Sustainable synthesis of drug intermediates via simultaneous utilization of carbon monoxide and ammonia over Pd@La-MOF

• Mitigation of hazardous CO and NH 3 to access the synthetically valuable primary aromatic amides via carbonylative amination of aryl halides over metal organic frameworks (MOFs). • Microwave assisted implantation of 3,4 nm pd nanoparticles on La-MOFs to generate flower shaped Pd@La-MOF composite. • LaMOFs acting as template induces the controlled growth of Pd NPs and stabilizes them over the outer surface. • Unsaturated metal sites in MOF via synergistic mode of σ and π bond binds CO more effectively which significantly enhances catalytic activity unlike other supported Pd nanoparticles. • Stability of the Pd nanoparticles on the surface of La-MOF by BTC −3 ligand which inhibits metal leaching and maintains heterogeneity of the catalyst system. Mitigation of carbon monoxide and ammonia to valuable primary aromatic amides is an imperative approach to control the environmentally harmful emissions thereby infusing towards sustainability. Designing of nanostructured catalyst for direct access to the synthetically valuable primary aromatic and heteroaromatic amides via carbonylative amination of aryl halides is always demanding since nano materials can bridge the gap between homogeneous and heterogeneous catalysis thus preserving the desirable attributes of both the systems towards sustainable catalysis. Herein, microwave assisted fabrication of highly uniform Pd NPs (3,4 nm) over La-MOFs has been performed and utilized efficiently for ligand free carbonylative amination of aryl iodides with carbon monoxide and ammonia. Moderate to high yields of benzamide derivatives, salicylamide, a drug having analgesic and antipyretic properties were achieved. The unsaturated metal sites in the MOF via synergistic mode of σ and π bonding binds with CO, which significantly enhances the catalytic activity of MOF-composite unlike other supported Pd NPs. DFT confirms the growth of pristine Pd 13 cluster within the framework, as active metal center for the carbonylative amination. Manideepa Sengupta, Subhasis Das, Sumantra Bhattacharya, Md Jahiruddin Gazi, V V D N Prasad, Sk Manirul Islam, * and Ankur Bordoloi.* Highly uniform Pd nanoparticles embedded La based MOF-composite has been synthesized for efficient carbonylative aminations of aryl halides with CO and NH 3 , utilizing the environmentally harmful emissions towards sustainable products. The unsaturated metal sites in MOF-composite via synergistic mode of σ and π bonding binds CO effectively, which is essential for the superior activity of the Pd@La-MOFs unlike other supported Pd nanoparticles.