Synthesis, Structure, and Properties of α,β‐Linked Oligothiazoles with Controlled Sequence

Abstract

α,β-Linked oligothiazoles with head-to-tail connectivity are presented as a new family of helical scaffolds. Combinations of palladium-catalyzed cross-coupling reactions at the 5- and 4-positions of 2-phenylthiazole led to the synthesis of oligo(2-phenylthiazoles) with ortho linkages with a variety of defined sequences. The secondary structures of the α,β-linked oligo(2-phenylthiazoles) showed a clear dependence on their sequences. X-ray crystallography of the trimer, tetramer, and hexamer with head-to-tail connection revealed the formation of a helical structure, which was stabilized by a combination of intramolecular forces, including interheteroatom (S⋅⋅⋅N), CH-π, and π-π interactions. The introduction of a chiral end-group successfully led to the induction of chirality into the helical conformations. Programmable sequences for controlled geometries and photofunctions have been demonstrated through the manifold connection pathways in α,β-linked oligothiazoles.