Reactions of Ferrocenium Hexafluorophosphate with P−OR Nucleophiles Give Ring C−H Functionalization or Ring Replacement Products Depending on the Phosphorus Reagent
作者:Aleksandr A. Chamkin、Vasily V. Krivykh、Arkady Z. Kreindlin、Fedor M. Dolgushin、Nikolai A. Ustynyuk
DOI:10.1002/ejic.202100153
日期:2021.4.26
nucleophiles (PR3=Ph2P(OMe), Ph2P(OEt), PhP(OiPr)2). The mechanism of the former reaction was established using DFT calculations. This reaction pathway is especially characteristic of π‐acceptor nucleophiles, which is presumably explained by their ability to stabilize the 19e intermediates. The result of the reaction with tertiary phosphines, aminophosphines, and P−OR nucleophiles can be reliably predicted
六氟磷酸铈与室温下CH 2 Cl 2中的不同P-OR亲核试剂(PR 3)反应,生成半夹心复合物[CpFe(PR 3)3 ](PF 6)(PR 3 = P(OMe)3, P(OEt)3,PhP(OMe)2)或二茂铁enyl盐[CpFe(C 5 H 4 PR 3)](PF 6)(PR 3 = i Pr 2 P(OMe),i Pr 2 P(OEt)) 。两种产物的混合物形成了其他一些亲核试剂(PR3= Ph 2 P(OMe),Ph 2 P(OEt),PhP(O i Pr)2)。前者的反应机理是通过DFT计算确定的。该反应途径特别是π受体亲核试剂的特征,大概是由其稳定19e中间体的能力来解释的。与叔膦,氨基膦,反应的结果P-OR亲核体可以可靠地基于所述电子托尔曼参数的值(下面2070厘米预测-1 -在2073厘米之间仅ferrocenylphosphonium盐,-1和2080厘米- 1 –仅是半三明治复合物,范围从2070