Abstract
The target research is regard of utilizing benzopyrazinobarrelene (BPB) and benzoquinoxalinobarrelene (BQB) as experimental platforms to examine the substituent effect on the di-π-methane (DPM) rearrangement of barrelene-like skeleton. By selecting the appropriate functionality on the pyrazine ring (in this case, the di-cyano groups or an extra benzene ring), the photoreaction could be limited into chemoselectivity of aza-di-π-methane reaction only, thus facilitate the examination of regioselectivity induced by installations of substituents on the bicyclo[2.2.2] skeleton of substrates. The result of the photoreaction was then given rationale by the relative stability of intermediate (biradical) along with theoretical calculation.