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Density Functional Theory Study of the Mechanisms of Iron‐Catalyzed Regioselective Anti‐Markovnikov Addition of C‐H Bonds in Aromatic Ketones to Alkenes
Author(s) -
Ren Qinghua,
An Shanshan,
Wang Yuling,
Tong Weiqi
Publication year - 2019
Publication title -
applied organometallic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.53
H-Index - 71
eISSN - 1099-0739
pISSN - 0268-2605
DOI - 10.1002/aoc.5183
Subject(s) - chemistry , markovnikov's rule , regioselectivity , catalytic cycle , catalysis , ketone , free energy relationship , density functional theory , reductive elimination , alkylation , medicinal chemistry , computational chemistry , organic chemistry , reaction rate constant , physics , quantum mechanics , kinetics
The mechanisms of iron‐catalyzed regioselective anti‐Markovnikov addition of C‐H bonds in the aromatic ketones to alkenes are studied using Density Functional Theory (DFT) calculations with the B3LYP‐D3 method. Our results show that the overall catalytic cycle includes the initial generation of aromatic ketone C‐H activation, the coordination and insertion of a styrene, and finally C‐C reductive elimination. Two different alkylation products are obtained through the linear or branched formation via several different paths. The formation of the linear product is energetically favorable over that of the branched product, which is in agreement with the experimental observation. The rate‐limiting step for the whole catalytic cycle to obtain the main linear product is the reductive elimination step where the Gibbs free energy in solvent THF Δ G sol is 13.5 kcal/mol computed using the SMD method.