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A metal‐ and oxidant‐free procedure for the three‐component haloazidation/cyclization of phenyl‐linked 1,6‐enynes with TMSN3 and N‐iodo(bromo)succinimide under the irradiation of visible light was described. Moreover, this reaction involved a radical addition/5‐exo‐dig cyclization/radical coupling process, and realized simultaneous construction of C−N, C−C, and C−X (I, Br) bonds in one step.
A visible‐light‐promoted three‐component haloazidation/cyclization of phenyl‐linked 1,6‐enynes with TMSN3 and N‐iodo/bromo‐succinimide under metal‐ and oxidant‐free conditions was presented. These methods provide an alternative and facile synthetic route to access a series of haloazidated 2,3‐dihydro‐1H‐indenes in moderate yields. This is a useful, time‐efficient, and scalable procedure for the construction of C−N, C−C, and C−X (I, Br) bonds in one step.