1044743-85-2Relevant academic research and scientific papers
Palladium-catalyzed nucleophilic isocyanation for the synthesis of α-aryl-α-isocyanoacetoamide derivatives
Ohkuma, Takeshi,Tange, Yuji,Yurino, Taiga
supporting information, p. 2155 - 2161 (2021/10/16)
α-Aryl-α-isocyanoacetoamide derivatives were synthesized through palladium-catalyzed nucleophilic isocyanation. Diethylphosphates derived from N,N-disubstituted mandelamide derivatives reacted with trimethylsilyl cyanide in the presence of a catalytic amount of Pd(OAC)2 to afford the titled isonitriles (13 examples) in moderate to high yield. The silyl cyanopalladate complex formed in situ was a proposed catalyst, which behaved as a Lewis acid promoting elimination of the phosphate group and also the N-nucleophilic cyanide reagent. The isocyanation was applied to a gram-scale reaction with 0.2 mol% of the catalyst. The obtained isocyanoacetoamide was employable for the further transformation into the trisubstituted oxazole without any purification procedure. DFT calculation suggested that the neighboring group effect of the carbonyl moiety in the substrate amide group assisted the elimination of phosphate and stabilized the carbocation intermediate. A plausible reaction mechanism of the isocyanation is also described.
Tertiary amines as synthetic equivalents of vinyl cations: Zinc bromide promoted coupling of propargylamines with α-isocyanoacetamides to give 2,4,5-trisubstituted oxazoles initiated by an internal redox process
Odabachian, Yann,Wang, Qian,Zhu, Jieping
supporting information, p. 12229 - 12233 (2013/09/23)
Crabee interrupted: Propargylamines 1 react with α-isocyanoacetamides 2 in the presence of zinc bromide to afford vinyl oxazoles 3. The transformation, wherein the propargylamine acts as a vinyl cation synthetic equivalent, involves a domino sequence incorporating a 1,5-hydride shift, intermolecular trapping/cyclization, and a 1,6-elimination (see scheme). Copyright
Selective formation of 2-imidazolines and 2-substituted oxazoles by using a three-component reaction
Elders, Niels,Ruijter, Eelco,De Kanter, Frans J. J.,Groen, Marinus B.,Orru, Romano V. A.
body text, p. 4961 - 4973 (2009/04/21)
Selective formation of 2H-2-imidazolines and 2-substituted oxazoles by using a multicomponent reaction of amines, either aldehydes or ketones, and a-acidic isocyano amides or esters is described. By selecting the appropriate solvent, AgI or CuI catalyst, or by employing a weak Bronsted acid, the product formation can be fully controlled and directed quantitatively to the desired heterocyclic scaffold. The described experimental procedures not only significantly increase the scope of compatible inputs for this complexitygenerating three-component reaction, but also allow for considerable chemical diversity: At least four diversity points in two distinct scaffolds can be exploited in this way.
