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Reaction Mechanism for the LiCl‐Mediated Directed Zinc Insertion: A Computational and Experimental Study
Author(s) -
Liu ChingYuan,
Wang Xuan,
Furuyama Taniyuki,
Yasuike Shuji,
Muranaka Atsuya,
Morokuma Keiji,
Uchiyama Masanobu
Publication year - 2010
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.200902957
Subject(s) - zinc , lithium (medication) , regioselectivity , insertion reaction , chemistry , mechanism (biology) , reaction mechanism , lithium chloride , computational chemistry , combinatorial chemistry , organic chemistry , catalysis , physics , psychology , quantum mechanics , psychiatry
Tired of wondering about the role of LiCl in the DoI reaction of zinc? Kinetic/thermodynamic competitive experiments and DFT calculations were performed to clarify the regioselectivity and reaction mechanism/pathways of lithium chloride‐promoted directed zinc insertion into bromobenzenes. The results strongly suggest that the LiCl‐containing “push–pull form” transition state ( TS b ) is formed at an early stage, thus accelerating the reaction rate of zinc insertion. (DoI=directed ortho insertion.)