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Syntheses of Tetrasubstituted [10]Cycloparaphenylenes by a Pd-catalyzed Coupling Reaction. Remarkable Effect of Strain on the Oxidative Addition and Reductive Elimination.
Chemistry - An Asian Journal ( IF 4.1 ) Pub Date : 2020-06-17 , DOI: 10.1002/asia.202000711
Eiichi Kayahara 1 , Masaya Nakano 1 , Liansheng Sun 1 , Kosuke Ishida 1 , Shigeru Yamago 1
Affiliation  

A small library of tetrasubstituted [10]cycloparaphenylene ([10]CPP) derivatives bearing alkyl, alkenyl, alkynyl and aryl substituents was constructed by a Pd‐catalyzed cross‐coupling reaction starting from tetratriflate [10]CPP 5e, which was readily available in high yields on a >2 g scale. The CPP skeleton increases the reactivity of aryl triflate for oxidative addition to the Pd species, and 5e is 10 times more reactive than its linear paraphenylene analogue, as determined by competition experiments. Theoretical calculations suggest that the accumulation of the small strain relief from each paraphenylene unit not involved in the reaction is responsible for the observed enhanced reactivity.

中文翻译:

通过Pd催化的偶联反应合成四取代的[10]环对亚苯基。应变对氧化添加和还原消除的显着影响。

四取代的[10]环的一小库([10] CPP)衍生物轴承烷基,烯基,炔基和芳基取代基是通过从tetratriflate [10] CPP开始Pd-催化的交叉偶联反应构建5 ë,这是容易获得的> 2 g规模的高产量。该CPP骨架增加芳基三氟甲磺酸酯的反应性的氧化除钯物种,和5 ë是10倍比其线性对苯类似物更具反应性的,如通过竞争实验来确定。理论计算表明,未参与反应的每个对亚苯基单元产生的小的应变释放的累积是观察到的增强的反应性的原因。
更新日期:2020-08-18
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