DFT Study on the Mechanisms of Iron-Catalyzed Ortho C-H Homoallylation of Aromatic Ketones with Methylenecyclopropanes

被引:2
作者
Zheng, Lin [1 ]
Wan, Xin [1 ]
Ren, Qinghua [1 ]
机构
[1] Shanghai Univ, Dept Chem, Shanghai 200444, Peoples R China
基金
上海市自然科学基金;
关键词
DENSITY-FUNCTIONAL THEORY; MOLECULAR-ORBITAL METHODS; CROSS-COUPLING REACTIONS; DIRECT ARYLATION; ACTIVATION; STABILITY; COMPLEXES; AMINATION; REAGENTS; MODEL;
D O I
10.1021/acs.organomet.2c00110
中图分类号
O61 [无机化学];
学科分类号
070301 ; 081704 ;
摘要
The mechanisms of iron-catalyzed ortho C-H homoallylation of aromatic ketones with methylenecyclopropanes are calculated using density functional theory calculations with B3LYP-D3BJ functionals and solvation model density (cyclohexane) model. Our results show that the catalytic cycle includes C-H bond oxidative addition, insertion of C-C double bond, ring -opening reaction, reductive elimination, ligand exchange, and the catalyst regeneration. Two possible catalytic cycles are calculated, where Path A is v where the iron active catalyst first combined with 2,2-dimethyl-1-[4-(trifluoromethyl) phenyl]-propan-1-one and Path B is where the iron active catalyst initially attacked 2-phenyl-1-methylenecyclopropane. Our calculated results show that the rate-determining step in the whole catalytic cycle for the favored Path A is the C-H bond oxidation addition step, where Gibbs free energy in solvent cyclohexane, Delta Gsol, is 10.8 kcal/mol.
引用
收藏
页码:632 / 640
页数:9
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