69429-70-5Relevant articles and documents
The direct electrophilic cyanation of β-keto esters and amides with cyano benziodoxole
Wang, Yao-Feng,Qiu, Jiashen,Kong, Dejie,Gao, Yongtao,Lu, Feipeng,Karmaker, Pran Gopal,Chen, Fu-Xue
supporting information, p. 365 - 368 (2015/02/05)
The direct electrophilic α-cyanation of β-keto esters and amides has been developed using a hypervalent iodine benziodoxole-derived cyano reagent. The procedure is accomplished within 10 min and without the use of any catalyst in DMF, at room temperature. Thus, the highly functionalized quaternary carbon-centered nitriles were produced in high to excellent yields.
Ethynylbenziodoxolones (EBX) as reagents for the ethynylation of stabilized enolates
Fernandez Gonzalez, Davinia,Brand, Jonathan P.,Mondiere, Regis,Waser, Jerome
, p. 1631 - 1639 (2013/07/05)
Herein, we report a detailed study on the electrophilic alkynylation of cyclic keto esters and amides with ethynylbenziodoxolone (EBX) reagents. The structure and stability of this class of reagents is first described more in details. Differential scannin
Ethynyl benziodoxolones for the direct alkynylation of heterocycles: Structural requirement, improved procedure for pyrroles, and insights into the mechanism
Brand, Jonathan P.,Chevalley, Clara,Scopelliti, Rosario,Waser, Jerome
, p. 5655 - 5666 (2012/06/01)
This report describes a full study of the gold-catalyzed direct alkynylation of indoles, pyrroles, and thiophenes using alkynyl hypervalent iodine reagents, especially the study of the structural requirements of alkynyl benziodoxolones for an efficient acetylene transfer to heterocycles. An improved procedure for the alkynylation of pyrroles using pyridine as additive is also reported. Nineteen alkynyl benziodoxol(on)es were synthesized and evaluated in the direct alkynylation of indoles and/or thiophenes. Bulky silyl groups as acetylene substituents were optimal. Nevertheless, transfer of aromatic acetylenes to thiophene was achieved for the first time. An accelerating effect of a methyl substituent in both the 3-and 6-position of triisopropylsilylethynyl-1,2-benziodoxol-3(1H)-one (TIPS-EBX) on the reaction rate was observed. Competitive experiments between substrates of different nucleophilicity, deuterium labeling experiments, as well as the regioselectivity observed are all in agreement with electrophilic aromatic substitution. Gold(III) 2-pyridinecarboxylate dichloride was also an efficient catalyst for the reaction. Investigations indicated that gold(III) could be eventually reduced to gold(I) during the process. As a result of these investigations, a π activation or an oxidative mechanism are most probable for the alkynylation reaction.