铁催化的苯并异吡喃鎓四氟硼酸盐的氧化自由基偶联行为研究

Study on Iron-Catalyzed Oxidative Free Radical Dimerization of Isochromenylium Tetrafluoroborate

苯并异吡喃鎓四氟硼酸盐是新近发现的一类新型有机盐,具有对空气和潮气的较高稳定性,同时保持苯并异吡喃鎓盐的高反应活性.研究了苯并异吡喃鎓四氟硼酸盐在几种铁盐和铁配合物催化剂存在下与过氧化氢之间的氧化反应行为,发现了一类具有特色的经高价铁物种催化氧化O—H键引发的自由基双分子偶联反应.本工作对该反应的条件进行了优化研究,对反应产物和主要副产物的形成机理进行了探讨.

Isochromenylium tetrafluoroborates（ICTBs） are a novel class of air-and moisture-stable organic salts recently developed by our group.These organic salts retain high reactivity of the unique isochromenylium intermediates in many chemical reactions.The dimerization of ICTBs via O—H bond oxidation with hyper-iron species in the presence of hydrogen peroxide and catalytic amount of iron com-plex has been studied in this work.Under the optimized conditions,two interesting dimeric products and some minor byproducts were identified,and the corresponding mechanisms were discussed.