Cascade cyclizations of terpenoid polyalkenes triggered by photoelectron transfer-biomimetics with photons

Article abstract of DOI:10.1002/hlca.19950780815

Light-induced cyclizations of suitably functionalized polyalkene terpenoids, such as geranyl, all-trans-farnesyl, and all-trans-geranylgeranyl derivatives, via formation of radical cations are proven to be a powerful method for the single-step synthesis of mono- and mostly all-trans-fused polycyclic compounds from readily available precursors. Whereas some of these highly stereo- and chemoselective transformations required the use of micellar media, they can now be conveniently performed in homogeneous solutions upon suitable choice of the electron acceptors and of the functionality pattern of the polyalkene substrates. Moreover, the mode of cyclization, i.e., 6- vs. 5-membered ring formation termination of the cyclization cascades, are steered efficiently by the substituents of the polyalkenes (polyalkenyl acetate vs. α,β-unsaturated ethyl polyalkenoate and polyalkene-1,1-dicarbonitrile). At the same time, the protic solvents used add highly stereoselectivity to the ω-alkene sites of the polyalkenes in anti-Markovnikov sense which strongly suggests that radical cations are intercepted. Interestingly, the transformations achieved here upon photoelectron transfer parallel the biosynthetic paths of non-oxidative terpene cyclizations which are thought to occur purely by protonation of the isoprenoid polyalkenes.