\u7269\u4e2d\u3002\u6b64\u5916\uff0c\u8be5\u5de5\u827a\u53ef\u80fd\u6709\u52a9\u4e8e\u5236\u5907\u5bf9\u6620\u4f53\u5bcc\u96c6\u7684\u6709\u673a\u950c\u8bd5\u5242\uff0c\u5e76\u6269\u5927\u70f7\u57fa\u787c\u9178\u916f\u7684\u5e94\u7528\u8303\u56f4\u3002<\/p>\n","protected":false},"excerpt":{"rendered":"
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