Applications Of Palladium-Catalyzed Carbonylative Reactions In The Synthesis Of Aromatic Aldehydes And Indene-1,3(2H)-diones

Objective:To investigate whether the isocyanide or aryl formate could be utilized in other novel palladium-catalyzed carbonylation reactions, which will expand their applications in both organic synthesis and bio-pharmaceutical development.Methods:1. By changing the solvents, catalysts, ligands, formate salts, etc., to find the optimal conditions of the palladium-catalyzed synthesis of aromatic aldehydes from aryl halides and isocyanide.2. By screening of the solvents, catalysts, ligands, bases, etc., to optimize the reaction conditions of the palladium-catalyzed intramolecular cyclization from aryl formate.Results:1. From the optimization results, the best reaction conditions are aromatic iodide,tert-butyl isocyanide, Pd(OAc)2, dppe, HCO2 Na, and anhydrous DMSO.2. According to the screening results, the optimal reaction conditions are 1-(2-iodo aryl)-1,3-dione, aryl formate, Pd Cl2(Me CN)2, Xant Phos, K3PO4, and DMSO.Conclusion:The palladium-catalyzed carbonylative cyclyzation reactions: I. Using isocyanide as a C1 source coupled with formate salt as hydrogen donor; II. Using aryl formate as a CO source to function with the oxygen-containing nucleophiles, has been successfully achieved. The results indicated that both isocyanide and aryl formate are potentially effective alternatives to toxic gas carbon monoxide, because they can react in a more environmentally friendly and safer fashion.