Free Radical Chain Reactions

芝加哥伊利诺伊大学化学系的大卫克里奇教授因其对自由基链反应的研究而得到有机合成计划的支持。 硒醇催化的锡烷介导的链式反应的发展允许在打开之前捕获环丙基原基自由基。 为了促进这种类型的催化后的纯化，Crich教授正在制备和测试用于氟相的新硒醇。 通过催化量的硒醇对环己二烯基自由基的有效捕获提供了对说明性目标分子的进入，而立体化学探针的引入导致了邻位亲核取代反应的机理理解和合成应用。 在这些研究过程中，Crich教授正在开发用于自由基链式反应的新型低温引发剂。虽然带有未成对电子的分子种类（“自由基”）早已为人们所知，但直到最近才发现这些固有的反应性种类是足够可控的，从而可以将其用于所需有机分子的选择性合成。 在有机合成计划的支持下，芝加哥伊利诺伊大学化学系的大卫克里奇教授正在开发产生自由基及其在有机合成中的应用的新方法。 他的研究还将自由基化学的潜力扩展到低温工艺和新开发的“氟相”溶剂，为简单和环境友好的分离和加工步骤提供了希望。

Professor David Crich, of the Department of Chemistry at the University of Illinois at Chicago, is supported by the Organic Synthesis Program for his studies of free radical chain reactions. Development of selenol catalyzed stannane mediated chain reactions allows the trapping, before opening, of cyclopropylcarbinyl radicals. In order to facilitate purification following this type of catalysis, Professor Crich is preparing and testing new selenols for use in fluorous phases. The efficient trapping of cyclohexadienyl radicals by catalytic quantities of selenols provides entry to illustrative target molecules, while the introduction of stereochemical probes is leading to both a mechanistic understanding and synthetic applications of the vicinal nucleophilic substitution reaction. In the course of these studies, Professor Crich is developing new low-temperature initiators for free radical chain reactions.Although molecular species with an unpaired electron ("free radicals") have long been known, it is only comparatively recently that these intrinsically reactive species have been found to be sufficiently controllable to allow their use in the selective synthesis of desired organic molecules. With the support of the Organic Synthesis Program, Professor David Crich, of the Department of Chemistry at the University of Illinois at Chicago, is developing new methods for the generation of free radicals and for their use in organic synthesis. His studies are also extending the potential of free radical chemistry to lower temperature processes and to newly-developed "fluorous phase" solvents, offering promise for simple and environmentally benign separation and processing steps.