The Selective Substitution of Saturated Hydrocarbons (Chemistry)

这项研究不寻常的多相有机铁反应的项目得到了有机化学和高分子化学项目的支持。这种化学的新奇之处在于，在特殊条件下，各种类型的碳氢键对金属铁提取氢原子具有前所未有的相对反应性。关于这些反应涉及有机铁试剂中间体的假设正在得到验证。这项研究的结果将对含有碳铁键的物种(例如某些酶)的化学性质提供重要的见解。这项研究计划正在研究迄今为止在GIF和GIF-Orsay体系中建立的饱和碳氢化合物选择性氧化方法。最近，GIF体系的一项新进展发现了一个值得注意的新反应，它在非常温和的条件下允许饱和碳氢化合物选择性地进行苯硒化反应。这一反应和之前的反应值得进一步应用，特别是值得进行机理研究。似乎对GIF取代负责的铁物种正在被合成。竞争捕获程序被提出使用分子内陷阱来展示铁-碳西格马键和铁-卡宾双键的作用。饱和碳氢化合物的进一步新反应将被发明。

This project which deals with the chemistry of unusual heterogeneous organo-iron reactions is being supported by the Organic and Macromolecular Chemistry Program. The novelty of this chemistry lies in the unprecedented relative reactivities of the various types of carbon-hydrogen bonds toward hydrogen atom abstraction by iron metal under special conditions. The hypothesis that these reactions involve the intermediacy of organoiron reagents is being tested. Results from this study will give important insights into the chemical nature of species (e.g. certain enzymes) which contain the carbon-iron bond. This research program is studying the methods so far established in the Gif and Gif-Orsay systems for selective oxidation of saturated hydrocarbons. Recently a new development of the Gif system has uncovered a remarkable new reaction, which under very mild conditions permits the selective phenylselenation of saturated hydrocarbons. This and the preceding reaction, deserve further application and, in particular, mechanistic investigation. The iron species which appear to be responsible for the Gif substitution are being synthesized. Competitive trapping procedures are proposed using intramolecular traps to demonstrate the role of the iron-carbon sigma-bond and of the iron-carbene double bond. Further new reactions of saturated hydrocarbons will be invented.