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o-Quinone methide with overcrowded olefin component as a dehydridation catalyst under aerobic photoirradiation conditions
Chemical Science ( IF 7.6 ) Pub Date : 2021-1-15 , DOI: 10.1039/d0sc06240e
Daisuke Uraguchi 1 , Kohsuke Kato 2 , Takashi Ooi 2
Affiliation  

An o-quinone methide (o-QM) featuring an overcrowded olefinic framework is introduced, which exhibits dehydridation activity owing to its enhanced zwitterionic character, particularly through photoexcitation. The characteristics of this o-QM enable the operation of dehydridative catalysis in the oxidation of benzylic secondary alcohols under aerobic photoirradiation conditions. An experimental analysis and density functional theory calculations provide mechanistic insights; the ground-state zwitterionic intermediate abstracts a hydride and proton simultaneously, and the active oxygen species facilitate catalyst regeneration.

中文翻译:

在好氧光辐照条件下,邻苯二甲醚甲基化过度拥挤作为脱水催化剂

介绍了一种具有过度拥挤的烯烃骨架的苯二甲酰亚胺(o- QM),由于其增强的两性离子特性(特别是通过光激发),因此具有脱水活性。该o- QM的特性使得在好氧光辐照条件下在苄基仲醇的氧化中能够进行脱水催化。实验分析和密度泛函理论计算提供了机械方面的见解;基态两性离子中间体同时提取氢化物和质子,而活性氧则促进催化剂的再生。
更新日期:2021-01-20
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