Quan Yangjian, Song Yang, Shi Wenjie, Xu Ziwan, Chen Justin S, Jiang Xiaomin, Wang Cheng, Lin Wenbin
Department of Chemistry, The University of Chicago, Chicago, Illinois 60637, United States.
College of Chemistry and Chemical Engineering, iCHEM, State Key Laboratory of Physical Chemistry of Solid Surface, Xiamen University, Xiamen 361005, People's Republic of China.
J Am Chem Soc. 2020 May 13;142(19):8602-8607. doi: 10.1021/jacs.0c02966. Epub 2020 Apr 29.
Here we report the design of an enzyme-inspired metal-organic framework (MOF), -OTf-Ir, by installing strong Lewis acid and photoredox sites in engineered mesopores. Al-MOF (), with mixed 2,2'-bipyridyl-5,5-dicarboxylate (dcbpy) and 1,4-benzenediacrylate (pdac) ligands, was oxidized with ozone and then triflated to generate strongly Lewis acidic Al-OTf sites in the mesopores, followed by the installation of [Ir(ppy)(dcbpy)] (ppy = 2-phenylpyridine) sites to afford -OTf-Ir with both Lewis acid and photoredox sites. -OTf-Ir effectively catalyzed reductive cross-coupling of -hydroxyphthalimide esters or aryl bromomethyl ketones with vinyl- or alkynyl-azaarenes to afford new azaarene derivatives. -OTf-Ir enabled catalytic synthesis of anticholinergic drugs Pheniramine and Chlorpheniramine.
在此，我们报告了一种受酶启发的金属有机框架（MOF）——-OTf-Ir的设计，通过在工程化介孔中引入强路易斯酸和光氧化还原位点来实现。具有混合的2,2'-联吡啶-5,5-二羧酸酯（dcbpy）和1,4-苯二丙烯酸酯（pdac）配体的Al-MOF（），先用臭氧氧化，然后进行三氟甲磺酰化，以在介孔中生成强路易斯酸性的Al-OTf位点，接着引入[Ir(ppy)(dcbpy)]（ppy = 2-苯基吡啶）位点，从而得到同时具有路易斯酸和光氧化还原位点的-OTf-Ir。-OTf-Ir有效地催化了α-羟基邻苯二甲酰亚胺酯或芳基溴甲基酮与乙烯基或炔基氮杂芳烃的还原交叉偶联反应，以得到新的氮杂芳烃衍生物。-OTf-Ir实现了抗胆碱能药物非尼拉敏和氯苯那敏的催化合成。
