{"id":37867,"date":"2021-03-30T08:00:18","date_gmt":"2021-03-30T00:00:18","guid":{"rendered":"\/\/www.gsbet888.com\/?p=37867"},"modified":"2021-03-29T15:23:08","modified_gmt":"2021-03-29T07:23:08","slug":"%e6%ad%a6%e6%b1%89%e5%a4%a7%e5%ad%a6%e5%88%98%e6%96%87%e5%8d%9a%e8%af%be%e9%a2%98%e7%bb%84jacs%ef%bc%9a-pdii%e5%82%ac%e5%8c%96%e6%b0%a8%e5%9f%ba%e7%8e%af%e5%8c%96%e5%92%8c%e5%8e%bb%e5%af%b9%e7%a7%b0","status":"publish","type":"post","link":"\/\/www.gsbet888.com\/%e5%8c%96%e5%ad%a6%e6%9d%82%e8%ae%b0\/recentpaper\/2021\/03\/%e6%ad%a6%e6%b1%89%e5%a4%a7%e5%ad%a6%e5%88%98%e6%96%87%e5%8d%9a%e8%af%be%e9%a2%98%e7%bb%84jacs%ef%bc%9a-pdii%e5%82%ac%e5%8c%96%e6%b0%a8%e5%9f%ba%e7%8e%af%e5%8c%96%e5%92%8c%e5%8e%bb%e5%af%b9%e7%a7%b0.html","title":{"rendered":"\u6b66\u6c49\u5927\u5b66\u5218\u6587\u535a\u8bfe\u9898\u7ec4JACS\uff1a Pd(II)\u50ac\u5316\u6c28\u57fa\u73af\u5316\u548c\u53bb\u5bf9\u79f0\u5316\u8148\u52a0\u6210\u5408\u6210\u5177\u6709\u03b1-\u5b63\u78b3\u4e2d\u5fc3\u5494\u5511\u916e"},"content":{"rendered":"

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

\u5bfc\u8bfb<\/h4>\n

\u8fd1\u65e5\uff0c\u6b66\u6c49\u5927\u5b66\u5218\u6587\u535a\u8bfe\u9898\u7ec4\u5728JACS<\/i><\/em>\u4e0a\u53d1\u8868\u8bba\u6587\uff0c\u901a\u8fc7\u4f7f\u7528\u542b\u6709\u7094\u70c3\u7684\u4e19\u4e8c\u8148\u5e95\u7269\uff081<\/b><\/strong>\uff09\uff0c\u5b9e\u73b0\u4e86Pd(II)\u50ac\u5316\u6c28\u57fa\u73af\u5316\u548c\u53bb\u5bf9\u79f0\u5316\uff08desymmetrizing\uff09\u8148\u52a0\u6210\u4e32\u8054\u53cd\u5e94\uff0c\u4ece\u800c\u5408\u6210\u5177\u6709\u03b1<\/i><\/em>-\u5b63\u78b3\u7acb\u4f53\u4e2d\u5fc3\u5494\u5511\u916e\uff08carbazolones\uff09\u884d\u751f\u7269\uff08er\u9ad8\u8fbe98:2\uff09\u3002\u540c\u65f6\uff0c\u8be5\u53cd\u5e94\u53ef\u901a\u8fc7\u4e00\u6b65\u64cd\u4f5c\u6784\u5efa\u4e24\u4e2a\u65b0\u73af\u548c\u4e00\u4e2a\u5b63\u78b3\u4e2d\u5fc3\u3002\u6b64\u5916\uff0c\u901a\u8fc7\u4ea7\u7269\u540e\u671f\u7684\u884d\u751f\u5316\u4ee5\u53ca\u76f8\u5173\u5929\u7136\u4ea7\u7269\u7684\u5408\u6210\uff0c\u8fdb\u4e00\u6b65\u8bc1\u660e\u4e86\u53cd\u5e94\u7684\u5b9e\u7528\u6027\u3002<\/p>\n

Enantioselective Synthesis of \u03b1\u2011All-Carbon Quaternary Center-Containing Carbazolones via Amino-palladation\/Desymmetrizing\u00a0Nitrile Addition Cascade<\/p>\n

Xu-Dong Hu, Zi-Hao Chen, Jing Zhao, Rui-Ze Sun, Hui Zhang, Xiaotian Qi, and Wen-Bo Liu*<\/p>\n

J.Am. Chem. Soc.<\/i><\/em>ASAPDOI:10.1021\/jacs.1c00840<\/u><\/a><\/p><\/blockquote>\n

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

\u6b63\u6587<\/h4>\n

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

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

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

\u7d27\u63a5\u7740\uff0c\u4f5c\u8005\u5bf9\u53cd\u5e94\u7684\u5b9e\u7528\u6027\u8fdb\u884c\u4e86\u7814\u7a76\uff08Scheme 3\uff09\u3002\u5728\u6807\u51c6\u6761\u4ef6\u4e0b\uff0c2b<\/b><\/strong>\u7684\u514b\u7ea7\u5b9e\u9a8c\uff0c\u6536\u7387\u4e3a87\uff05\uff0cer\u4e3a96:4\u3002\u540c\u65f6\uff0c\u76f8\u5e94\u4ea7\u72692<\/b><\/strong>\u53ef\u8fdb\u884c\u591a\u79cd\u540e\u671f\u884d\u751f\u5316\u30022b<\/b><\/strong>\u7ecfNaN3<\/sub>\u5904\u7406\u53ef\u53bb\u9664Ms\u57fa\u56e2\uff0c\u83b7\u5f97\u5f53\u91cf\u6536\u7387\u7684\u65e0\u4fdd\u62a4\u5494\u5511\u916e4<\/b><\/strong>\u3002\u5728Virgil\u548cGrubbs[8]<\/sup>\u62a5\u9053\u7684\u94c2\u50ac\u5316\u6c34\u5408\u53cd\u5e94\u4e4b\u540e\uff0c\u5177\u6709\u4f4d\u963b\u7684\u8148\u57fa\u5f88\u5bb9\u6613\u8f6c\u5316\u4e3a\u9170\u80fa5<\/b><\/strong>\uff0c\u6536\u738795%\u30022b<\/b><\/strong>\u7ecf\u6c34\u5408\u548cHofmann\u91cd\u6392\uff0c\u53ef\u83b7\u5f9783\uff05\u6536\u7387\u7684\u5f02\u6c30\u9178\u916f6<\/b><\/strong>\u30022p<\/b><\/strong>\u7ecf\u5206\u5b50\u5185Aldol\u7f29\u5408\uff0c\u53ef\u83b7\u5f9788\uff05\u6536\u7387\u7684\u73af\u5316\u4ea7\u72697<\/b><\/strong>\u30022r<\/b><\/strong>\u7ecfPPh3<\/sub>\/CBr4<\/sub>\u3001NaN3<\/sub>\u548cTiCl4<\/sub>\u5904\u7406\u540e\uff0c\u53ef\u83b7\u5f9767\uff05\u6536\u7387\u7684\u87ba-\u56db\u55118<\/b><\/strong>\u30022b<\/b><\/strong>\u901a\u8fc7\u4e00\u9505\u6cd5NaBH4<\/sub>\u548cEt3<\/sub>SiH\u8fd8\u539f\u540e\uff0c\u53ef\u83b7\u5f9791\uff05\u6536\u7387\u7684\u03b2<\/i><\/em>-\u5b63\u56db\u6c22\u5494\u55119<\/b><\/strong>\u3002\u6700\u540e\uff0c\u8fd8\u539f2c<\/b><\/strong>\u4e2d\u7684\u7fb0\u57fa\uff0c\u7136\u540e\u8fdb\u884c\u9178\u4fc3\u8fdbFriedel-Crafts\u53cd\u5e94\uff0c\u4ee5\u6781\u597d\u7684\u6536\u7387\u83b7\u5f97\u73af\u7a20\u5408\u5316\u5408\u726910<\/b><\/strong>\u3002\u503c\u5f97\u6ce8\u610f\u7684\u662f\uff0c\u5728\u6240\u6709\u884d\u751f\u5316\u53cd\u5e94\u4e2d\uff0cer\u503c\u5747\u4e0d\u53d7\u5f71\u54cd\u3002<\/p>\n

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

\u6b64\u5916\uff0c\u542b\u6709\u03b1<\/i><\/em>-\u5b63\u78b3\u4e2d\u5fc3\u5494\u5511\u916e\u4f5c\u4e3a\u4e00\u4e9b\u5929\u7136\u4ea7\u7269\u7684\u5173\u952e\u4e2d\u95f4\u4f53\uff0c\u53ef\u901a\u8fc7\u5494\u5511\u916e2s<\/b><\/strong>\u548c2u<\/b><\/strong>\u9ad8\u6548\u7684\u5408\u6210\u5355\u841c\u5432\u54da\u751f\u7269\u78b1\u6838\u5fc3\u7684\u987a\u5f0f\u548c\u53cd\u5f0f\u7a20\u5408\u7684\u516b\u6c22\u55b9\u5549\u9aa8\u67b6\uff08Scheme 4A\uff09\u3002\u5982\u901a\u8fc7\u6c34\u5408\u80bc\u9664\u53bb2s<\/b><\/strong>\u4e2d\u7684\u90bb\u82ef\u4e8c\u7532\u9170\u57fa\uff0c\u53ef\u5b9e\u73b0\u81ea\u53d1\u73af\u5316\u5f62\u6210\u4e9a\u80fa\uff0c\u518d\u7ecfPd\/C\u548cH2<\/sub>\u6c22\u5316\u53cd\u5e94\u4ee5\u5f62\u6210\u53cd\u5f0f\u7a20\u5408\u4ea7\u726911<\/b><\/strong>\uff08Kopsia\u751f\u7269\u78b1\u6838\u5fc3\u9aa8\u67b6\uff09\uff0c\u6536\u7387\u4e3a76\uff05\u30022u<\/b><\/strong>\u901a\u8fc7\u4e00\u9505\u6cd5\u7684\u916e\u8fd8\u539f\u548c\u9178\u4fc3\u8fdb\u73af\u5316\uff0c\u53ef\u83b7\u5f97\u987a\u5f0f\u7a20\u5408\u4ea7\u726912<\/b><\/strong>\uff08\u5373Aspidosperma\u751f\u7269\u78b1\u7684\u9aa8\u67b6\uff09\uff0c\u6536\u7387\u4e3a89\uff05\u3002\u5176\u6b21\uff0c\u4ece\u5494\u5511\u916e2s<\/b><\/strong>\u5f00\u59cb\uff0c\u4e5f\u53ef\u76f4\u63a5\u5408\u6210\u4e86\u87ba\u73af14<\/b><\/strong>\uff0c\u4e00\u79cdLeucomidine\u00a0A\u7684\u7c7b\u4f3c\u7269\uff08Scheme 4B\uff09\u3002\u6700\u540e\uff0cent<\/i><\/em>–2s<\/b><\/strong>\u7ecf\u8131\u4fdd\u62a4\/\u73af\u5316\u53cd\u5e94\uff0c\u83b7\u5f9780%\u6536\u7387\u7684ent<\/i><\/em>–13<\/b><\/strong>\uff0c\u518d\u7ecf\u4e9a\u80fa\u548c\u8148\u7684\u8fd8\u539f\uff0c\u5373\u53ef\u83b7\u5f9767\uff05\u6536\u7387\u7684\u56db\u73af\u7a20\u5408\u919b\u5316\u5408\u726915<\/b><\/strong>\uff0c\u53ef\u4f5c\u4e3a\u5408\u6210Kopsia\u751f\u7269\u78b1\u3001Kopsinidine C\u548cKopsinitarine E\u7684\u5173\u952e\u6027\u4e2d\u95f4\u4f53\uff08Scheme 4C\uff09\u3002<\/p>\n

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

\u6839\u636e\u76f8\u5173\u6587\u732e\u7684\u67e5\u9605[9]<\/sup>\uff0c\u4f5c\u8005\u63d0\u51fa\u4e86\u4e00\u79cd\u53ef\u80fd\u7684\u53cd\u5e94\u673a\u7406\uff08Scheme 5A\uff09\u3002\u9996\u5148\uff0cPd(II)\u914d\u5408\u7269I<\/b><\/strong>\u4e0e1b<\/b><\/strong>\u4e2d\u7684\u7094\u70c3\u914d\u4f4d\uff0c\u7ecf\u53cd\u5f0f-\u80fa\u94af\u5316\u53cd\u5e94\u5f62\u6210\u5432\u54da\u57fa\u94af(II)\u914d\u5408\u7269III<\/b><\/strong>\u3002\u968f\u540e\uff0c\u914d\u5408\u7269III<\/b><\/strong>\u4e2d\u7ecf\u5206\u5b50\u5185\u4eb2\u6838\u52a0\u6210\u751f\u6210\u914d\u5408\u7269IV<\/b><\/strong>\uff0c\u7ecf\u8d28\u5b50\u5316\uff0c\u5f62\u6210\u4e9a\u80fa\u4e2d\u95f4\u4f53V<\/b><\/strong>\u5e76\u518d\u751f\u50ac\u5316\u5242I<\/b><\/strong>\u3002\u5176\u4e2d\uff0c\u4e2d\u95f4\u4f53V<\/b><\/strong>\u7ecf\u8fdb\u4e00\u6b65\u9178\u6027\u6c34\u89e3\uff0c\u5373\u53ef\u83b7\u5f97\u5494\u5511\u916e2b<\/b><\/strong>\u3002\u6b64\u5916\uff0c\u5728\u6761\u4ef6\u4f18\u5316\u8fc7\u7a0b\u4e2d\u53d1\u73b0\uff0c\u914d\u5408\u7269III<\/b><\/strong>\u7ecf\u8d28\u5b50\u5206\u89e3\u53ef\u5f62\u6210\u526f\u4ea7\u72693b<\/b><\/strong>\uff0c\u4e5f\u6697\u793a\u4e86\u53e6\u4e00\u79cd\u53ef\u80fd\u7684\u673a\u7406\uff0c\u5373\u94af(II)\u50ac\u53163b<\/b><\/strong>\u7ecf\u4e2d\u95f4\u4f53VI<\/b><\/strong>\u7684Friedel-Crafts\u53cd\u5e94\u5f62\u6210IV<\/b><\/strong>\uff0c\u4f46\u5c063b<\/b><\/strong>\u7f6e\u4e8e\u6807\u51c6\u6761\u4ef6\u4e0b\u4e0d\u4f1a\u751f\u62102b<\/b><\/strong>\uff0c\u4ece\u800c\u6392\u9664\u8fd9\u79cd\u53ef\u80fd\u6027\u3002\u6b64\u5916\uff0c\u4f5c\u8005\u8fd8\u5bf9\u8148\u57fa\u7684\u63d2\u5165\u8fdb\u884c\u4e86DFT\u8ba1\u7b97\uff0c\u4ee5\u9610\u660e\u4e8c\u8148\u57fa\u7684\u5bf9\u6620\u5f02\u6784\u5206\u5316\uff08Scheme 5B\uff09\u3002\u8ba1\u7b97\u7ed3\u679c\u8868\u660e\uff0cTS-I<\/b><\/strong>\u7684\u80fd\u5792\u6bd4TS-II<\/b><\/strong>\u4f4e\uff0c\u8fd9\u662f\u7531\u4e8e\u4f53\u79ef\u8f83\u5927\u7684Bn\u57fa\u56e2\u4f4d\u4e8e\u534a\u6905\u72b6\u73af\u7684\u7a7a\u95f4\u8f83\u5c11\u7684\u4f4d\u7f6e\u5bfc\u81f4\u3002<\/p>\n

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

\u603b\u7ed3<\/h4>\n

\u6b66\u6c49\u5927\u5b66\u5218\u6587\u535a\u6559\u6388\u8bfe\u9898\u7ec4\u5f00\u53d1\u4e86\u4e00\u79cd\u4e0d\u5bf9\u79f0\u94af(II)\u50ac\u5316\u6c28\u57fa\u73af\u5316\u548c\u53bb\u5bf9\u79f0\u5316\u8148\u52a0\u6210\u4e32\u8054\u53cd\u5e94\uff0c\u53ef\u5408\u6210\u9ad8\u6536\u7387\u548c\u9ad8\u5bf9\u6620\u9009\u62e9\u6027\u4e14\u542b\u6709\u03b1<\/i><\/em>-\u5168\u78b3\u56db\u7ea7\u7acb\u4f53\u4e2d\u5fc3\u5494\u5511\u916e\u884d\u751f\u7269\u3002\u503c\u5f97\u6ce8\u610f\u7684\u662f\uff0c\u5494\u5511\u916e\u53ef\u4f5c\u4e3a\u4e00\u4e9b\u751f\u7269\u78b1\u7684\u901a\u7528\u7ed3\u6784\u5355\u5143\u548c\u6838\u5fc3\u9aa8\u67b6\uff08\u5982Leucomidine\u00a0A\uff09\u3002\u6b64\u5916\uff0c\u901a\u8fc7\u4ea7\u7269\u540e\u671f\u7684\u884d\u751f\u5316\uff0c\u8fdb\u4e00\u6b65\u8bc1\u660e\u4e86\u53cd\u5e94\u7684\u5b9e\u7528\u6027\u3002<\/p>\n

\u53c2\u8003\u6587\u732e<\/h4>\n[1] Li, Z.; Zhang, S.; Wu, S.; Shen, X.; Zou, L.; Wang, F.; Li, X.;\u00a0Peng, F.; Zhang, H.; Shao, Z. Enantioselective Palladium-Catalyzed\u00a0DecarboxylativeAllylation of Carbazolones: Total Synthesis of\u00a0(\u2212)-Aspidospermidine and (+)-Kopsihainanine A. Angew. Chem.<\/i><\/em>\u00a0<\/i><\/em>Int. Ed.<\/i><\/em>\u00a02013<\/b><\/strong>, 52, 4117\u22124121.<\/p>\n[2] Gartshore, C. J.; Lupton, D. W. Enantioselective Palladium-Catalyzed Decarboxylative\u00a0Allylation of Carbazolones and Indolones:\u00a0Formal Synthesis of (+)-Kopsihainanine A. Angew.<\/i><\/em>\u00a0<\/i><\/em>Chem. Int. Ed.<\/i><\/em>\u00a02013<\/b><\/strong>, 52, 4113\u22124116.<\/p>\n[3] Wei, Y.; Zhao, D.; Ma, D. Total Synthesis of the Indole\u00a0Alkaloid (\u00b1)- and (+)-Methyl N-Decarbomethoxychanofruticosinate.\u00a0Angew.Chem. Int. Ed.<\/i><\/em>\u00a02013<\/b><\/strong>, 52, 12988\u221212991.<\/p>\n[4] Leng, L.; Zhou, X.; Liao, Q.; Wang, F.; Song, H.; Zhang, D.;\u00a0Liu, X.-Y.; Qin, Y. Asymmetric Total Syntheses of Kopsia Indole\u00a0Alkaloids.Angew.Chem. Int. Ed.<\/i><\/em>\u00a02017<\/b><\/strong>, 56, 3703\u22123707.<\/p>\n[5] Numajiri, Y.; Pritchett, B. P.; Chiyoda, K.; Stoltz, B. M.\u00a0Enantioselective Synthesis of \u03b1-Quaternary Mannich Adducts by\u00a0Palladium-Catalyzed Allylic Alkylation: Total Synthesis of (+)-Sibirinine.\u00a0J. Am. Chem. Soc.<\/i><\/em>\u00a02015<\/b><\/strong>, 137, 1040\u22121043.<\/p>\n[6] Xu, H.; Huang, H.; Zhao, C.; Song, C.; Chang, J. Total\u00a0Synthesis of (+)-Aspidospermidine. Org. Lett.<\/i><\/em>\u00a02019<\/b><\/strong>, 21, 6457\u22126460.<\/p>\n[7] Ni, D.; Wei, Y.; Ma, D. Thiourea-Catalyzed Asymmetric\u00a0Michael Addition of Carbazolones to 2-Chloroacrylonitrile: Total\u00a0Synthesis of 5,22-Dioxokopsane, Kopsinidine C, and Demethoxycarbonylkopsin.\u00a0Angew.<\/i><\/em>\u00a0<\/i><\/em>Chem. Int. Ed.<\/i><\/em>\u00a02018<\/b><\/strong>, 57, 10207\u221210211.<\/p>\n[8] Xing, X.; Xu, C.; Chen, B.; Li, C.; Virgil, S. C.; Grubbs, R. H.\u00a0Highly Active Platinum Catalysts for Nitrile and Cyanohydrin\u00a0Hydration: Catalyst Design and Ligand Screening via Highthroughput\u00a0Techniques.\u00a0J. Am. Chem. Soc.<\/i><\/em>\u00a02018<\/b><\/strong>, 140, 17782\u221217789.<\/p>\n[9] (a) Chen, J.; Han, X.; Lu, X. Palladium(II)-Catalyzed Asymmetric\u00a0Tandem Cyclization of 2-Aminoaryl Alkynones: An Approach to\u00a0Chiral 1,2,3,4-Tetrahydro-\u03b2-carbolines. Org. Lett.<\/i><\/em>\u00a02018<\/b><\/strong>, 20, 7470\u22127473.\u00a0(b) For a recent example: He, Y.-P.; Cao, J.; Wu, H.; Wang, Q.;\u00a0Zhu, J. Catalytic Enantioselective Aminopalladation\u2212Heck Cascade.\u00a0Angew. Chem. Int. Ed. <\/i><\/em>2020<\/b><\/strong>, DOI: 10.1002\/anie.202016001. (c) Vicente, J.; Abad, J.-A.; Gil-Rubio, J. Palladium-Assisted Formation of Carbon\u2212Carbon Bonds. 6.1 Study of the Reactivity of (o-Formylaryl)- or (o-Acetylaryl)palladium Complexes with\u00a0Alkynes.Synthesis of Indenones and Indenols. Organometallics<\/i><\/em>\u00a01996<\/b><\/strong>, 15, 3509\u22123519.<\/p>\n","protected":false},"excerpt":{"rendered":"\u672c\u6587\u4f5c\u8005\uff1a\u6749\u6749 \u5bfc\u8bfb \u8fd1\u65e5\uff0c\u6b66\u6c49\u5927\u5b66\u5218\u6587\u535a\u8bfe\u9898\u7ec4\u5728JACS\u4e0a\u53d1\u8868\u8bba\u6587\uff0c\u901a\u8fc7\u4f7f\u7528\u542b\u6709\u7094\u70c3\u7684\u4e19\u4e8c\u8148\u5e95\u7269\uff081\uff09\uff0c\u5b9e\u73b0\u4e86Pd(II)\u50ac\u5316\u6c28\u57fa\u73af\u5316\u548c\u53bb\u5bf9\u79f0\u5316\uff08desymmetrizing\uff09\u8148\u52a0\u6210\u4e32\u8054\u53cd\u5e94\uff0c\u4ece\u800c\u5408\u6210\u5177\u6709\u03b1-\u5b63\u78b3\u7acb\u4f53\u4e2d\u5fc3\u5494\u5511\u916e\uff08carbazolones\uff09\u884d\u751f\u7269\uff08er\u9ad8\u8fbe98:2\uff09\u3002\u540c\u65f6\uff0c\u8be5\u53cd\u5e94\u53ef\u901a\u8fc7\u4e00\u6b65\u64cd\u4f5c\u6784\u5efa\u4e24\u4e2a\u65b0\u73af\u548c\u4e00\u4e2a\u5b63\u78b3\u4e2d\u5fc3\u3002\u6b64\u5916\uff0c\u901a\u8fc7\u4ea7\u7269\u540e\u671f\u7684\u884d\u751f\u5316\u4ee5\u53ca\u76f8\u5173\u5929\u7136\u4ea7\u7269\u7684\u5408\u6210\uff0c\u8fdb\u4e00\u6b65\u8bc1\u660e\u4e86\u53cd\u5e94\u7684\u5b9e\u7528\u6027\u3002 Enantioselective Synthesis of \u03b1\u2011All-Carbon Quaternary Center-Containing Carbazolones via Amino-palladation\/Desymmetrizing\u00a0Nitrile Addition Cascade Xu-Dong Hu, Zi-Hao Chen, Jing Zhao, Rui-Ze Sun, Hui Zhang, Xiaotian Qi, and Wen-Bo Liu* J.Am. Chem. Soc.ASAPDOI:10.1021\/jacs.1c00840 \u6b63\u6587 \u5494\u5511\u916e\u662f\u751f\u7269\u5b66\u4e2d\u4e00\u7c7b\u91cd\u8981\u7684\u9aa8\u67b6\u3002\u76ee\u524d\uff0c\u5229\u7528\u5494\u5511\u916e\u4f5c\u4e3a\u5173\u952e\u4e2d\u95f4\u4f53\uff0c\u5df2\u5b9e\u73b0\u8d85\u8fc710\u79cdAspidosperma\u548cKopsia\u690d\u7269\u78b1\u7684\u5168\u5408\u6210\uff08Scheme 1A\uff09\u3002\u8fd9\u4e9b\u7814\u7a76\u5177\u6709\u7edf\u4e00\u7279\u5f81\uff0c\u5373\u5145\u5206\u5229\u7528C20\u7684\u5168\u78b3\u7acb\u4f53\u4e2d\u5fc3\uff0c\u4ece\u800c\u5b9e\u73b0\u7acb\u4f53\u9009\u62e9\u6027\u7684\u63a7\u5236\u3002\u7136\u800c\uff0c\u4ec5\u6709\u4e24\u79cd\u7c7b\u578b\u7684\u4e0d\u5bf9\u79f0\u50ac\u5316\u65b9\u6cd5\u88ab\u62a5\u9053\uff0c\u5373Pd(0)\u50ac\u5316\u8131\u7fa7\u70ef\u4e19\u57fa\u70f7\u57fa\u5316\u53cd\u5e94\u548c\u786b\u8132\u50ac\u5316Michael\u52a0\u6210\u53cd\u5e94\uff08Scheme 1B,C\uff09\u30022013\u5e74\uff0cShao[1]\u548cLupton[2]\u7b49\u5b9e\u73b0\u4e86\u5bf9\u6620\u53d1\u6563\u6027Pd(0)\u50ac\u5316\u7684\u8131\u7fa7\u70ef\u4e19\u57fa\u70f7\u57fa\u5316\u53cd\u5e94\uff0c\u4ece\u800c\u6784\u5efa\u5177\u6709\u5b63\u78b3\u4e2d\u5fc3\u7684\u5494\u5511\u916e\uff08Scheme 1B\uff09\u3002\u968f\u540e\uff0c\u5176\u4ed6\u7684\u8bfe\u9898\u7ec4\u4e5f\u62a5\u9053\u4e86\u76f8\u4f3c\u7684\u53cd\u5e94\u5408\u6210\u5177\u6709\u4e0d\u540c\u73af\u5916\u53d6\u4ee3\u57fa\u7684\u5494\u5511\u916e\uff0c\u5982Ma[3]\u3001Qin[4]\u3001Stoltz[5]\u3001Song\u548cChang[6]\u3002\u6700\u8fd1\uff0cMa\u7b49[7]\u8fd8\u5b9e\u73b0\u4e86\u786b\u8132\u50ac\u5316\u5494\u5511\u916e\uff08\u542b\u9170\u80fa\u53d6\u4ee3\uff09\u548c2-\u6c2f\u4e19\u70ef\u8148\u7684\u4e0d\u5bf9\u79f0Michael\u52a0\u6210\/\u8fd8\u539f\u53cd\u5e94\u3002\u867d\u7136\u5df2\u53d6\u5f97\u4e00\u5b9a\u7684\u6210\u679c\uff0c\u4f46\u6b64\u7c7b\u65b9\u6cd5\u9700\u9884\u5148\u8fdb\u884c\u7acb\u4f53\u5316\u5b66\u5408\u6210\u5494\u5511\u916e\uff08\u53ea\u80fd\u5f15\u5165\u6709\u9650\u7684\u5b98\u80fd\u56e2\uff09\uff0c\u4ece\u800c\u5bfc\u81f4\u65b9\u6cd5\u53d7\u5230\u9650\u5236\u3002\u56e0\u6b64\uff0c\u5f00\u53d1\u4e00\u79cd\u65b0\u578b\u4e32\u8054\u53cd\u5e94\u4ee5\u6784\u5efa\u5177\u6709\u03b1-\u5168\u78b3\u56db\u5143\u4e2d\u5fc3\u7684\u5494\u5511\u916e\u9aa8\u67b6\u5177\u6709\u91cd\u8981\u7684\u610f\u4e49\u3002\u6b64\u5916\uff0c\u53d7\u7094\u70c3\u94af\u5316\u53cd\u5e94\u548c\u78b3-\u6742\u539f\u5b50\u4e0d\u9971\u548c\u952e\u63d2\u5165\u4e32\u8054\u53cd\u5e94\u7684\u542f\u53d1\uff0c\u4f5c\u8005\u8bbe\u60f3\u4e86\u4e00\u79cd\u53bb\u5bf9\u5316\u7684\u7b56\u7565\uff0c\u901a\u8fc7\u6613\u5408\u6210\u7684\u7094\u57fa\u5316\u4e19\u4e8c\u8148\u4e3a\u5e95\u7269\uff0c\u7ecf\u53cd\u5f0f-\u80fa\u94af\u53cd\u5e94\u5f62\u6210\u82b3\u57fa\u94af(II)\u4e2d\u95f4\u4f53\uff0c\u968f\u540e\u7ecf\u6c34\u89e3\u540e\u63d2\u5165\u8148\u57fa\uff0c\u4ece\u800c\u83b7\u5f97\u5177\u6709\u03b1-\u5b63\u78b3\u4e2d\u5fc3\u7684\u5494\u5511\u916e\u884d\u751f\u7269\uff08Scheme 1D\uff09\u3002 \u9996\u5148\uff0c\u4f5c\u8005\u4ee5\u542b\u7094\u70c3\u7684\u4e19\u4e8c\u81481a\u548c1b\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\u7528\u542b\u6709Ms\u57fa\u56e2\u76841b\u4e3a\u5e95\u7269\uff0c\u4ee5Pd(TFA)2\u548c(S)-tBu-Phox\u539f\u4f4d\u53cd\u5e94\u751f\u6210\u5316\u5408\u7269\u4e3a\u50ac\u5316\u5242\uff0c\u53ef\u5728\u7532\u82ef\u6eb6\u5242\u4e2d\u53cd\u5e94\uff0c\u83b7\u5f97\u5494\u5511\u916e2b\uff0c\u6536\u7387\u4e3a88%\uff0cer\u4e3a97:3\u3002 \u5728\u83b7\u5f97\u4e0a\u8ff0\u6700\u4f73\u53cd\u5e94\u6761\u4ef6\u540e\uff0c\u4f5c\u8005\u5f00\u59cb\u5bf9\u5e95\u72691\u8fdb\u884c\u4e86\u6269\u5c55\uff08Scheme 2\uff09\u3002\u9996\u5148\uff0c\u5728\u5bf9\u5e95\u7269\u4e2d\u03b1-\u4f4d\u5b98\u80fd\u56e2\u8010\u53d7\u6027\u7814\u7a76\u8868\u660e\uff0c\u5177\u6709\uff08\u6742\uff09\u82b3\u57fa\u7532\u57fa\uff082b–2g\uff09\u548c\u70ef\u4e19\u57fa\u53d6\u4ee3\u57fa\uff082h\uff09\u7684\u4e19\u4e8c\u8148\u662f\u53ef\u884c\u7684\u5e95\u7269\uff0c\u83b7\u5f9780-94\uff05\u6536\u7387\u7684\u4ea7\u7269\u3002\u800c\u542b\u7094\u70c3\u7684\u5e95\u7269\uff082i\uff09\u5177\u6709\u8f83\u4f4e\u7684\u53cd\u5e94\u6027\uff0c\u6536\u7387\u4e3a59\uff05\u3002\u4e00\u7cfb\u5217\u5177\u6709\u7b80\u5355\u70f7\u57fa\u53d6\u4ee3\u57fa\u7684\u5e95\u7269\uff0c\u5747\u53ef\u987a\u5229\u53cd\u5e94\uff0c\u83b7\u5f97\u8f83\u9ad8\u6536\u7387\u7684\u4ea7\u72692j–2n\u3002\u503c\u5f97\u6ce8\u610f\u7684\u662f\uff0c\u8be5\u53cd\u5e94\u4e5f\u53ef\u83b7\u5f9772\uff05\u6536\u7387\u7684\u03b1-\u82ef\u57fa\u5494\u5511\u916e2o\u3002\u540c\u65f6\uff0c\u03b1-\u4f4d\u53d6\u4ee3\u542b\u6709\u4e00\u4e9b\u6d3b\u6027\u57fa\u56e2\u65f6\uff0c\u5982\u916e\u3001\u4e59\u7f29\u919b\u3001\u9187\u3001\u916f\u7b49\uff0c\u5747\u4e0e\u4f53\u7cfb\u517c\u5bb9\uff0c\u83b7\u5f97\u4ea7\u72692p–2u\u3002\u5176\u6b21\uff0c\u5728\u5bf9\u5e95\u7269\u4e2d\u82b3\u57fa\u73af\u7684\u8010\u53d7\u6027\u7814\u7a76\u8868\u660e\uff0c\u5177\u6709\u7ed9\u7535\u5b50\u53d6\u4ee3\u57fa\uff08Me-\u548cMeO-\uff09\u7684\u5e95\u7269\u5728\u6807\u51c6\u6761\u4ef6\u4e0b\u5747\u80fd\u987a\u5229\u53cd\u5e94\uff0c\u83b7\u5f9789-94\uff05\u6536\u7387\u7684\u5494\u5511\u916e2v–2x\u3002\u5364\u5316\u7269\uff08F-\u3001Cl-\u3001Br-\uff09\u3001\u4e09\u6c1f\u7532\u57fa\u548c\u916f\u53d6\u4ee3\u7684\u5e95\u7269\uff082y–2ad\uff09\u4e5f\u4e0e\u4f53\u7cfb\u517c\u5bb9\uff0c\u4f46\u6536\u7387\u7565\u4f4e\u3002\u6700\u540e\uff0c\u8be5\u53cd\u5e94\u4e5f\u53ef\u5408\u6210\u5432\u54da\u7a20\u5408\u7684\u4e03\u5143\u73af\u4ea7\u72692ae\uff0c\u6536\u7387\u4e3a75\uff05\u3002\u7136\u800c\uff0c\u5176\u5b83\u4e00\u4e9b\u5177\u6709\u8f83\u77ed\u6216\u8f83\u957f\u78b3\u94fe\u7b49\u7684\u5e95\u7269\u65e0\u6cd5\u83b7\u5f97\u76f8\u5e94\u7684\u4ea7\u7269\u3002\u503c\u5f97\u6ce8\u610f\u7684\u662f\uff0c\u4e0a\u8ff0\u4ea7\u7269\u5747\u5177\u6709\u8f83\u9ad8\u7684\u5bf9\u6620\u9009\u62e9\u6027\u3002 \u7d27\u63a5\u7740\uff0c\u4f5c\u8005\u5bf9\u53cd\u5e94\u7684\u5b9e\u7528\u6027\u8fdb\u884c\u4e86\u7814\u7a76\uff08Scheme 3\uff09\u3002\u5728\u6807\u51c6\u6761\u4ef6\u4e0b\uff0c2b\u7684\u514b\u7ea7\u5b9e\u9a8c\uff0c\u6536\u7387\u4e3a87\uff05\uff0cer\u4e3a96:4\u3002\u540c\u65f6\uff0c\u76f8\u5e94\u4ea7\u72692\u53ef\u8fdb\u884c\u591a\u79cd\u540e\u671f\u884d\u751f\u5316\u30022b\u7ecfNaN3\u5904\u7406\u53ef\u53bb\u9664Ms\u57fa\u56e2\uff0c\u83b7\u5f97\u5f53\u91cf\u6536\u7387\u7684\u65e0\u4fdd\u62a4\u5494\u5511\u916e4\u3002\u5728Virgil\u548cGrubbs[8]\u62a5\u9053\u7684\u94c2\u50ac\u5316\u6c34\u5408\u53cd\u5e94\u4e4b\u540e\uff0c\u5177\u6709\u4f4d\u963b\u7684\u8148\u57fa\u5f88\u5bb9\u6613\u8f6c\u5316\u4e3a\u9170\u80fa5\uff0c\u6536\u738795%\u30022b\u7ecf\u6c34\u5408\u548cHofmann\u91cd\u6392\uff0c\u53ef\u83b7\u5f9783\uff05\u6536\u7387\u7684\u5f02\u6c30\u9178\u916f6\u30022p\u7ecf\u5206\u5b50\u5185Aldol\u7f29\u5408\uff0c\u53ef\u83b7\u5f9788\uff05\u6536\u7387\u7684\u73af\u5316\u4ea7\u72697\u30022r\u7ecfPPh3\/CBr4\u3001NaN3\u548cTiCl4\u5904\u7406\u540e\uff0c\u53ef\u83b7\u5f9767\uff05\u6536\u7387\u7684\u87ba-\u56db\u55118\u30022b\u901a\u8fc7\u4e00\u9505\u6cd5NaBH4\u548cEt3SiH\u8fd8\u539f\u540e\uff0c\u53ef\u83b7\u5f9791\uff05\u6536\u7387\u7684\u03b2-\u5b63\u56db\u6c22\u5494\u55119\u3002\u6700\u540e\uff0c\u8fd8\u539f2c\u4e2d\u7684\u7fb0\u57fa\uff0c\u7136\u540e\u8fdb\u884c\u9178\u4fc3\u8fdbFriedel-Crafts\u53cd\u5e94\uff0c\u4ee5\u6781\u597d\u7684\u6536\u7387\u83b7\u5f97\u73af\u7a20\u5408\u5316\u5408\u726910\u3002\u503c\u5f97\u6ce8\u610f\u7684\u662f\uff0c\u5728\u6240\u6709\u884d\u751f\u5316\u53cd\u5e94\u4e2d\uff0cer\u503c\u5747\u4e0d\u53d7\u5f71\u54cd\u3002 \u6b64\u5916\uff0c\u542b\u6709\u03b1-\u5b63\u78b3\u4e2d\u5fc3\u5494\u5511\u916e\u4f5c\u4e3a\u4e00\u4e9b\u5929\u7136\u4ea7\u7269\u7684\u5173\u952e\u4e2d\u95f4\u4f53\uff0c\u53ef\u901a\u8fc7\u5494\u5511\u916e2s\u548c2u\u9ad8\u6548\u7684\u5408\u6210\u5355\u841c\u5432\u54da\u751f\u7269\u78b1\u6838\u5fc3\u7684\u987a\u5f0f\u548c\u53cd\u5f0f\u7a20\u5408\u7684\u516b\u6c22\u55b9\u5549\u9aa8\u67b6\uff08Scheme 4A\uff09\u3002\u5982\u901a\u8fc7\u6c34\u5408\u80bc\u9664\u53bb2s\u4e2d\u7684\u90bb\u82ef\u4e8c\u7532\u9170\u57fa\uff0c\u53ef\u5b9e\u73b0\u81ea\u53d1\u73af\u5316\u5f62\u6210\u4e9a\u80fa\uff0c\u518d\u7ecfPd\/C\u548cH2\u6c22\u5316\u53cd\u5e94\u4ee5\u5f62\u6210\u53cd\u5f0f\u7a20\u5408\u4ea7\u726911\uff08Kopsia\u751f\u7269\u78b1\u6838\u5fc3\u9aa8\u67b6\uff09\uff0c\u6536\u7387\u4e3a76\uff05\u30022u\u901a\u8fc7\u4e00\u9505\u6cd5\u7684\u916e\u8fd8\u539f\u548c\u9178\u4fc3\u8fdb\u73af\u5316\uff0c\u53ef\u83b7\u5f97\u987a\u5f0f\u7a20\u5408\u4ea7\u726912\uff08\u5373Aspidosperma\u751f\u7269\u78b1\u7684\u9aa8\u67b6\uff09\uff0c\u6536\u7387\u4e3a89\uff05\u3002\u5176\u6b21\uff0c\u4ece\u5494\u5511\u916e2s\u5f00\u59cb\uff0c\u4e5f\u53ef\u76f4\u63a5\u5408\u6210\u4e86\u87ba\u73af14\uff0c\u4e00\u79cdLeucomidine\u00a0A\u7684\u7c7b\u4f3c\u7269\uff08Scheme 4B\uff09\u3002\u6700\u540e\uff0cent–2s\u7ecf\u8131\u4fdd\u62a4\/\u73af\u5316\u53cd\u5e94\uff0c\u83b7\u5f9780%\u6536\u7387\u7684ent–13\uff0c\u518d\u7ecf\u4e9a\u80fa\u548c\u8148\u7684\u8fd8\u539f\uff0c\u5373\u53ef\u83b7\u5f9767\uff05\u6536\u7387\u7684\u56db\u73af\u7a20\u5408\u919b\u5316\u5408\u726915\uff0c\u53ef\u4f5c\u4e3a\u5408\u6210Kopsia\u751f\u7269\u78b1\u3001Kopsinidine C\u548cKopsinitarine E\u7684\u5173\u952e\u6027\u4e2d\u95f4\u4f53\uff08Scheme 4C\uff09\u3002 \u6839\u636e\u76f8\u5173\u6587\u732e\u7684\u67e5\u9605[9]\uff0c\u4f5c\u8005\u63d0\u51fa\u4e86\u4e00\u79cd\u53ef\u80fd\u7684\u53cd\u5e94\u673a\u7406\uff08Scheme 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Enantioselective Palladium-Catalyzed\u00a0DecarboxylativeAllylation of Carbazolones: Total Synthesis of\u00a0(\u2212)-Aspidospermidine and (+)-Kopsihainanine A. Angew. Chem.\u00a0Int. Ed.\u00a02013, 52, 4117\u22124121. [2] Gartshore, C. J.; Lupton, D. W. Enantioselective Palladium-Catalyzed Decarboxylative\u00a0Allylation of Carbazolones and Indolones:\u00a0Formal Synthesis of (+)-Kopsihainanine A. Angew.\u00a0Chem. 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