自由基环化制备内酰胺地理论研究.pdfVIP

2008 年第 28 卷 有 机 化 学 Vol. 28, 2008 第 4 期, 685～692 Chinese Journal of Organic Chemistry No. 4, 685～692 ·研究论文· 自由基环化制备β- 内酰胺的理论研究 孟祥明 俞一赟 石 景 傅 尧* ( 中国科学技术大学化学系 合肥 230026) 摘要 使用密度泛函方法在 UB3LYP/6-311 ＋＋G(3df, 2p)水平上对自由基环化合 β - 内酰胺的四种反应途径进行理论 研究. 结合 Marcus 理论对影响反应的热力学及动力学因素进行分析, 发现氨基甲酰基自由基 4-exo 环合反应是理想的 动力学控制过程; 酰胺自由基的 4-exo 环合反应与 5-endo 环合反应相比是动力学有利的转化过程; 单取代的酰胺烷基 自由基的4-exo 环合反应是一类动力学和热力学都较为不利的反应; 羰基自由基加成亚胺 N ＝C 双键的 4-exo 环合反应 与 5-endo 环合反应相比动力学不利而热力学有利. 关键词 β - 内酰胺; 自由基环化反应; 密度泛函方法; Marcus 理论 Theoretical Study on Radical Cyclizations for Preparation of β-Lactams MENG, Xiang-Ming YU, Yi-Yun SHI, Jing FU, Yao* (Department of Chemistry , University of Science and Technology of China, Hefei 230026) Abstract The preparation of β -lactams through four different radical cyclization reactions was studied by density functional theory calculations at the UB3LYP/6-311 ＋＋G(3df, 2p) level. Thermodynamics and ki- netics of these radical cyclizations were analyzed using the Marcus theory. The calculated results showed that the 4-exo cyclization of carbamoyl radical was an ideal kinetic-control process. The 4-exo cyclization of carbamoylalkyl radical was predicted to be kinetically competitive with the 5-endo process. The 4-exo cy- clization of amido radical was less favorable both kinetically and thermodynamically. Finally, the 4-exo ring closure of an acyl radical onto an imine acceptor was thermodynamically competitive with the 5-endo proc- ess but less favorable kinetically. Keywords