A Noble‐Metal‐Free Metal–Organic Framework (MOF) Catalyst for the Highly Efficient Conversion of CO 2 with Propargylic Alcohols

Cyclization of propargylic alcohols with CO 2 is an important reaction in industry, and noble‐metal catalysts are often employed to ensure the high product yields under environmentally friendly conditions. Herein a porous noble‐metal‐free framework 1 with large 1D channels of 1.66 nm diameter was synthesized for this reaction. Compound 1 exhibits excellent acid/base stability, and is even stable in corrosive triethylamine for one month. Catalytic studies indicate that 1 is an effective catalyst for the cyclization of propargylic alcohols and CO 2 without any solvents under mild conditions, and the turnover number (TON) can reach to a record value of 14 400. Furthermore, this MOF catalyst also has rarely seen catalytic activity when the biological macromolecule ethisterone was used as a substrate. Mechanistic studies reveal that the synergistic catalytic effect between Cu I and In III plays a key role in the conversion of CO 2 .