Synthesis and Reactions of Biradicals and o-Quinodimethanes

9307994王，这项研究的重点是开发新的方法来合成烯二炔和烯-烯-烯，这些方法可以方便地进入各种碳双基，并对随后的自由基过程进行机理研究。第一个目标是开发利用硅烯基硼与乙酰醛和烯丙醛的缩合反应来合成具有不同化学结构的烯二炔和烯-烯-烯。通过有机硼配合物的分子内迁移反应合成二炔、二烯-烯、二烯-二烯、二烯及其他相关结构的新路线也将被开发。通过在分子内捕获初始形成的具有合适位置的碳-碳双键或三键的双自由基来研究从这些不饱和化合物中形成碳二自由基的策略。这将允许自由基中心在分子周围移动，并可能导致其他活性物种的形成，如邻奎诺二甲烷。有了这个奖项，合成有机计划支持西弗吉尼亚大学化学系的Kung K.Wang博士的研究。王教授将专注于合成方法，产生新型的碳双自由基，以及随后的自由基过程的机制研究，这些过程最近在生物系统中找到了对应的东西。***

9307994 Wang The focus of this research is the development of new methods for the synthesis of enediynes and enyne-allenes which provide easy entries to a variety of carbon diradicals and mechanistic studies of the subsequent radical processes. The first objective is to develop the use of the condensation reaction of sillylallenylboranes with acetylenic and allenic aldehydes for the synthesis of enediynes and enyne-allenes having diverse chemical structures. New synthetic routes to enediynes, enyne-allenes, diene-allenes, enediallenes and other related structures via the intramolecular migration reaction of organoborate complexes will also be developed. The formation of carbon diradicals from these unsaturated compounds will be studied using the strategy of generating new types of diradicals by intramolecularly capturing the initially formed diradical with a properly situated carbon-carbon double or triple bond. This will allow the radical centers to be moved around the molecule and can lead to the formation of other reactive species, such as o-quinodimethanes. %%% With this award, the Synthetic Organic Program is supporting the research of Dr. Kung K. Wang of the Department of Chemistry at West Virgina University. Professor Wang will focus his work on synthetic methods generating new types of carbon diradicals and the mechanistic studies of the subsequent radical processes which have recently found their counterpart in biological systems. ***