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Influence of Base Strength on the Proton‐Transfer Reaction by Density Functional Theory
Author(s) -
Yuan Binfang,
He Rongxing,
Shen Wei,
Li Ming
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.201700562
Subject(s) - chemistry , catalysis , bond cleavage , lewis acids and bases , density functional theory , proton , hydrogen bond , cleavage (geology) , base (topology) , medicinal chemistry , computational chemistry , molecule , organic chemistry , mathematical analysis , physics , geotechnical engineering , mathematics , quantum mechanics , fracture (geology) , engineering
DFT methods have been used to investigate base‐assisted effects on proton‐transfer reactions, including the cleavage of C–H bonds in metal‐catalyzed organic synthesis. Anion ligands (OTf – , BF 4 – , or SbF 6 – ) have been shown to effectively promote cleavage of the C–H bond and then assist proton migration as a proton‐transfer shuttle. Importantly, the calculations revealed that the catalytic activity (OTf – > BF 4 – > SbF 6 – ) in the C–H bond‐breaking step is controlled by the Brønsted/Lewis basicity of the anion ligand (OTf – > BF 4 – > SbF 6 – ) through a hydrogen‐bonding (base ··· C–H) interaction. Additives play a similar role to the anion ligands, and the use of a strong base as an additive is much more effective in promoting cleavage of the C–H bond than a weak base. In short, the present study has provided a greater understanding of the effects of base strength on proton‐transfer reactions involving C–H bond cleavage and offers guidance for the future design of new catalysts and new reactions.