Regioregulated Syntheses of Poly(aminopyridine)s by Pd-catalyzed Amination Reaction.
Regioregulated Syntheses of Poly(aminopyridine)s by Pd-catalyzed Amination Reaction.
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DOI：
10.1002/marc.200900033
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发表时间：
2009-06
影响因子：
4.6
通讯作者：
J. Kuwabara;H. Mori;Takuya Teratani;M. Akita;T. Kanbara
中科院分区：
文献类型：
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作者：
J. Kuwabara;H. Mori;Takuya Teratani;M. Akita;T. Kanbara
通过钯催化的C-N偶联反应合成了区域调控的聚氨基吡啶。使用Pd（0）和大体积单齿膦配体的聚合反应不同地产生对位连接和间位连接的聚（氨基吡啶），而不需要保护过程。聚合物的区域规整性由（1）H NMR光谱证实。模型反应进行了研究，以评估在聚合物中的交联的可能性。在5-氨基-2-溴吡啶和2-氨基-5-溴吡啶之间观察到反应性的很大差异，这应该得到相同的产物。密度泛函理论（DFT）计算表明，Br-结合的碳原子和吡啶-氮原子的电子密度决定的单体的反应性。
Regioregulated poly(aminopyridine)s were synthesized by a Pd-catalyzed CN coupling reaction. The polymerization using Pd(0) and a bulky monodentate phosphine ligand distinctively produced the para-linked and meta-linked poly(aminopyridine)s, without the need for a protection process. The regioregularity of the polymer was confirmed by (1) H NMR spectroscopy. Model reactions were studied to evaluate the possibility of crosslinkage in the polymer. A large difference in reactivity was observed between 5-amino-2-bromopyridine and 2-amino-5-bromopyridine, which should have afforded same product. Density functional theory (DFT) calculations indicated that electron densities of the Br-bound carbon atom and the pyridine-nitrogen atom determine the reactivity of the monomers.