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Preparation of 6-aminocyclohepta-2,4-dien-1-one Derivatives via Tricarbonyl(tropone)iron
Published on: August 12, 2019
DFT Study of Iron-Catalyzed [4 + 4] Cycloaddition of 1,3-Dienes: Mechanism and Diastereoselectivity
Baotong Huang1, Zhenfeng Shang1, Ruifang Li1
1Department of Chemistry, Key Laboratory of Advanced Energy Materials Chemistry (Ministry of Education), College of Chemistry, Nankai University, Tianjin300071, P. R. China.
Abstract:
The mechanism of diastereoselective [4 + 4] cycloaddition of 1,3-dienes catalyzed by Fe complexes bearing 2-(imino)pyridine (PI) ligands was investigated using density functional theory calculations. The results reveal that the reaction proceeds via diene coordination, oxidative cyclization, allyl isomerization and reductive elimination. Reductive elimination is identified as the rate-determining step. The computational study indicates that the steric repulsion between substituents on 1-substituted dienes and (iPrPI)Fe moiety governs the diastereoselectivity. These computational findings elucidate the detailed reaction pathway and clarify several ambiguities observed experimentally.
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