Electrooxidative CH/PH functionalization as a novel way to synthesize benzo[<i>b</i>]phosphole oxides mediated by catalytic amounts of silver acetate
作者:V. V. Khrizanforova、K. V. Kholin、M. N. Khrizanforov、M. K. Kadirov、Yu. H. Budnikova
DOI:10.1039/c7nj03717a
日期:——
Electrochemical joint oxidation of diphenylphosphine oxide with acetylenes in the presence of silver acetate (10%) as a catalyst yields benzo[b]phosphole oxide derivatives undermildconditions at room temperature without additional oxidants or initiators and with yields up to 100%. The redox properties of the key intermediate of the catalytic cycle have been investigated by cyclic voltammetry and EPR
在乙酸银(10%)作为催化剂的存在下,二苯膦氧化物与乙炔的电化学联合氧化可在室温下在温和条件下在无其他氧化剂或引发剂的情况下生成苯并[ b ]磷氧化物衍生物,产率最高可达100%。通过循环伏安法和EPR光谱研究了催化循环关键中间体的氧化还原性质。相较于所有反应前体,Ph 2 P(O)Ag中间体氧化更容易(+0.05 V vs. Fc + / Fc)形成次膦酸酯基Ph 2 P(O)3,被ESR固定为自旋加合物。因此,通过Ag + / Ag 0的基本机理类型 对是为电催化条件而开发的。
Gold nanoparticle-initiated free radical oxidations and halogen abstractions
作者:Petre Ionita、Marco Conte、Bruce C. Gilbert、Victor Chechik
DOI:10.1039/b711573c
日期:——
containing active hydrogenatoms, such as amines and phosphine oxides. Nanoparticles protected by stronger bound ligands (e.g., thiols) were inactive in these reactions. We also found that gold nanoparticles are able to abstract a halogen atom from the halogenated compounds, presumably due to the high affinity of gold metal for halogens. Reaction of Au nanoparticles with chloroform showed an unusual