Reduction of Ethynylenes to Vinylenes in a Macrocyclic π-Extended Thiophene Skeleton Under McMurry Coupling Conditions
Reduction of Ethynylenes to Vinylenes in a Macrocyclic π-Extended Thiophene Skeleton Under McMurry Coupling Conditions
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McMurry 耦合条件下大环 π-延伸噻吩骨架中亚乙炔还原为亚乙烯基
DOI：
10.1021/acs.joc.0c02080
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发表时间：
2020
期刊：
影响因子：
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通讯作者：
Iyoda Masahiko
中科院分区：
文献类型：
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作者：
Shirahata Keigo;Takashika Masataka;Hirabayashi Kazunori;Hasegawa Masashi;Otani Hiroyuki;Yamamoto Keitaro;Ie Yutaka;Shimizu Toshio;Aoyagi Shinobu;Iyoda Masahiko
McMurry偶联反应是制备π共轭分子最有用和最方便的工具之一。然而，对于含亚乙炔基键的应变大环的合成，有时会发生亚乙炔基还原为亚乙烯基键。特别地，对于使用由三个亚噻吩基、两个亚乙炔基和两个甲酰基组成的二聚体1的McMurry偶联来合成大环π-延伸的噻吩六聚体，亚乙炔基到亚乙烯基的还原经常发生以在一锅法中产生独特的产物，这取决于非常小的空间和电子效应，例如反应温度、钛试剂的量和噻吩六聚体的取代基。利用X射线衍射分析和OFET测量确定了还原噻吩六聚体的吸引人的结构和功能性质。
McMurry coupling is one of the most useful and convenient tools for the preparation of π-conjugated molecules. However, for the synthesis of strained macrocycles containing ethynylene linkages, reduction of ethynylene to vinylene linkage sometimes took place. Especially, for the synthesis of macrocyclic π-extended thiophene hexamers using McMurry coupling of dialdehyde1composed of three thienylene, two ethynylene, and two formyl groups, reduction of ethynylenes to vinylenes often takes place to produce unique products in a one-pot procedure, depending on very small steric and electronic effects such as reaction temperature, amounts of titanium reagent, and substituents of thiophene hexamers. The attractive structures and functional properties of reduced thiophene hexamers have been determined using X-ray analysis and OFET measurements.