Premium
Mechanistic Study of the Fluoride‐Induced Activation of a Kobayashi Precursor: Pseudo‐S N 2 Pathway via a Pentacoordinated Silicon Ate Complex
Author(s) -
Liu Song,
Li Yang,
Lan Yu
Publication year - 2017
Publication title -
european journal of organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.825
H-Index - 155
eISSN - 1099-0690
pISSN - 1434-193X
DOI - 10.1002/ejoc.201701249
Subject(s) - chemistry , aryne , fluoride , trimethylsilyl , trifluoromethanesulfonate , dissociation (chemistry) , computational chemistry , density functional theory , fluorine , silicon , reaction mechanism , aryl , leaving group , solvent , basis set , bond dissociation energy , medicinal chemistry , organic chemistry , inorganic chemistry , catalysis , alkyl
Density functional theory calculations were used to reveal the mechanistic pathway of benzyne formation from a Kobayashi precursor, for which two methods were employed: (1) direct geometry optimization in solvent; (2) single‐point energy calculations in solvent on the basis of the gas‐phase‐optimized geometries. The first method suggested that the overall process involved fluoride ion attack to afford a pentacoordinate silicon ate complex, aryl–Si bond cleavage, and consequent irreversible triflate dissociation to produce the benzyne intermediate. The rate‐determining step was found to be the addition of the fluoride ion to the trimethylsilyl group. However, this step was missing in the second method. Moreover, the mechanism and reactivity of this transformation were also studied by natural population charge analysis and the Hammett model.