Mechanism of PdCl2-Catalyzed Cyclization of 3-alkyne-1,2-diols and isocyanate insertion to furanyl-3-carboxamides: A DFT Study

• Main Authors: XU, RUI-YOU, 徐睿佑
• Other Authors: LEE, SHYI-LONG
• Format: Others
• Language: en_US
• Published: 2017
• Online Access: http://ndltd.ncl.edu.tw/handle/k9gkyv

碩士 === 國立中正大學 === 化學暨生物化學研究所 === 105 === Abstract The Rajesh-Puri-Kant-Reddy mechanism of palladium coupling reaction has been investigated using DFT methods. The solution phase calculations were carried out using acetonitrile as a solvent in PCM model. It is found that the four step RPKR reaction mechanism actually consists of seven steps which are complexation, nucleophilic addition, dehydrochlorination, isocyanate insertion, dehydration, hydrogen chloride addition and catalyst regeneration. The dehydrochlorination is the rate-determining step for RPKR mechanism with relative Gibbs free energy values of 38.1 kcal/mol and 24.6 kcal/mol at B3LYP/6-31+G(d)//B3LYP/6-311++G(d,p) (LANL2TZ(f) for Pd) levle in gas and acetonitrile. However, the PCM model is not suitable for simulating the different results of different solvents in this experiment. Keyword: isocyanate insertion, palladium-catalyzed