将过渡金属催化与自由基化学相结合：二芳基碘鎓盐显著加速钯催化的C-H芳基化反应
Combining Transition Metal Catalysis with Radical Chemistry: Dramatic Acceleration of Palladium-Catalyzed C-H Arylation with Diaryliodonium Salts.
作者信息
Neufeldt Sharon R, Sanford Melanie S
机构信息
Department of Chemistry, University of Michigan, 930 North University Avenue, Ann Arbor, Michigan 48109, United States.
出版信息
Adv Synth Catal. 2012 Dec 14;354(18):3517-3522. doi: 10.1002/adsc.201200738.
Abstract
This paper describes a photoredox palladium/iridium-catalyzed C-H arylation with diaryliodonium reagents. Details of the reaction optimization, substrate scope, and mechanism are presented along with a comparison to a related method in which aryldiazonium salts are used in place of diaryliodonium reagents. The unprecedentedly mild reaction conditions (25 ºC in methanol), the requirement for light and a photocatalyst, the inhibitory effect of radical scavengers, and the observed chemoselectivity trends are all consistent with a radical-thermal reaction with diaryliodonium reagents that is believed to proceed an 'ionic' 2 pathway and requires a much higher reaction temperature (100 ºC).
摘要
本文描述了一种光氧化还原钯/铱催化的用二芳基碘鎓试剂进行的C-H芳基化反应。文中介绍了反应优化、底物范围和反应机理的细节，并与一种相关方法进行了比较，该相关方法使用芳基重氮盐代替二芳基碘鎓试剂。前所未有的温和反应条件（甲醇中25℃）、对光和光催化剂的要求、自由基清除剂的抑制作用以及观察到的化学选择性趋势，都与二芳基碘鎓试剂的自由基-热反应一致，据信该反应通过“离子”2途径进行，且需要更高的反应温度（100℃）。
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2
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3
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