An Efficient Route to 3,3'-Biindolinylidene-diones by Iron-Catalyzed Dimerization of Isatins

Iron-catalyzed dimerization of various isatin derivatives is described for the efficient synthesis of 3,3'-biindolinylidene-diones (isoindigos). The reaction provides easy access to self-coupled and cross-coupled 3,3'-indolinylidene-diones that have high relevance to biology and materials. This Fe(0)- or Fe(II)-catalyzed dimerization reaction tolerates a wide range of functionalities, such as fluoro, chloro, bromo, alkenyl, nitrile, ether, ester, pyrrolyl, indolyl and carbazolyl groups, including cyclic and acyclic alkyls as well as an alkyl-bearing fatty-alcohol moiety. Especially, the coupling between two distinct isatins provided excellent selectivity for the cross-dimerization with trace of self-couplings. The single-crystal X-ray diffraction study established the molecular structure of eight dimerized products. A preliminary mechanistic study of the Fe-catalyzed dimerization supported the radical pathway for the reaction.