Aryne Radical Chemistry

芳烃在有机合成中引起了极大的关注，离子加成、Sigma键插入、环加成和过渡金属介导级联偶联等都得到了很好的发展。然而，以芳烃为自由基受体的自由基化学几乎没有被探索过。芳烃自由基化学领域的最大挑战在于芳烃中间体和自由基物种(在连锁反应中)的低浓度，这使得这两个活性中间体不太可能偶联。在第一个项目期间取得的成果的鼓舞下，将在第二个供资期间调查寿命较长的自由基对芳烃的反应性。这些稳定的自由基与芳烃反应生成相应的芳基加成物，进而进行氢原子转移反应、环化反应和官能团迁移反应。芳烃上的这种转化不能通过使用离子类型的化学或环加成来实现。因此，本文提出的自由基化学大大扩展了芳烃化学的范围。所提出的自由基级联以一种概念新颖的方法提供了密集替代和有价值的芳烃。

Arynes have gained great attention in organic synthesis and ionic additions, sigma-bond insertions, cycloadditions and transition-metal mediated cascade couplings have been developed. However, radical chemistry comprising arynes as radical acceptors is nearly unexplored. The great challenge in the field of aryne radical chemistry lies in the low concentration of both the aryne intermediate and also the radical species (in a chain reaction) that renders the coupling of these two reactive intermediates highly unlikely. Encouraged by results obtained in the first project period, the reactivity of longer-lived radicals towards arynes will be investigated in the second funding period. The addition of such stable radicals to arynes will lead to the corresponding adduct aryl radicals which can further engage in hydrogen atom transfer reactions, cyclizations and functional group migration reactions. Such transformations on arynes cannot be achieved by using ionic type chemistry or cycloadditions. Hence, the herein suggested radical chemistry significantly expands the scope of aryne chemistry. The suggested radical cascades provide densely substituted and valuable arenes in a conceptually novel approach.