Aryne Radical Chemistry

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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.