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Poloxotungstate Photoinduced Alkylation of Electrophiic Alkenes by cycloalkanes

机译:泊托钨酸环烷烃光诱导静电烯烃的烷基化

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摘要

Alkyl radica obtained by irradiation of tetrabutylammonium decatungstate in acetonitrile in the presence of cycloalkanes (C_5H_(10),C_(6H_(12),C_7H_(14))are efficiently trapped by electrophilic alkenes (acrylonitrile,isopropylydenmalonitrile,isopropylydencyanoacetate)to give the corresponding alkylated aliphatic nitriles.The reaction can be carried out up to complete conversion of the alkene with reasonable (in most cases 60-65%)yields.Addition of the radicals to the alkene is followed by electron transfer from reduced decatungstate regenerating the sensitizer (turn over number up to 60).Steadystate measurements,EPR evidence,deuteration experimnets and attempted intramoleuclar trapping of the adduct radical support he mechanistic proposal.
机译:在环烷烃(C_5H_(10),C_(6H_(12),C_7H_(14))存在下,在乙腈中辐射四丁基癸二酸铵获得的烷基基团被亲电子烯烃(丙烯腈,异丙基丙二甲基丙烯腈,异丙基对甲基十一烷酸酯)有效地捕获可以进行反应以完成烯烃的完全转化,并获得合理的收率(在大多数情况下为60-65%)。将自由基加到烯烃中,然后由还原的十分解碳酸盐进行电子转移,使敏化剂再生(转最多可达到60个)。稳态测量,EPR证据,氘代实验以及试图分子内捕获加合物自由基的机理建议。

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