Aminomethyl-Substituted Ferrocenes and Derivatives: Straightforward Synthetic Routes, Structural Characterization, and Electrochemical Analysis

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• 作者：Nejib Dwadnia ; Fatima Allouch ; Nadine Pirio ; Julien Roger ; H茅l猫ne Cattey ; Sophie Fournier ; Marie-Jos茅e Penouilh ; Charles H. Devillers ; Dominique Lucas ; Daoud Naoufal ; Ridha Ben Salem ; Jean-Cyrille Hierso
• 刊名：Organometallics
• 出版年：2013
• 出版时间：October 28, 2013
• 年：2013
• 卷：32
• 期：20
• 页码：5784-5797
• 全文大小：697K
• 年卷期：v.32,no.20(October 28, 2013)
• ISSN：1520-6041

文摘

A variety of aminomethyl-substituted ferrocenes and the parent compounds (iminomethyl)ferrocenes, azaferrocenophanes, and diferrocenylamines can be selectively synthesized from reductive amination of 1,1鈥?diformylferrocene or formylferrocene. The optimized one- or two-step reactions have delivered 13 new compounds, isolated in 65鈥?7% yields, which include tertiary (ferrocenylmethyl)amines and azaferrocenophanes by using NaBH(OAc)₃ as a mild reducing agent and (iminomethyl)ferrocenes and secondary (ferrocenylmethyl)amines by using LiAlH₄. X-ray structures of representative members of these ferrocene derivative families have evidenced the preferred conformation adopted by ferrocene backbones, in which surprisingly the steric hindrance is apparently not systematically minimized. ¹⁵N NMR measurements on aminomethyl-substituted ferrocenes and derivatives are provided for the first time, establishing benchmark values ranging from 鈭?30 to 鈭?05 ppm (nitromethane 未 0 ppm). The cyclic voltammetry of these species evidences two clearly distinct oxidation potentials related to the iron(II) center and the amino function. These aminomethyl-substituted ferrocenes are potentially valuable for further ortho-directed functionalization of ferrocene.