Bicyclo[2.2.0]hexene derivatives as a proaromatic platform for group transfer and chemical sensing

Here we report the design, preparation, synthetic utility, and sensing application of a class of proaromatic structures, namely bicyclo[2.2.0]hexene (BCH) derivatives. Building on a valence isomerism concept, they feature modular and easy synthesis as well as high thermal stability, and can be oxidatively activated under mild conditions. New alkyl transfer reactions using BCHs as a radical donor have been developed to showcase the utility of their proaromaticity. Moreover, the redox-triggered valence isomerization of a quinoline-derived BCH led to colorimetric and fluorescent responses toward vapors of electrophilic reagents in solution and solid phase, respectively. This optical response was shown to involve a 1,3-cyclohexadiene structure that possesses an intramolecular charge transfer excited state with interesting aggregation induced emission (AIE) character. Thus, the potential of BCHs has been demonstrated as a versatile platform for the development of new reagents and functional materials. Cyclohexadienes have been widely explored as proaromatic surrogates for group transfer reactions but limited storage stability and difficult accessibility of these compounds limits the application range. Here, the authors present a class of proaromatic bicyclo[2.2.0]hexene derivatives and demonstrate their application in alkyl transfer reactions and sensing applications.