Non‐Noble Metal Anchored 2D Covalent Organic Framework for Ambient CO2 Fixation to High‐Value Compounds.

The catalytic functionalization of CO2 into high‐value compounds comprises a promising approach to mitigate its atmospheric content and sustainable generation of fine chemicals. Herein, we report application of a crystalline, nano‐porous 2D COF (ET‐BP‐COF) for utilization of CO2. The ET‐BP‐COF features a unique 2D kagome (kgm) topology composed of hexagonal and triangular 1D channels decorated with bipyridine sites, which were exploited for covalent anchoring of eco‐friendly Cu(I) by post‐synthetic method. The Cu(I) engrafted COF was applied as a recyclable catalyst for coupling CO2 with alkynes to generate two high‐value compounds, α‐alkylidene cyclic carbonates (α‐ACCs) and 2‐oxazolidinones. Notably, Cu(I)@ET‐BP‐COF demonstrated excellent catalytic performance for transforming propargylic amine and CO2 to 2‐oxazolidinone, an essential building block for antibiotics. Besides, an efficient transformation of propargylic alcohols to generate α‐ACCs, valuable commodity chemicals, has been achieved by utilizing carbon dioxide. Further, detailed theoretical simulations disclosed the insight mechanistic path of Cu(I) catalyzed coupling of CO2 with alkynes to produce 2‐oxazolidinones and α‐ACCs. Significantly, Cu(I)@COF was reusable for multiple cycles without losing framework rigidity and catalytic performance. This study showcases the potential application of ET‐BP‐COF for stable anchoring of eco‐friendly metals as catalytic sites for effective utilization of CO2 to produce two high‐value products.