Sustainable Radical Chemistry under Microwave Irradiation

同时，自由基化学在现代有机合成中达到了很高的水平。然而，仍有许多问题有待解决。一大挑战是开发对环境无害的自由基反应。这将允许该行业使用这种有趣的化学物质提供的所有强大方法。在该项目中，建议使用微波加热来进行各种自由基反应。德国团队将与雷诺教授的团队合作，尝试扩大有机硼化合物作为稳定的C-自由基前体的用途。本课程将研究微波条件下的硼氢化反应，以及有机硼烷生成烯基和乙烯基自由基的自由基化学扩展。使用德国团队开发的环己二烯化学延伸的无锡还原环化工艺的开发将在瑞士进行调查。还将研究使用二烷氧基硼取代基作为迁移基团的新的自由基转移化学。将考察在微波条件下以烷氧胺为C-自由基前驱体的自由基环化反应和分子间加成反应。从硼化合物出发合成烷氧基胺的一般方法将被开发，烷氧基胺将用于热自由基异构化反应。这些过程由所谓的持久自由基热异构化控制，利用原子和基团转移反应在微波加热下卤化物和相关自由基前驱体的热异构化将由瑞士小组基于德国团队对烷氧基胺强相关异构化所获得的结果进行研究。将研究避免使用过渡金属催化剂和使用TiN试剂的反应条件。

Radical chemistry has meanwhile reached a very high standard in modern organic synthesis. However, many problems still remain to be solved. A big challenge is the development of environmentally benign radical reactions. This will allow the industry to use all the powerful methods offered by this interesting chemistry. In the project the application of microwave heating to perform various radical reactions is suggested. The German team in collaboration with the group of Prof. Renaud will try to expand the use of organoboron compounds as stable C-radical precursors. Hydroborations under microwave conditions will be examined as well as the extension of the radical chemistry of organoboranes for the generation alkenyl and vinyl radicals. The development of tin-free reductive cyclization processes using an extension of the cyclohexadiene chemistry developed by the German team will be investigated in Switzerland. New radical group transfer chemistry using dialkoxyboryl substituents as migrating groups will also be studied. Radical cyclizations and intermolecular additions reactions using alkoxyamines as C-radical precursors under microwave conditions will be examined. A general approach to alkoxyamines starting from boron compounds will be developed and the alkoxyamines will be used in thermal radical isomerization reactions. These processes are controlled by the so-called Persistent Radical Thermal isomerization of halides and related radical precursors under microwave heating using atom and group transfer reactions will be investigated by the Swiss group based on the results obtained by the German team for the strongly related isomerization of alkoxyamines. Reaction conditions avoiding the use of transition metal catalysts and the use of tin reagent will be examined.