使用 HO 作为氧化剂制备的孤立 Pd(IV)酰胺芳基配合物的还原 C(sp)-N 消除反应。
Reductive C(sp)-N Elimination from Isolated Pd(IV) Amido Aryl Complexes Prepared Using HO as Oxidant.
机构信息
Department of Chemistry and Biochemistry, University of Maryland , College Park, Maryland 20742, United States.
出版信息
J Am Chem Soc. 2017 Jan 18;139(2):643-646. doi: 10.1021/jacs.6b12648. Epub 2017 Jan 5.
Di-2-pyridyl ketone (dpk)-supported amidoarylpallada(II)cycles derived from various 2-(N-R-amino)biphenyls (R = H, Me, CFCO, MeSO, CFSO) react with hydrogen peroxide in MeOH, THF, MeCN or AcOH to form the corresponding C-N coupled products, N-R-substituted carbazoles, in 82-98% yield. For R = MeSO and CFSO, the corresponding reaction intermediates, amidoaryl Pd(IV) complexes were isolated and characterized by single crystal X-ray diffraction and/or NMR spectroscopy. For the first time, the C(sp)-N reductive elimination from isolated amidoaryl Pd(IV) complexes has been studied in detail.
二吡啶酮（dpk）支持的酰胺芳基钯（II）环衍生自各种 2-（N-R-氨基）联苯（R = H、Me、CFCO、MeSO、CFSO），在 MeOH、THF、MeCN 或 AcOH 中与过氧化氢反应，以 82-98%的产率形成相应的 C-N 偶联产物，N-R-取代的咔唑。对于 R = MeSO 和 CFSO，相应的反应中间体，酰胺芳基 Pd（IV）配合物通过单晶 X 射线衍射和/或 NMR 光谱进行了分离和表征。首次详细研究了从分离的酰胺芳基 Pd（IV）配合物中进行的 C（sp）-N 还原消除。
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