Highly Selective Enamination of β-ketoesters Catalyzed by Interlocked [Cu8 ] and [Cu18 ] Nanocages

Angew Chem Int Ed Engl. 2019 Sep 16;58(38):13302-13307. doi: 10.1002/anie.201906306. Epub 2019 Aug 7.

Abstract

Interlocking cages are of great interest due to their fascinating structures and potential applications. However, the interlocking of different cages has not been previously reported. Herein, quadruply interlocked [Cu8 ] and [Cu18 ] nanocages have been constructed and structurally characterized in cationic metal-organic framework {[CuI Cu4 II (XN)4 (PTA)4 (H2 O)4 ]0.5 SO4 ⋅5 H2 O⋅EtOH}n (1). 1 can trap the anionic pollutant CrO4 2- and the radioactive-contaminant simulant ReO4 - with an uptake capacity of 83.2 and 218 mg g-1 , respectively. Catalytic investigations reveal 1 is an efficient heterogeneous catalyst for the enamination of ethyl acetoacetate with aniline and the turnover frequency (TOF) can reach a record value of 4000 h-1 . More importantly, 1 represents the first of a catalyst of enamination to exhibit excellent size selectivity on different substrates. The robust catalyst can be reused at least ten times without obvious loss in catalytic activity.

Keywords: cage compounds; enamination; heterogeneous catalysis; metal-organic framework; microporous materials.

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