{"id":31440,"date":"2020-04-17T08:08:26","date_gmt":"2020-04-17T00:08:26","guid":{"rendered":"\/\/www.gsbet888.com\/?p=31440"},"modified":"2020-04-14T15:40:03","modified_gmt":"2020-04-14T07:40:03","slug":"%e5%8f%8c%e6%b0%a2%e9%94%ae%e5%82%ac%e5%8c%96%e5%89%82%e6%89%8b%e6%80%a7%e8%84%b2%e5%82%ac%e5%8c%96%e5%af%b9%e6%98%a0%e9%80%89%e6%8b%a9%e6%80%a7%e5%b0%be-%e5%a4%b4%e7%8e%af%e5%8c%96%e5%8f%8d","status":"publish","type":"post","link":"\/\/www.gsbet888.com\/%e5%8c%96%e5%ad%a6%e6%9d%82%e8%ae%b0\/recentpaper\/2020\/04\/%e5%8f%8c%e6%b0%a2%e9%94%ae%e5%82%ac%e5%8c%96%e5%89%82%e6%89%8b%e6%80%a7%e8%84%b2%e5%82%ac%e5%8c%96%e5%af%b9%e6%98%a0%e9%80%89%e6%8b%a9%e6%80%a7%e5%b0%be-%e5%a4%b4%e7%8e%af%e5%8c%96%e5%8f%8d.html","title":{"rendered":"\u53cc\u6c22\u952e\u50ac\u5316\u5242(\u624b\u6027\u8132)\u50ac\u5316\u5bf9\u6620\u9009\u62e9\u6027\u5c3e-\u5934\u73af\u5316\u53cd\u5e94"},"content":{"rendered":"

\u672c\u6587\u4f5c\u8005\uff1aalberto-caeiro<\/p>\n

\u5bfc\u8bfb<\/strong><\/h4>\n

Jacobsen\u8bfe\u9898\u7ec4\u62a5\u9053\u4e86\u624b\u6027\u8132\u50ac\u5316\u5242\u50ac\u5316neryl chloride\u884d\u751f\u7269\u7684\u624b\u6027\u5c3e-\u5934\u73af\u5316\u53cd\u5e94\u3002\u5b9e\u9a8c\u8868\u660e\u8fdc\u7aef\u7684\u70ef\u70c3\u5728\u6c2f\u79bb\u5b50\u79bb\u53bb\u4e2d\u8d77\u5230\u4e86\u4f5c\u7528\uff0c\u5e76\u6291\u5236\u4e86\u6d88\u9664\u53cd\u5e94\uff0c\u5e76\u5bf9\u53cd\u5e94\u901f\u7387\u548c\u5bf9\u6620\u9009\u62e9\u6027\u6709\u8d21\u732e\u3002\u52a8\u529b\u5b66\u5b9e\u9a8c\u548cDFT\u8ba1\u7b97\u90fd\u8868\u660e\u8be5\u53cd\u5e94\u4e2d\u6709\u4e24\u5206\u5b50\u7684\u624b\u6027\u8132\u50ac\u5316\u5242\uff0c\u5e76\u901a\u8fc7\u8fc7\u6e21\u6001\u7684\u9009\u62e9\u6027\u7a33\u5b9a\u4f5c\u7528\u5b9e\u73b0\u4e86\u53cd\u5e94\u7684\u5bf9\u6620\u9009\u62e9\u6027\u3002<\/p>\n

\u201cEnantioselective Tail-to-Head Cyclizations Catalyzed by Dual-Hydrogen-Bond Donors\u201d<\/em><\/strong><\/p>\n

Dennis A. Kutateladze, Daniel A. Strassfeld and Eric N. Jacobsen* J. Am. Chem. Soc.<\/em> 2020<\/strong>. DOI: 10.1021\/jacs.0c02665<\/a>.<\/p><\/blockquote>\n

\u8bba\u6587\u4ecb\u7ecd<\/strong><\/h4>\n

\u841c\u7c7b\u548c\u7c7b\u841c\u5316\u5408\u7269\u662f\u4e00\u7c7b\u91cd\u8981\u7684\u5929\u7136\u4ea7\u7269\uff0c\u4ed6\u4eec\u5728\u81ea\u7136\u754c\u4e2d\u901a\u5e38\u662f\u4ee5\u5f02\u620a\u4e8c\u70ef\u4e3a\u539f\u6599\uff0c\u7ecf\u841c\u70ef\u73af\u5316\u9176\u50ac\u5316\u5408\u6210\u7684\u3002\u5728\u8fd9\u4e9b\u591a\u70ef\u73af\u5316\u4e2d\uff0c\u6709\u4e24\u79cd\u5408\u6210\u6a21\u5f0f(Figure 1A)\uff1a\uff081\uff09\u901a\u8fc7\u70ef\u70c3\u8d28\u5b50\u5316\u5b9e\u73b0\u7684\u5934-\u5c3e\u73af\u5316(Head to tail HT)\uff1b\uff082\uff09\u901a\u8fc7\u70ef\u4e19\u57fa\u7126\u78f7\u9178\u916f\u79bb\u53bb\u5b9e\u73b0\u7684\u5c3e-\u5934\u73af\u5316(Tail to head TH)\u3002\u5e95\u7269\u9884\u7ec4\u7ec7\u548c\u9176\u6d3b\u6027\u4f4d\u70b9\u4e2d\u7684\u975e\u5171\u4ef7\u7a33\u5b9a\u76f8\u4e92\u4f5c\u7528\u53ef\u7528\u6765\u8c03\u8282\u6240\u5f97\u78b3\u6b63\u79bb\u5b50\u4e2d\u95f4\u4f53\u7684\u53cd\u5e94\u6027\uff0c\u4ece\u800c\u5b9e\u73b0\u9009\u62e9\u6027\u91cd\u6392\u548cC-C\u952e\u751f\u6210\uff0c\u6700\u7ec8\u4ea7\u751f\u5404\u6837\u7684\u5929\u7136\u4ea7\u7269(Figure 1B)\u3002<\/p>\n

Jacobsen\u6559\u6388\u8bbe\u60f3\u901a\u8fc7\u4f7f\u7528\u5c0f\u5206\u5b50\u50ac\u5316\u5242\u6a21\u62df\u9176\u5728\u53cd\u5e94\u4e2d\u5bf9\u78b3\u6b63\u79bb\u5b50\u4e2d\u95f4\u4f53\u53cd\u5e94\u6027\u7684\u8c03\u8282\u5b9e\u73b0\u5c3e-\u5934\u73af\u5316\u53cd\u5e94\u3002\u5177\u6709\u4e24\u4e2a\u6c22\u952e\u7684\u624b\u6027\u8132\u50ac\u5316\u5242\u5df2\u88ab\u8bc1\u5b9e\u53ef\u5bf9\u901a\u8fc7\u79bb\u53bb\u79bb\u5b50\u7684\u652b\u53d6\u4ea7\u751f\u7684\u78b3\u6b63\u79bb\u5b50\u6709\u826f\u597d\u7684\u624b\u6027\u63a7\u5236[1]<\/sup>\uff0c\u4e14\u5177\u6709\u7c7b\u4f3c\u9176\u7684\u975e\u5171\u4ef7\u7a33\u5b9a\u78b3\u6b63\u79bb\u5b50\u7684\u80fd\u529b\u3002\u5728\u6b64\uff0cJacobsen\u6559\u6388\u5b9e\u73b0\u4e86\u624b\u6027\u8132\u50ac\u5316neryl chloride\u884d\u751f\u7269\u5bf9\u6620\u9009\u62e9\u6027\u5c3e-\u5934\u73af\u5316\u53cd\u5e94(Figure 1C)\u3002<\/p>\n

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

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

Figure 1. (A) Head-to-tail and tail-to-head cyclization reactions. (B) Schematic illustrating Nature\u2019s strategy for controlled ionization-dependent cyclizations. (C) Proposed strategy for enantioselective tail-to-head cyclizations catalyzed by chiral hydrogen-bond donors.<\/em><\/p>\n

\u70ef\u70c3\u7684\u987a\u53cd\u5bf9\u53cd\u5e94\u6709\u5de8\u5927\u7684\u5f71\u54cd\u3002\u53cd\u5f0f\u70ef\u70c3geranyl chloride\u5728\u6807\u51c6\u6761\u4ef6\u4e0b\u53cd\u5e94\u5f88\u6162\uff0c\u4e14\u76f8\u5f53\u4e00\u90e8\u5206\u53d1\u751f\u6d88\u9664\u800c\u975e\u73af\u5316\u4ea7\u7269(Figure 2)\u3002\u800c\u4f7f\u7528\u987a\u5f0f\u70ef\u70c3neryl chloride(1a)\u65f6\uff0c\u76f8\u540c\u6761\u4ef6\u4e0b\u53cd\u5e94\u670988%\u7684\u8f6c\u5316\uff0c\u4e14\u7edd\u5927\u90e8\u5206\u4e3a\u73af\u5316\u4ea7\u7269\u3002\u5f53\u4f7f\u7528\u624b\u6027\u8132\u50ac\u5316\u8be5\u53cd\u5e94\u65f6\uff0c\u5728\u5bf9\u624b\u6027\u50ac\u5316\u5242\u8fdb\u884c\u5e7f\u6cdb\u7b5b\u9009\u540e(see SI for details<\/a>)\uff0c\u6700\u597d\u7684\u7ed3\u679c\u4ecd\u53ea\u670934% ee\u503c\u3002<\/p>\n

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

Figure 2. Differing reactivity observed in the urea-catalyzed cyclization of E and Z isomers. Conversions and yields were assessed from crude reaction mixtures using 1<\/sup>H-NMR with mesitylene as an internal quantitative standard.<\/em><\/p>\n

\u8003\u8651\u52301a\u5728\u4e0d\u5bf9\u79f0\u53cd\u5e94\u4e2d\u662f\u5f88\u96be\u7684\u5e95\u7269\uff0c\u4e8e\u662f\u4ed6\u4eec\u5c06C-3\u4f4d\u6362\u4e3a\u82ef\u57fa\u8fdb\u884c\u540e\u7eed\u7814\u7a76\u3002\u5bf9\u4e8e\u5e95\u72691b\uff0c\u8be5\u53cd\u5e94\u80fd\u670963%\u7684NMR\u6536\u7387\u548c87% ee\u503c\uff0c\u53e6\u4e00\u624b\u6027\u73af\u5316\u4ea7\u72693b\u5219\u670920%\u6536\u7387\uff0c86% ee\u503c\uff0c\u7c7b\u4f3c\u7684ee\u503c\u4e0e\u540c\u4e00\u53cd\u5e94\u8fc7\u6e21\u6001\u6709\u5173\u3002\u975e\u624b\u6027\u73af\u5316\u4ea7\u72694b\u548c5b\u7684\u6536\u7387\u5206\u522b\u662f12%\u548c5%\uff0c\u5176\u4e2d5b\u662f\u8fc7\u6e21\u6001\u7ecf[1,2]-H\u8fc1\u79fb\u540e\u6d88\u9664\u5f97\u5230\u3002\u4f46\u4f7f\u7528\u987a\u5f0f\u70ef\u70c32b\u65f6\uff0c\u53cd\u5e94\u901f\u7387\u5219\u53d8\u6162\uff0824 h, 7% conv.\uff09\uff0c\u4e14\u53ea\u670950% ee\u503c\u3002<\/p>\n

\u5e95\u7269\u8303\u56f4\u4e2d(Figure 3)\uff0c\u5438\u7535\u5b50\u82b3\u73af\u76f8\u8f83\u4e8e\u7ed9\u7535\u5b50\u82b3\u73af\u6709\u66f4\u597d\u7684\u53cd\u5e94\u6027\u548c\u624b\u6027\u63a7\u5236\uff0c\u90bb\u4f4d\u6709\u53d6\u4ee3\u57fa\u65f6\u5bf9\u53cd\u5e94\u6027\u548c\u5bf9\u6620\u9009\u62e9\u6027\u4e5f\u6709\u63d0\u9ad8\u3002\u800c\u4f7f\u7528\u73af\u5df1\u70f7\u4f5c\u4e3a\u53d6\u4ee3\u57fa\u65f6\uff0c\u53cd\u5e94\u6027\u548c\u5bf9\u6620\u9009\u62e9\u6027\u8f83\u7532\u57fa\u65f6\u6709\u660e\u663e\u7684\u63d0\u9ad8\u3002\u8fd9\u4e9b\u8bf4\u660e\u53d6\u4ee3\u57fa\u4f4d\u963b\u548c\u7535\u6027\u5bf9\u53cd\u5e94\u90fd\u6709\u5f71\u54cd\u3002<\/p>\n

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

Figure 3. Substrate scope. All reactions were performed on 0.15 mmol scale and proceeded to complete conversion. The ee values are for products 2a-i. Alkyl chlorides 3b, 3h, and 3i were generated in 86% ee, 91% ee, and 70% ee, respectively.<\/em><\/p>\n

\u5728KIE\u5b9e\u9a8c\u4e2d(Figure 4A)\uff0ckH<\/sub><\/em>\/kD<\/sub><\/em> = 0.944(3)\u3002\u6b64\u76f8\u53cd\u7684\u4e8c\u7ea7\u540c\u4f4d\u7d20\u6548\u5e94\u503c\u8868\u660e\u8fdc\u7aef\u70ef\u70c3\u53c2\u4e0e\u5230\u51b3\u901f\u6b65\u30020.944\u7684\u6570\u503c\u53ef\u80fd\u662f\u7531\u8fc7\u6e21\u6001\u4e2d\u70ef\u70c3\u5df2\u7ecf\u90e8\u5206\u7531sp2\u6742\u5316\u81f3sp3\uff0cC-C\u952e\u4e5f\u90e8\u5206\u5f62\u6210\u3002\u9633\u79bb\u5b50\u53d6\u4ee3\u57fa\u6548\u5e94\u7684\u5b9e\u9a8c\u4e2d(Figure 4B)\uff0c\u03c1=-1.3\u8868\u660e\u53cd\u5e94\u7ecf\u8fc7\u4e86\u78b3\u6b63\u79bb\u5b50\u8fc7\u6e21\u6001\u3002\u5728\u52a8\u529b\u5b66\u5206\u6790\u4e2d\uff0c\u53cd\u5e94\u5bf9\u5e95\u7269\u662f\u4e00\u7ea7\u53cd\u5e94\uff0c\u5bf9\u78b1\u662f\u96f6\u7ea7\u53cd\u5e94\uff0c\u800c\u5bf9\u50ac\u5316\u5242\u662f1.17\uff0c\u8fd9\u8bf4\u660e\u53cd\u5e94\u8fc7\u6e21\u6001\u4e2d\u50ac\u5316\u6d3b\u6027\u7269\u79cd\u662f\u624b\u6027\u8132\u7684\u5355\u4f53\u548c\u4e8c\u805a\u4f53\u7684\u590d\u5408\u7269\u3002\u542b\u6709\u4e24\u4e2a\u6c22\u952e\u7684\u624b\u6027\u8132\u5728\u6db2\u76f8\u548c\u56fa\u76f8\u90fd\u53ef\u4ee5\u4e8c\u805a\u5f62\u5f0f\u5b58\u5728\uff0c\u8be5\u53cd\u5e94\u4e2d\u4e5f\u662f\u5982\u6b64(see SI for details)\u3002<\/p>\n

\u6839\u636e\u5df2\u6709\u4fe1\u606f\uff0c\u4f5c\u8005\u63a8\u6d4b\u4e86\u5982\u4e0b\u7684\u53cd\u5e94\u673a\u7406(Figure 4C)\uff1a\u6c2f\u539f\u5b50\u5728\u50ac\u5316\u6d3b\u6027\u7269\u79cd\u548c\u8fdc\u7aef\u70ef\u70c3\u7684\u5171\u540c\u4f5c\u7528\u4e0b\u79bb\u53bb\u8fbe\u5230\u70ef\u70c3\u79bb\u5b50\u5316\u7684\u53cd\u5e94\u8fc7\u6e21\u6001\uff0c\u968f\u540e\u70ef\u70c3\u5b8c\u6210\u8fdb\u653b\u5f97\u5230\u78b3\u6b63\u79bb\u5b50\u4e2d\u95f4\u4f53\uff0c\u968f\u540e\u53cd\u5e94\u5f97\u5230\u4ea7\u7269\u3002<\/p>\n

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

Figure 4. Mechanistic studies. (A) One-pot competition secondary H\/D KIE experiment. (B) Hammett studies. In red: Relative rates of reaction of 1b-1f promoted by catalyst 7b. In blue: Enantioselectivities in the formation of 2b-2f promoted by 7a. (C) Proposed catalytic cycle based on the KIE data and the experimentally determined rate law. (D) Transition state model for the pathway leading to the major enantiomeric product in the cyclization of 1d. <\/em><\/p>\n

\u540e\u7eed\u7684DFT\u8ba1\u7b97\u5f97\u5230\u7684\u8fc7\u56fa\u6001\u4e5f\u8868\u660e\u53cd\u5e94\u7684\u6d3b\u6027\u50ac\u5316\u7269\u79cd\u662f\u624b\u6027\u8132\u7684\u5355\u4f53\u548c\u4e8c\u805a\u4f53\u7684\u590d\u5408\u7269(Figure 4D)\u3002\u5728\u8fc7\u6e21\u6001\u4e2d\uff0c\u50ac\u5316\u5242\u4e0a\u7684\u8418\u57fa\u56e2\u4e0e\u7535\u8377\u4e2d\u5fc3\u9760\u8fd1\u4ee5\u7a33\u5b9a\u8fc7\u6e21\u6001\uff0c\u4ece\u800c\u5b9e\u73b0\u4e86\u624b\u6027\u4e2d\u5fc3\u7684\u8bf1\u5bfc\u3002\u5b9e\u9a8c\u6570\u636e\u4e5f\u8bc1\u5b9e\u4e86\u53d6\u4ee3\u57fa\u4e0d\u540c\u5bf9\u53cd\u5e94\u9009\u62e9\u6027\u6709\u5f71\u54cd(Figure 5)\u3002\u5bf9\u4e8e\u4e0d\u540c\u7684\u53d6\u4ee3\u57fa\uff0c\u53cd\u5e94\u901f\u7387\u548c\u5bf9\u6620\u9009\u62e9\u6027\u6709\u6b63\u76f8\u5173\uff0c\u8fd9\u8bf4\u660e\u5f53\u50ac\u5316\u5242\u7684\u53d6\u4ee3\u57fa\u8d8a\u80fd\u7a33\u5b9a\u8fc7\u6e21\u6001\u65f6\uff0c\u53cd\u5e94\u901f\u5ea6\u548c\u5bf9\u6620\u9009\u62e9\u6027\u90fd\u4f1a\u968f\u4e4b\u63d0\u9ad8\uff0c\u8fd9\u4e0e\u8fdc\u7aef\u70ef\u70c3\u53c2\u4e0e\u7684\u51b3\u901f\u6b65\u76f8\u7b26\u3002<\/p>\n

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

Figure 5. Effect of catalyst aryl substituents on reaction rate and enantioselectivity.<\/em><\/p>\n

\u603b\u7ed3<\/strong><\/h4>\n

Jacobsen\u8bfe\u9898\u7ec4\u62a5\u9053\u4e86\u624b\u6027\u8132\u50ac\u5316\u5242\u50ac\u5316neryl chloride\u884d\u751f\u7269\u7684\u624b\u6027\u5c3e-\u5934\u73af\u5316\u53cd\u5e94\u3002\u8fdc\u7aef\u70ef\u70c3\u534f\u540c\u6c2f\u79bb\u5b50\u79bb\u53bb\u751f\u6210\u8fc7\u6e21\u6001\u65e2\u662f\u53cd\u5e94\u51b3\u901f\u6b65\u4e5f\u662f\u5bf9\u6620\u9009\u62e9\u6027\u51b3\u5b9a\u6b65\u3002\u52a8\u529b\u5b66\u5b9e\u9a8c\u548cDFT\u8ba1\u7b97\u90fd\u8868\u660e\u8be5\u53cd\u5e94\u4e2d\u6709\u4e24\u5206\u5b50\u7684\u624b\u6027\u8132\u50ac\u5316\u5242\uff0c\u5e76\u901a\u8fc7\u8fc7\u6e21\u6001\u7684\u9009\u62e9\u6027\u7a33\u5b9a\u4f5c\u7528\u5b9e\u73b0\u4e86\u53cd\u5e94\u7684\u5bf9\u6620\u9009\u62e9\u6027\u3002<\/p>\n

\u53c2\u8003\u6587\u732e<\/strong><\/h4>\n