氧化还原催化中自由基中间体的对映选择性官能团化：铜催化的烯烃不对称氧三氟甲基化反应
Enantioselective functionalization of radical intermediates in redox catalysis: copper-catalyzed asymmetric oxytrifluoromethylation of alkenes.
作者信息
Zhu Rong, Buchwald Stephen L
机构信息
Department of Chemistry, Room 18-490, Massachusetts Institute of Technology, Cambridge, MA 02139 (USA).
出版信息
Angew Chem Int Ed Engl. 2013 Nov 25;52(48):12655-8. doi: 10.1002/anie.201307790. Epub 2013 Oct 16.
Abstract
A method for the efficient enantioselective oxytrifluoromethylation of alkenes has been developed using a copper catalyst system. Mechanistic studies are consistent with a metal-catalyzed redox radical addition mechanism, in which a C–O bond is formed via the copper-mediated enantioselective trapping of a prochiral alkyl radical intermediate derived from the initial trifluoromethyl radical addition.
摘要
已开发出一种使用铜催化剂体系对烯烃进行高效对映选择性氧三氟甲基化的方法。机理研究与金属催化的氧化还原自由基加成机理一致，其中通过铜介导对映选择性捕获由最初的三氟甲基自由基加成产生的前手性烷基自由基中间体形成C-O键。
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2
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Chem Commun (Camb). 2013 Aug 25;49(66):7346-8. doi: 10.1039/c3cc43936d.
3
Trifluoromethylation reactions for the synthesis of β-trifluoromethylamines.三氟甲基化反应在β-三氟甲基胺合成中的应用。
Angew Chem Int Ed Engl. 2013 Jul 22;52(30):7841-4. doi: 10.1002/anie.201303350. Epub 2013 Jun 13.
4
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Angew Chem Int Ed Engl. 2013 Jul 1;52(27):6962-6. doi: 10.1002/anie.201302673. Epub 2013 May 27.
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Org Lett. 2013 May 3;15(9):2136-9. doi: 10.1021/ol4006272. Epub 2013 Apr 19.
7
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8
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9
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J Am Chem Soc. 2013 Apr 17;135(15):5557-60. doi: 10.1021/ja4023557. Epub 2013 Apr 3.
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Chem Rev. 2013 Jul 10;113(7):5322-63. doi: 10.1021/cr300503r. Epub 2013 Mar 19.
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