Formation of phosphorus heterocycles using a cationic electrophilic phosphinidene complex
作者:Kandasamy Vaheesar、Colin M. Kuntz、Brian T. Sterenberg
DOI:10.1016/j.jorganchem.2013.07.076
日期:2013.11
electrophilic terminal aminophosphinidene complex [CpFe(CO)2PN-i-Pr2}][X] (Cp = cyclopentadienyl, i-Pr = isopropyl, X = AlCl4 or NaBPh4), generated from [CpFe(CO)2P(Cl)N-i-Pr2}] by chloride abstraction, reacts with alkynes and alkenes via (1 + 2) cycloaddition to form phosphirenes and phosphiranes respectively. Conjugated alkenes react with [CpFe(CO)2PN-i-Pr2}]+ to form phosphirane intermediates,
由[CpFe(CO)生成的亲电子末端氨基次膦配合物[CpFe(CO)2 P N -i- Pr 2 }] [X](Cp =环戊二烯基,i -Pr =异丙基,X = AlCl 4或NaBPh 4) )2 P(Cl)N -i- Pr 2 }]通过氯化物提取,通过(1 + 2)环加成反应与炔烃和烯烃反应,分别形成膦酮和膦酮。共轭烯烃与[CpFe(CO)2 P N -i- Pr 2 }] +发生反应形成膦酸酯中间体,然后将其重排为3-膦烯。次膦配合物与亚苄基丙酮反应,生成氧代3-膦烯配合物。偶氮苯与[CpFe(CO)2 P N -i- Pr 2 }] +反应,通过C–H活化形成苯并重氮唑。在二苯基膦铁络合物和苯并重氮磷铁络合物中添加HCl或HBF 4 ·Et 2 O会导致P–N键断裂,从而产生各自的氯磷杂环络合物。可以通过添加三甲基或三乙基膦从金属络合物中除去杂环以制备无金属的磷杂环。