Stabilising fleeting intermediates of stilbene photocyclization with amino-borane functionalisation: the rare isolation of persistent dihydrophenanthrenes and their [1,5] H-shift isomers

Abstract

The key intermediate, 4a,4b-dihydrophenanthrene (DPH), involved in the photocyclization of stilbene and derivatives is known to be unstable, and is therefore poorly characterized/understood. We have found that functionalising stilbenes with NMe₂ and BMes₂ groups can greatly enhance the stability of 4a,4b-DPHs, allowing quantitative isolation and full characterization of these rare species. Furthermore, we discovered that the new amino-borane decorated 4a,4b-DPHs can undergo thermal [1,5] H sigmatropic shift, forming isomers 4a,10a-DPHs. Both 4a,4b-DHPs and 4a,10a-DHPs are stable towards air and moisture, while only the former were found to undergo oxidative dehydrogenation upon irradiation at 365 nm under air, yielding brightly blue/green fluorescent NMe₂ and BMes₂ functionalised phenanthrene analogues. Control studies established that the trans-Mes₂B–Ph–NMe₂ unit is responsible for the stability of these isolated 4a,4b-DHPs and their [1,5]-H shift isomers.