Theoretical investigation on the Rh(Ⅰ)-catalyzed [6+2] cycloaddition reactions of 4-allenal

• 作 者: Lingli Han Chunmei Du Tao Liu
• 机 构: Department of Chemistry and Chemical Engineering, Jining University, Qufu 273155, Shandong,China
• 出 处: 第六届全国物理无机化学会议
• 发表日期: 2012年8期
• 关键词: cycloisomerization mechanism catalysts DFT

　　On the basis of a broad density functional theory (DFT) computational study, mechanistic understandings of the cycloisomerization reaction of 4-allenal 1 catalyzed by the two catalysts, RhCl(pph3)3 and Rh(dppe)ClO4, which result in bicyclic ketone and bicyclic alcohol products, respectively, are provided.The calculated results confirm that the C-C multiple bond can insert into the oxo-rhodacycle intermediate and the free energy barrier for the process is 19.75 kcal/mol.Our results agree with experimental findings.