The development of a 'safety-catch' arylgermane for biaryl synthesis by palladium-catalysed germyl-Stille cross-coupling
The development of a 'safety-catch' arylgermane for biaryl synthesis by palladium-catalysed germyl-Stille cross-coupling
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DOI：
10.1002/aoc.1270
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发表时间：
2007-07-01
影响因子：
3.9
通讯作者：
Scicinski, Jan J.
中科院分区：
文献类型：
--
作者：
Spivey, Alan C.;Gripton, Christopher J. G.;Scicinski, Jan J.
Pd（0）催化的芳基锗烷与芳基溴的交叉偶联显示需要Ge中心上的至少两个不稳定的杂原子配体以允许通过氟化物的有效亲核活化。二氯芳基锗烷7a和7 b显示出交叉偶联到一系列的芳基溴与中等效率使用KF在DMF中的活化。双（2-萘甲基）芳基锗烷18 b被确定为这种类型的交叉耦合基板的“安全捕获”前体。在Cu（BF 4）（2）的存在下，2-萘甲基取代基可以通过光解氧化除去，并且所得到的物质虽然没有表征，但使用DMF中的TBAF活化参与交叉偶联。版权所有（c）2007约翰威利父子有限公司。
The Pd(0) catalysed cross-coupling of arylgermanes with aryl bromides is shown to require at least two labile heteroatom ligands on the Ge centre to allow efficient nucleophilic activation by fluoride. Dichloroarylgermanes 7a and 7b are shown to cross-couple to a series of aryl bromides with moderate efficiency using activation by KF in DMF. Bis(2-naphthylmethyl)arylgermane 18b is identified as a 'safety-catch' precursor to this type of cross-coupling substrate. The 2-naphthylmethyl substituents can be removed via photolytic oxidation in the presence of Cu(BF4)(2) and the resulting species, although not characterized, participates in cross-coupling using activation by TBAF in DMF. Copyright (c) 2007 John Wiley & Sons, Ltd.