NiCl2(dppe)-catalyzed cross-coupling of aryl mesylates, arenesulfonates, and halides with arylboronic acids
NiCl2(dppe)-catalyzed cross-coupling of aryl mesylates, arenesulfonates, and halides with arylboronic acids
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DOI：
10.1021/jo049940i
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发表时间：
2004-05-14
影响因子：
3.6
通讯作者：
Weichold, O
中科院分区：
文献类型：
--
作者：
Percec, V;Golding, GM;Weichold, O
报道了NiCl2(Dppe)-、NiCl2(Dppb)-、NiCl2(Dppf)-、NiCl2(PCy3)(2)-和NiCl2(PPh3)(2)催化的芳基甲磺酸酯、芳基磺酸盐、氯化物、溴化物和碘化物与芳基硼酸在无还原剂条件下的交叉偶联反应。NiCl2(Dppe)是唯一一种在甲苯和二氧六环两种溶剂中表现出高活性和非溶剂活性的催化剂。含有过量dppe的NiCl2(Dppe)/dppe在贫电子的芳基甲磺酸盐、对甲苯磺酸盐、氯化物、溴化物和碘化物的交叉偶联中起反应。该催化剂对含给电子基的芳基溴化物和碘化物的交叉偶联反应也是有效的。最令人惊讶的是，用过量的PPh3取代NiCl2(Dppe)/dppe中的过剩dppe会产生NiCl2(Dppe)/PPh3，这被发现对富电子和贫电子的芳基甲磺酸盐和氯化物的交叉偶联都有反应。因此，NiCl2的非溶剂反应性(Dppe)为芳基甲磺酸、对甲苯磺酸盐、氯化物、溴化物和碘化物与芳基硼酸的交叉偶联提供了一种廉价和通用的镍催化剂。
An investigation of the NiCl2(dppe)-, NiCl2(dppb)-, NiCl2(dppf)-, NiCl2(PCy3)(2)-, and NiCl2(PPh3)(2)-catalyzed cross-coupling of the previously unreported aryl mesylates, and of aryl arenesulfonates, chlorides, bromides, and iodides containing electron-withdrawing and electron-donating substituents with aryl boronic acids, in the absence of a reducing agent, is reported. NiCl2(dppe) was the only catalyst that exhibited high and solvent-independent activity in the two solvents investigated, toluene and dioxane. NiCl2(dppe) with an excess of dppe, NiCl2(dppe)/dppe, was reactive in the cross-coupling of electron-poor aryl mesylates, tosylates, chlorides, bromides, and iodides. This catalyst was also efficient in the cross-coupling of aryl bromides and iodides containing electron-donating substituents. Most surprisingly, the replacement of the excess dppe from NiCl2(dppe)/dppe with excess PPh3 generated NiCl2(dppe)/PPh3, which was found to be reactive for the cross-coupling of both electron-rich and electron-poor aryl mesylates and chlorides. Therefore, the solvent-independent reactivity of NiCl2(dppe) provides an inexpensive and general nickel catalyst for the cross-coupling of aryl mesylates, tosylates, chlorides, bromides, and iodides with aryl boronic acids.