Shi Dongying, He Cheng, Qi Bo, Chen Cong, Niu Jingyang, Duan Chunying
State Key Laboratory of Fine Chemicals , Dalian University of Technology , Dalian , 116024 , P. R. China . Email:
College of Chemistry and Chemical Engineering , Henan University , Kaifeng , 475004 , P. R. China.
Chem Sci. 2015 Feb 1;6(2):1035-1042. doi: 10.1039/c4sc02362e. Epub 2014 Oct 30.
The direct formation of new C-C bonds through photocatalytic oxidative coupling from low reactive sp C-H bonds using environmentally benign and cheap oxygen as oxidant is an important area in sustainable chemistry. By incorporating the photoredox catalyst [SiWORu(HO)] into the pores of Cu-based metal-organic frameworks, a new approach for merging Cu-catalysis/Ru-photocatalysis within one single MOF was achieved. The direct Cu-O-W(Ru) bridges made the two metal catalyses being synergetic, enabling the application on the catalysis of the oxidative coupling C-C bond formation from acetophenones and -phenyl-tetrahydroisoquinoline with excellent conversion and size-selectivity. The method takes advantage of visible light photoredox catalysis to generate iminium ion intermediate from -phenyl-tetrahydroisoquinoline under mild conditions and the easy combination with Cu-catalyzed activation of nucleophiles. Control catalytic experiments using similar Cu-based sheets but with the photoredox catalytic anions embedded was also investigated for comparison.
利用环境友好且廉价的氧气作为氧化剂，通过光催化氧化偶联从低反应活性的sp C-H键直接形成新的C-C键，是可持续化学中的一个重要领域。通过将光氧化还原催化剂[SiWORu(HO)]纳入铜基金属有机框架的孔中，实现了在单个金属有机框架内融合铜催化/钌光催化的新方法。直接的Cu-O-W(Ru)桥使两种金属催化具有协同作用，能够应用于催化苯乙酮和β-苯基四氢异喹啉的氧化偶联C-C键形成，具有优异的转化率和尺寸选择性。该方法利用可见光光氧化还原催化在温和条件下从β-苯基四氢异喹啉生成亚胺离子中间体，并易于与铜催化的亲核试剂活化相结合。还研究了使用类似的铜基片材但嵌入光氧化还原催化阴离子的对照催化实验进行比较。
