Alkylation Reactions Involving Electron Transfer

这项有机和大分子化学基金资助了爱荷华州立大学格伦·a·罗素博士的工作，他的研究重点是链式和非链式过程中中性自由基的单电子还原或氧化。这项工作扩展到涉及烷基汞卤化物的自由基链过程的应用，主要目的是为电子贫乏和电子丰富的取代烯烃开发选择性添加剂烷基化过程。这类烯烃可以产生可分为受体或给体的加合自由基，可以通过加合自由基与添加的给体受体分子或离子之间的电子转移诱导参与链式反应。选择添加的供体或受体分子或离子，使电子转移产生新的自由基或能与烷基卤化汞迅速反应以再生烷基自由基的自由基离子。该研究还涉及烷基自由基反应性的物理有机研究，特别是对不饱和体系的反应性，并包括有关自由基攻击的区域化学，自由基加成的立体选择性和由加成-消除序列发生的自由基取代的立体特异性的新研究。该数据将应用于诊断方式，以确定或消除其他有机金属叔丁化剂反应中自由基过程的存在。

This grant in Organic and Macromolecular Chemistry provides support for work by Dr. Glen A. Russell, Iowa State University, focused on the one-electron reduction or oxidation of neutral radicals in chain and non-chain processes. The work extends to the application of free radical chain processes involving alkylmercury halides with the primary objective of developing selective additive alkylation processes for electron-poor and electron-rich substituted alkenes. It is believed that such alkenes, which yield adduct radicals that can be classified as acceptor or donor species, can be induced to participate in chain reactions by electron transfer between the adduct radicals and added donor acceptor molecules or ions. The added donor or acceptor molecule or ion will be chosen so that electron transfer yields a new radical or radical ion capable of rapidly reacting with the alkylmercury halide to regenerate an alkyl radical. The study also involves physical organic studies on the reactivity of alkyl radicals, particularly towards unsaturated systems, and includes new studies concerning the regiochemistry of radical attack, the stereoselectivity of radical addition and the stereospecificity of radical substitution occurring by an addition-elimination sequence. This data will be applied in a diagnostic fashion to establish or eliminate the presence of radical processes in reactions of other organometallic tert-butylating agents.