The Selective Functionalisation of Saturated Hydrocarbons

这项研究描述了各种GIF类型的体系，它们通过非自由基机制将选择性饱和碳氢化合物氧化成酮。通过修饰，可以选择性地合成饱和碳氢化合物和二次多硫化物的二次苯硫基、苯基硒、氯和溴衍生物。在GoAggII体系(吡啶-醋酸-三氯化铁+过氧化氢)的一个变体中，已经发展了一种体系(GoAggIII)，它几乎定量地将饱和碳氢化合物氧化(30%转化率)成酮。对该体系中的两个中间体进行了表征，这两个中间体将通过物理技术和选择性捕集进行研究。前者包括动态C-13核磁共振、0-17核磁共振、ESCA谱、穆斯堡尔谱和共振拉曼光谱。有机合成计划正在支持巴顿博士开发的复杂氧化系统的继续研究，以选择性地使饱和碳氢化合物功能化。这种化学与甲烷单加氧酶催化的反应有相似之处。这项工作应该会导致一个系统，能够以一种综合有用的方式执行这一重要的反应。

This research describes the various Gif-type systems which oxidize selectively saturated hydrocarbons to ketones by non-radical mechanisms. Modifications will enable the selective synthesis of secondary phenylthio-, phenylseleno-, chloro- and bromo-derivatives of saturated hydrocarbons and of secondary polysulfides. In a variation of the GoAggII system (pyridine - acetic acid - ferric chloride + hydrogen peroxide), a system (GoAggIII) has been developed that oxidizes (30% conversion) saturated hydrocarbons to ketones nearly quantitatively. Two intermediates in this system have been characterised which will be studied by physical techniques and by selective trapping. The former are dynamic C-13 NMR, 0-17 NMR, ESCA spectroscopy, Mossbauer spectroscopy and resonance Raman spectroscopy. The Organic Synthesis Program is supporting a continuation of the studies of the complex oxidation system developed by Dr. Barton to selectively functionalize saturated hydrocarbons. The chemistry has parallels in the reactions that are catalyzed by the enzyme methane monooxygenase. This work should lead to a system that can perform this important reaction in a synthetically useful manner.