41072-84-8Relevant academic research and scientific papers
Direct conversion of carboxylic acids to various nitrogen-containing compounds in the one-pot exploiting curtius rearrangement
Kumar, Arun,Kumar, Naveen,Sharma, Ritika,Bhargava, Gaurav,Mahajan, Dinesh
, p. 11323 - 11334 (2019/09/10)
Herein we report, a single-pot multistep conversion of inactivated carboxylic acids to various N-containing compounds using a common synthetic methodology. The developed methodology rendered the use of carboxylic acids as a direct surrogate of primary amines, for the synthesis of primary ureas, secondary/tertiary ureas, O/S-carbamates, benzoyl ureas, amides, and N-formyls, exploiting the Curtius reaction. This approach has a potential to provide a diversified library of N-containing compounds, starting from a single carboxylic acid, based on the selection of the nucleophile.
Electrophilic activation of aminocarboxylic acid by phosphate ester promotes Friedel-Crafts acylation by overcoming charge-charge repulsion
Sumita, Akinari,Otani, Yuko,Ohwada, Tomohiko
supporting information, p. 9398 - 9407 (2017/11/22)
Friedel-Crafts acylation of aromatic compounds with aminocarboxylic acids proceeds efficiently in the presence of a tailored phosphate ester and a strong Br?nsted acid, despite the strong charge-charge repulsion associated with acylium ion formation. Here, we investigate the mechanism of this electrophilic aromatic acylation reaction, focusing on how the aminocarboxylic acid is activated by the phosphate ester and how the charge-charge repulsion is overcome. In the first step of the reaction, an acyl phosphate is generated from the aminocarboxylic acid through the intervention of the phosphate ester, which possesses three methyl salicylate ester linkages. The o-methyl salicylates enhance the reactivity of the phosphate ester via a protonation-induced conformational change, thereby overwhelming the charge-charge repulsion associated with the acylium ion formation. Weakening of the resonance interaction in the C(O)-O(P) bond by the lone-pair electrons of the ether oxygen atom of the carboxylic acid functionality contributes to the rapid formation of the acylium ion. Thus, our results show that the formation of aromatic ketones from various carboxylic acids proceeds because the strong leaving ability of the acyl phosphate overwhelms the charge-charge repulsion associated with the formation of the acylium ion. This information will be helpful to improve the design of tailored phosphate reagents.
Preparation of esters and amides from carboxylic acids by activation with dialkyl phosphite-carbon tetrachloride mixture
Jaszay, Zsuzsa M.,Petnehazy, Imre,Toke, Laszlo
, p. 2761 - 2768 (2007/10/03)
A simple one pot phase transfer catalytic method is described for the synthesis of carboxylic amides and esters from carboxylic acids and amines or alcohols, respectively. For the activation of the carboxylic acids 'in situ' generated phosphoric acid diester chlorides were applied.
The N-Phosphobiotin Route: a Possible New Pathway for Biotin Coenzyme
Blonski, Casimir,Belghith, Hachemi,Klaebe, Alain,Perie, Jean-Jacques
, p. 1369 - 1374 (2007/10/02)
The formation of N-acylureas from N-phosphorylated ureas under very mild conditions is presented as a possible route to the formation of carboxybiotin from biotin in biotin-mediated enzymatic carboxylations in which an N-phosphobiotin is the activated form.The detailed mechanistic pathway for the model reaction indicates that an intermediate acylphosphate is formed, the rate-determining step being a nucleophilic attack of the ureido anion or its enol on this acylphosphate.In no case was an O-phosphorylated intermediate (of the phosphobiotin type) involved.
