Stereospecific Single-Pot Route to Chiral Imidazolidines from Aziridines Using a 2D Cu Metal–Organic Framework

Abstract

The role of coordinatively unsaturated sites (CUS) in metal-organic framework (MOF)-catalyzed organic transformation is vital; however, the design and generation of such sites are challenging. We, therefore, report the synthesis of a novel two-dimensional (2D) MOF, [Cu(BTC)(Mim)]n (Cu-SKU-3), with pre-existing unsaturated Lewis acid sites. The presence of these active CUS facilitates a ready-to-use attribute in Cu-SKU-3, thereby subsiding the lengthy activation processes associated with MOF-based catalysis. The material has been completely characterized using single crystal X-ray diffraction (SCXRD), powder XRD (PXRD), thermogravimetric analysis (TGA), carbon, hydrogen, and nitrogen (CHN), Fourier-transform infrared (FTIR), and Brunauer-Emmett-Teller (BET) surface area analyses. We directly utilize Cu-SKU-3 for the synthesis of biologically valued chiral imidazolidine motifs in a one-pot fashion starting from aziridines. The chiral imidazolidines are synthesized in good yield (up to 89%) and with high optical purity (ee > 98-99%). Mechanistically, the transformation proceeds in a tandem fashion through stereospecific ring-opening of aziridines followed by the intramolecular cyclization (via sp3 C-H functionalization) reaction forming chiral imidazolidines. The material has an excellent heterogeneous attribute and can be reused several times for one-pot catalytic cycles.