Base-Induced Mechanistic Variation in Palladium-Catalyzed Carbonylation of Aryl Iodides was written by Hu, Yanhe;Liu, Jing;Lu, Zhixin;Luo, Xiancai;Zhang, Heng;Lan, Yu;Lei, Aiwen. And the article was included in Journal of the American Chemical Society in 2010.Name: Sodium 2-methyl-2-propanethiolate This article mentions the following:
A mechanism, which is distinct from the traditional one when sodium alkoxide was used instead of tertiary amines, was proposed for the alkoxycarbonylation of aryl iodides. The catalytic cycle was composed of oxidative addition, subsequent ArPdOR formation, CO insertion to Pd-OR, and final reductive elimination of ArPdCOOR. The kinetic simultaneity of the formation of deiodinated side product from the aryl iodide and aldehyde from corresponding alc. provided strong evidence for the existence of ArPdOR species. The observation of thioether, as the other competitive product in palladium catalyzed thiocarbonylation of aryl iodides and sodium alkylthiolate, also indicate the possibility of metathesis between ArPdI and sodium alkylthiolate. Preliminary kinetic studies revealed that neither oxidative addition nor reductive elimination was rate limiting. DFT calculation displayed preference for CO insertion into Pd-OR bond. The advantage of this novel mechanism had been demonstrated in the facile alkoxycarbonylation and thiocarbonylation. The ethoxycarbonylation of aryl iodides under room temperature and balloon pressure of CO in the presence of EtONa were examined, and good to high yields were obtained; the t-butoxycarbonylation reactions in the presence of t-BuONa were achieved, and the alkylthiocarbonylation (including the t-butylthiocarbonylation) of aryl iodides in the presence of sodium alkylthiolate were also investigated. In the experiment, the researchers used many compounds, for example, Sodium 2-methyl-2-propanethiolate (cas: 29364-29-2Name: Sodium 2-methyl-2-propanethiolate).
Sodium 2-methyl-2-propanethiolate (cas: 29364-29-2) belongs to alcohols. Similar to water, an alcohol can be pictured as having an sp3 hybridized tetrahedral oxygen atom with nonbonding pairs of electrons occupying two of the four sp3 hybrid orbitals. Under carefully controlled conditions, simple alcohols can undergo intermolecular dehydration to give ethers. This reaction is effective only with methanol, ethanol, and other simple primary alcohols.Name: Sodium 2-methyl-2-propanethiolate
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