1-(omega-Azidoalkyl)pyrrolyl-terminated polyisobutylene (PIB) was successfully synthesized both by substitution of the terminal halide of 1-(omega-haloalkyl)pyrrolyl-terminated PIB with sodium azide and by in situ quenching of quasiliving PIB with a 1-(omega-azidoalkyl)pyrrole Azide substitution of the terminal halide was carried out in 50/50 heptane/DMF at 90 degrees C for 24 h using excess azide The 1-(omega-haloalkyl)pyrrolyl-PIB precursors included 1-(2-chloroethyl)pyrrolyl-PIB, 1-(2-bromoethyl)pyrrolyl-PIB, and 1-(3-bromopropyl)pyrrolyl-PIB. In situ quenching involved direct addition of 1-(2-azidoethyl)pyrrole to quasiliving PIB initiated from 5-tert-butyl-1,3-di(1-chloro-1-methylethyl)benzene (bDCC)/TiCl4 at -70 degrees C in hexane/CH3Cl (60/40, v/v). H-1 NMR analysis of the quenched product revealed mixed isomeric end groups in which PIB was attached at either C-2 or C-3 of the pyrrole ring (C-2/C-3 = 0 40/0 60) SEC indicated the absence of coupled PIB under optimized conditions, confirming exclusive mono-substitution on each pyrrole ring 1-(3-Azidopropyl)pyrrolyl-PIB was reacted in modular fashion with various functional alkynes, propargyl alcohol, propargyl acrylate, glycidyl propargyl ether, and 3-dimethylamino-1-propyne, via a Huisgen 1,3-dipolar cycloaddition (Click) reaction, using Cu(I)Br/N,N,N',N '',N ''-pentamethyldiethylenetriamine or bromtris(triphenylphosphine)Cu(I) as catalyst The reactions were quantitative and produced PIBs bearing terminal hydroxyl, acrylate, glycidyl, or dimethylaminomethyl groups attached via exclusively four-substituted triazole linkages (C) 2010 Wiley Periodicals, Inc J Polym Sci Part A Polym Chem 48 25332545, 2010