Friedel-Crafts Ring-Coupling Reactions Promoted by Tungsten Dearomatization Agent
Friedel-Crafts Ring-Coupling Reactions Promoted by Tungsten Dearomatization Agent
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DOI：
10.1021/om3012008
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发表时间：
2013-01-28
期刊：
影响因子：
2.8
通讯作者：
Harman, W. Dean
中科院分区：
文献类型：
--
作者：
Pienkos, Jared A.;Zottig, Victor E.;Harman, W. Dean
络合物TpW（NO）（PMe 3）（L）（其中L =苯酚、N，N-二甲基苯胺或萘）经历质子化，然后加入芳族亲核试剂。芳族分子的加成发生在苯酚或苯胺环的帕拉碳或萘的β碳上。通过X射线晶体学测定，加成反应与金属碎片相反。在其中L =苯酚或N，N-二甲基苯胺的情况下，用亲电杂原子随后用芳香族亲核试剂处理结合的芳烃设置两个立构中心，两个加成都与金属反方向发生。用硝酸铈铵氧化解络，将所得配体从金属中除去。
The complexes TpW(NO)(PMe3)(L), where L = phenol, N,N-dimethylanilinium, or naphthalene, undergo protonation followed by addition of an aromatic nucleophile. The addition of aromatic molecules occurs at the para carbon of the phenol or aniline ring or the beta carbon of the naphthalene. The addition occurs anti to the metal fragment, as determined by X-ray crystallography. In the case where L = phenol or N,N-dimethylanilinium, treatment of the bound arene with an electrophilic heteroatom followed by an aromatic nucleophile sets two stereocenters, with both additions occurring anti to the metal. The resultant ligands have been removed from the metal by oxidative decomplexation using ceric ammonium nitrate.