Synthesis and protein degradation capacity of photoactivated enediynes.

[structure: see text] The viability of proteins as targets of thermally and photoactivated enediynes has been confirmed at the molecular level. Model studies using a labeled substrate confirmed the efficacy of atom transfer from diyl radicals produced from enediynes to form captodatively stabilized carbon centered aminoacyl radicals, which then undergo either fragmentation or dimerization. To exploit this finding, a family of enediynes was developed using an intramolecular coupling strategy.

Protein degradation with photoactivated enediyne-amino acid conjugates.

A series of photoactivated enediynes was prepared, and successfully employed for the selective degradation of target proteins.

Halo-enediynes: probing the electronic and stereoelectronic contributions to the Bergman cycloaromatization.

A series of halogen-substituted cyclic enediynes were prepared with use of carbenoid coupling strategy. DFT analysis, initially used to identify synthesis candidates, was also employed to rationalize the propensity for cycloaromatization of the compounds. In all cases studied the halogen atom had a strongly retardative effect on the thermal Bergman cycloaromatization reaction.