Kazuyuki Nakata

Palladium(II) and/or copper(II)-catalyzed carboxylation of small alkanes such as methane and ethane with carbon monoxide

Abstract Small alkanes such as methane and ethane react with carbon monoxide in the presence of transition metal catalysts to give the corresponding carboxylic acids in high yields. For the reaction of ethane, the Pd(OAc) 2 /Cu(OAc) 2 mixed catalyst is the best, whereas that of methane proceeds most efficiently by the Cu(OAc) 2 catalyst system. Kw]Palladium; Carbon monoxide; Alkane activation; Copper; Methane; Ethane

Carboxylation of gaseous alkanes with CO catalyzed by PdCu-based catalysts: a spectroscopic study

Abstract The Pd(OAc)2Cu(OAc)2K2S2O8CF3COOH (TFA) system causes the carboxylation of small alkanes such as methane, ethane and propane under mild conditions to give the corresponding carboxylic acids with high yields. The interaction between Pd(OAc)2 and Cu(OAc)2 in TFA was studied by visible-UV spectroscopy, electron spectroscopy for chemical analysis (ECSA), and 19F NMR measurements. It was found that in this system Pd(OCOCF3) and Cu(OCOCF3)2 could be generated in situ and then the PdCu (1:1) complex would be formed in which Pd was more positive than that in Pd(OAc)2 alone. The Cu salt plays an important role of strengthening the electrophilicity of Pd(OAc)2.

Organic synthesis via C-H bond activation of small alkanes such as methane, ethane, and propane

Publisher Summary Alkane activation/functionalization under mild conditions is one of the most challenging fields of modern chemistry because hydrocarbons, especially methane, are the most abundant natural source of organic molecules on the earth. In continuing work on C–H bond activation, we investigated the reactions of methane, ethane, and propane with CO using transition metal complex catalysts. It has been found that reactions of methane, ethane, and propane with CO (20 atm) give the corresponding acetic, propionic, and n- and iso-butyric acids, respectively in high yields (1800–6000% based on catalyst). The chapter highlights the reactions of propane, ethane, and methane with suitable examples.