Intramolecular nucleophilic capture of radical cations by tethered hydroxy functions

Abstract

Abstract A range of systems bearing hydroxy functions tethered to the molecular framework gives rise to a family of interesting radical cations, 5 + – 11 + , upon electron transfer to photo-excited cyanoaromatics. Geraniol ( 5 ), nerol ( 6 ), citronellol ( 7 ), chrysanthemol ( 8 ), homochrysanthemol ( 9 ), trans -1- o -hydroxyphenyl-2-phenylcyclopropane ( 10 ), and endo -5-hydroxymethylnorbornene ( 11 ), generate a series of mono-, bi-, or tricyclic ethers via a series of four- to seven-membered transition states. Two of the radical cations, 5 + and 6 + , undergo tandem cyclizations where 1,5- and/or 1,6-C–C cyclizations precede nucleophilic capture.