C-H Polyaddition of Dimethoxyarenes to Unconjugated Dienes by Rare Earth Catalysts
C-H Polyaddition of Dimethoxyarenes to Unconjugated Dienes by Rare Earth Catalysts
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DOI：
10.1021/jacs.6b03859
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发表时间：
2016-05-18
影响因子：
15
通讯作者：
Hou, Zhaomin
中科院分区：
文献类型：
--
作者：
Shi, Xiaochao;Nishiura, Masayoshi;Hou, Zhaomin
利用阳离子半夹心稀土烷基催化剂，首次实现了1,4-二甲氧基苯、4,4'-二甲氧基联苯等二甲氧基芳烃与降冰片二烯、1,4-二乙烯基苯等非共轭二烯的C-H加成反应。该方案提供了由二甲氧基芳烃部分和非极性烃结构基序（环状、线性和芳香族）组成的新型聚合物材料，这些材料以完美交替的顺序排列，否则很难制造。该反应通过 C=C 双键插入两个甲氧基邻位的 C-H 键以逐步聚合的方式进行。
The C-H polyaddition of dimethoxyarenes such as 1,4-dimethoxybenzene and 4,4'-dimethoxybiphenyl to unconjugated dienes such as norbomadiene and 1,4-divinylbenzene has been achieved for the first time by using cationic half-sandwich rare earth alkyl catalysts. This protocol afforded novel polymer materials consisting of dimethoxyarene moieties and nonpolar hydrocarbon structure motifs (cyclic, linear, and aromatic) in perfectly alternating sequences that are otherwise difficult to make. The reaction proceeded via C=C double bond insertion into a C-H bond ortho to each of the two methoxy groups in a step-growth polymerization fashion.