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

机译:序列受控的α,β-连接的噻唑的合成,结构和性质

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摘要

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.
机译:具有头到尾连通性的α,β-连接的寡噻唑被介绍为一个新的螺旋支架家族。在2-苯基噻唑的5-位和4-位上钯催化的交叉偶联反应的组合导致合成具有邻位键且具有各种定义序列的寡聚(2-苯基噻唑)。 α,β-连接的寡聚(2-苯基噻唑)的二级结构显示出对它们序列的明显依赖性。三聚体,四聚体和六聚体具有首尾相连的X射线晶体学分析表明形成了螺旋结构,该结构通过分子内力(包括杂原子(S···N),CH-π)的结合而得以稳定。和π-π相互作用。手性端基的引入成功地导致手性被诱导成螺旋构象。通过α,β-连接的低聚噻唑中的歧管连接途径已经证明了控制几何形状和光功能的可编程序列。

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