Kubisiak Marcin, Zelga Karolina, Bury Wojciech, Justyniak Iwona, Budny-Godlewski Krzysztof, Ochal Zbigniew, Lewiński Janusz
Department of Chemistry , Warsaw University of Technology , Noakowskiego 3 , 00-664 Warsaw , Poland . Email:
Institute of Physical Chemistry , Polish Academy of Sciences , Kasprzaka 44/52 , 01-224 Warsaw , Poland . Email:
Chem Sci. 2015 May 1;6(5):3102-3108. doi: 10.1039/c5sc00600g. Epub 2015 Mar 19.
This paper reports a series of comparative experiments on the activity of carbon- and oxygen-centred radical species in a model reaction of the radical addition of THF to imines mediated by a series of zinc alkyl/air reaction systems. The study strongly contradicts the notion that generally R˙ radicals are the initiating species in organic reactions mediated by R M/air systems, and simultaneously demonstrates that oxygen-centred radical species are the key intermediates responsible for the initiation process. In addition, a new efficient RZn(L)/air initiating system for radical organic reactions exampled by a model reaction of radical addition of THF to imines is developed. Moreover, the isolation and structural characterization of the first zinc alkylperoxide supported by a carboxylate ligand, [Zn(μ-OOBu)(μ-O)(OCEt)], as well as the novel octanuclear zinc oxo(alkoxide) aggregate with entrapped O-THF species, [Zn(μ-O)(μ-2-O-THF)(OCEt)], provide clear mechanistic signatures for the mode of function of the RZn(OCR')/air system.
本文报道了一系列关于碳中心和氧中心自由基物种活性的对比实验，这些实验是在由一系列锌烷基/空气反应体系介导的四氢呋喃（THF）与亚胺的自由基加成模型反应中进行的。该研究强烈反驳了通常R˙自由基是由R - M/空气体系介导的有机反应中的引发物种这一观点，同时表明氧中心自由基物种是引发过程的关键中间体。此外，还开发了一种用于自由基有机反应的新型高效RZn(L)/空气引发体系，以THF与亚胺的自由基加成模型反应为例。此外，首次分离并对由羧酸酯配体支撑的锌烷基过氧化物[Zn(μ - OOBu)(μ - O)(OCEt)]以及含有O - THF物种的新型八核锌氧（醇盐）聚集体[Zn(μ - O)(μ - 2 - O - THF)(OCEt)]进行了结构表征，为RZn(OCR')/空气体系的作用模式提供了明确的机理特征。
