Construction of 3,12-Diazatetracyclododecane-dienes through Unexpected Visible-Light-Induced Radical Cascade Cyclization

Abstract

A novel visible-light-induced cascade radical cyclization reaction of 3-cyano-4-aryl-1,4-dihydropyridines for the construction of 3,12-diazatetracyclododecane-diene derivatives is reported for the first time. In the presence of 410 nm blue LED lamp as the light source and ethanol as the solvent, the reactions proceed smoothly to afford photocyclization products in good yields. The process is carried out through the breaking of original CC double bonds and the formation of three new single bonds in one pot and proved to be able to tolerate different substituents.

Chemoselective [2 + 2]/[3 + 2] Photocycloaddition of 1,4-Dihydropyridines: Experimental and Theoretical Investigation

“…They have achieved diverse medical applications in antitumor, antimicrobial, analgesic, and anticonvulsant treatments and especially clinical treatment of cardiovascular diseases such as hypertension and angina pectoris due to their recognized capacity as calcium channel blockers and antioxidant activity . They are also important intermediates of photocycloaddition for the preparation of cage compounds with structural complexity, such as 3,9-diazatetraasterane, 3,6-diazatetraasterane, 3,9-diazatetracyclododecane, 6,12-diazaterakishomocubanes, and 3,12-diazatetracyclododecane-diene . These cage compounds, which are similar to common cages such as cubane, homocubane, tetraastarane, and pentacycloundecane, have received increasing attention in drug discovery for their high conformational rigidity and lipophilicity .…”