1176756-82-3Relevant academic research and scientific papers
Carboboration-Driven Generation of a Silylium Ion for Vinylic C?F Bond Functionalization by B(C6F5)3 Catalysis
Yata, Tetsuji,Nishimoto, Yoshihiro,Yasuda, Makoto
supporting information, (2021/12/23)
Strong main-group Lewis acids such as silylium ions are known to effectively promote heterolytic C(sp3)?F bond cleavage. However, carrying out the C(sp2)?F bond transformation of vinylic C?F bonds has remained an unmet challenge. Herein, we describe our development of a new and simple strategy for vinylic C?F bond transformation of α-fluorostyrenes with silyl ketene acetals catalyzed by B(C6F5)3 under mild conditions. Our theoretical calculations revealed that a stabilized silylium ion, which is generated from silyl ketene acetals by carboboration, cleaves the C?F bond of α-fluorostyrenes. A comparative study of α-chloro or bromostyrenes demonstrated that our reaction can be applied only to α-fluorostyrenes because the strong silicon-fluorine affinity facilitates an intramolecular interaction of silylium ions with fluorine atom to cleave the C?F bond. A broad range of α-fluorostyrenes as well as a range of silyl ketene acetals underwent this C?F bond transformation.
Coupling Reaction of Enol Derivatives with Silyl Ketene Acetals Catalyzed by Gallium Trihalides
Nishimoto, Yoshihiro,Kita, Yuji,Ueda, Hiroki,Imaoka, Hiroto,Chiba, Kouji,Yasuda, Makoto,Baba, Akio
, p. 11837 - 11845 (2016/08/05)
A cross-coupling reaction between enol derivatives and silyl ketene acetals catalyzed by GaBr3took place to give the corresponding α-alkenyl esters. GaBr3showed the most effective catalytic ability, whereas other metal salts such as BF3?OEt2, AlCl3, PdCl2, and lanthanide triflates were not effective. Various types of enol ethers and vinyl carboxylates as enol derivatives are amenable to this coupling. The scope of the reaction with silyl ketene acetals was also broad. We successfully observed an alkylgallium intermediate by using NMR spectroscopy, suggesting a mechanism involving anti-carbogallation among GaBr3, an enol derivative, and a silyl ketene acetal, followed by syn-β-alkoxy elimination from the alkylgallium. Based on kinetic studies, the turnover-limiting step of the reaction using a vinyl ether and a vinyl carboxylate involved syn-β-alkoxy elimination and anti-carbogallation, respectively. Therefore, the leaving group had a significant effect on the progress of the reaction. Theoretical calculations analysis suggest that the moderate Lewis acidity of gallium would contribute to a flexible conformational change of the alkylgallium intermediate and to the cleavage of the carbon?oxygen bond in the β-alkoxy elimination process, which is the turnover-limiting step in the reaction between a vinyl ether and a silyl ketene acetal.
Iodine-Catalyzed Decarboxylative Amidation of β,γ-Unsaturated Carboxylic Acids with Chloramine Salts Leading to Allylic Amides
Kiyokawa, Kensuke,Kojima, Takumi,Hishikawa, Yusuke,Minakata, Satoshi
supporting information, p. 15548 - 15552 (2015/11/03)
The iodine-catalyzed decarboxylative amidation of β,γ-unsaturated carboxylic acids with chloramine salts is described. This method enables the regioselective synthesis of allylic amides from various types of β,γ-unsaturated carboxylic acids containing sub
Gallium tribromide catalyzed coupling reaction of alkenyl ethers with ketene silyl acetals
Nishimoto, Yoshihiro,Ueda, Hiroki,Yasuda, Makoto,Baba, Akio
supporting information; experimental part, p. 8073 - 8076 (2012/08/29)
A 'Ga'llant couple: The α-alkenylation of esters was accomplished by GaBr3-catalyzed coupling between alkenyl ethers and ketene silyl acetals. In this reaction system, various alkenyl ethers, including those with vinyl and substituted alkenyl groups, were applicable, and the scope of applicable ketene silyl acetals was sufficiently broad. The mechanism is also discussed. Copyright
