Synthesis of Stereoregular Uniform Oligomers Possessing a Dense 1,2,3-Triazole Backbone

Abstract

Recent remarkable progress of precision polymerization techniques has allowed researchers to synthesize polymers of controlled molecular weight, tacticity, and monomer sequence with narrow distributions. However, it is still a challenging subject to synthesize uniform polymers and oligomers, which possess specific molecular weight, tacticity, and monomer sequence. Utilizing the advantages of t-butyl 4-azido-5-hexynoate (tBuAH), which we designed recently, for the synthesis of uniform polymers and oligomers, uniform oligomers of different stereoregularities possessing a dense 1,2,3-triazole backbone were synthesized using optically active tBuAH precursors by iterative procedures containing azidation, deprotection of the protecting group, and copper(I)-catalyzed azide–alkyne cycloaddition (CuAAC). The stereoregular uniform oligomers were characterized in the solid state by powder X-ray diffraction (PXRD) and in the solution state by pulse-field-gradient spin-echo (PGSE) NMR, ultraviolet (UV) absorption, and circular dichroism (CD) spectroscopic techniques. While the solubility of stereoregular uniform oligomers was investigated using common organic solvents, gelation was observed for solutions of two octamers of different stereoregularities in some solvents, e.g., toluene, tetrahydrofuran (THF), acetone, and methanol. It is noteworthy that the intermolecular attractive interaction depended on the stereoregularity in aprotic polar solvents, i.e., THF and acetone, presumably because of the different polarities of octamers.