28122-28-3Relevant articles and documents
Br?nsted Acid and H-Bond Activation in Boronic Acid Catalysis
Zhang, Shaofei,Leb?uf, David,Moran, Joseph
supporting information, p. 9883 - 9888 (2020/06/10)
Boronic acid catalysis has emerged as a mild method for promoting a wide variety of reactions. It has been proposed that the mode of catalysis involves Lewis acid or covalent activation of hydroxyl groups by boron, but limited mechanistic evidence exists. In this work, representative boronic acid catalyzed reactions of alcohols and oximes have been reinvestigated. A series of control experiments with boronic and Br?nsted acids were interpreted along with correlations between their reactivity and their acidity measured by the Gutmann–Beckett method. Overall, it was concluded that the major modes of catalysis involve either dual H-bond catalysis or Br?nsted acid catalysis. Strong Br?nsted acids were shown to be generated in situ from covalent assembly of the boronic acids with hexafluoroisopropanol, explaining why the solvent had such a major impact on the reactivity. This new insight should guide the future development of boronic acid catalysis, where the diverse and solvent-specific nature of catalytic modes has been overlooked.
Benzylation with Benzyl Alcohol Catalyzed By [ChCl][TfOH]2, a Br?nsted Acidic DES with Reaction Control Self-Separation Performance
Yuan, Bing,Li, Yinglian,Yu, Fengli,Li, Xiaoqiang,Xie, Congxia,Yu, Shitao
, p. 2133 - 2138 (2018/05/29)
Abstract: A deep eutectic solvent with strong Br?nsted acidity was prepared easily by choline chloride and trifluoromethanesulfonic acid. The obtained [ChCl][TfOH]2 catalyst which was characterized by FT-IR, 1H NMR and TG, possessed greatly enhanced stability than trifluoromethanesulfonic acid, and exhibited excellent catalytic performance in benzylation with benzyl alcohol. Especially, the prepared [ChCl][TfOH]2 catalyst could dissolve into the reactants to realize homogeneous catalysis, and then self-separate from the organic phase after reaction due to the entire consumption of benzyl alcohol. As a result, the catalyst could be recovered and reused simply for six-runs without noticeable loss of catalytic performance. Graphical Abstract: [Figure not available: see fulltext.].
Mild Friedel–Crafts Reactions inside a Hexameric Resorcinarene Capsule: C?Cl Bond Activation through Hydrogen Bonding to Bridging Water Molecules
La Manna, Pellegrino,Talotta, Carmen,Floresta, Giuseppe,De Rosa, Margherita,Soriente, Annunziata,Rescifina, Antonio,Gaeta, Carmine,Neri, Placido
, p. 5423 - 5428 (2018/04/09)
A novel catalytic feature of a hexameric resorcinarene capsule is highlighted. The self-assembled cage was exploited to promote the Friedel–Crafts benzylation of several arenes and heteroarenes with benzyl chloride under mild conditions. Calculations showed that there are catalytically relevant hydrogen-bonding interactions between the bridging water molecules of the capsule and benzyl chloride, which is fundamental for the activation of the C?Cl bond. The capsule controls the reaction outcome. Inside the inner cavity of the capsule, N-methylpyrrole is preferentially benzylated in the unusual β-position while mesitylene reacts faster than 1,3-dimethoxybenzene despite the greater π-nucleophilicity of the latter compound.