58379-67-2Relevant academic research and scientific papers
Mechanism of thio acid/azide amidation
Kolakowski, Robert V.,Shangguan, Ning,Sauers, Ronald R.,Williams, Lawrence J.
, p. 5695 - 5702 (2007/10/03)
A combined experimental and computational mechanistic study of amide formation from thio acids and azides is described. The data support two distinct mechanistic pathways dependent on the electronic character of the azide component. Relatively electron-rich azides undergo bimolecular coupling with thiocarboxylates via an anion-accelerated [3+2] cycloaddition to give a thiatriazoline. Highly electron-poor azides couple via bimolecular union of the terminal nitrogen of the azide with sulfur of the thiocarboxylate to give a linear adduct. Cyclization of this intermediate gives a thiatriazoline. Decomposition to amide is found to proceed via retro-[3+2] cycloaddition of the neutral thiatriazoline intermediates. Computational analysis (DFT, 6-31+G(d)) identified pathways by which both classes of azide undergo [3+2] cycloaddition with thio acid to give thiatriazoline intermediates, although these paths are higher in energy than the thiocarboxylate amidations. These studies also establish that the reaction profile of electron-poor azides is attributable to a prior capture mechanism followed by intramolecular acylation.
The reaction of thio acids with azides: A new mechanism and new synthetic applications
Shangguan, Ning,Katukojvala, Sreenivas,Greenberg, Rachel,Williams, Lawrence J.
, p. 7754 - 7755 (2007/10/03)
A new amide synthesis strategy based on a fundamental mechanistic revision of the reaction of thio acids and organic azides is presented. The data demonstrate that amines are not formed as intermediates in this reaction. Alternative mechanisms proceeding through a thiatriazoline intermediate are suggested. The reaction has been applied to the preparation of simple and architecturally complex amides that are difficult to access using conventional methods. The reaction is chemoselective, effective for unprotected substrates, and compatible with aprotic and protic solvents, including water. Copyright
Benzamidomethylation with (benzamidomethyl)triethylammonium chloride. 2. A simple method for benzamidomethylation of thiols, amines and carboxylic acids
Popovski, Emil,Klisarova, Ljiljana,Vikic-Topic, Drazen
, p. 927 - 936 (2007/10/03)
Thiols and amines were benzamidomethylated in water solution at room temperature with (benzamidomethyl)triethylammonium chloride (1) in the presence of a small quantity of triethylamine (pH>9). Benzamidomethyl thioethers (3a-d) and (benzamidomethyl)amines or di(benzamidomethyl)amines (5) were obtained in high yields (>90%) as well as S(CH2NHBz)2 in a reaction of 1 with Na2S. Benzamidomethyl esters RCOOCH 2NHBz were obtained (60-75%) in reactions of carboxylic acids with 1 in chloroform or dioxane.
N-[1-(benzotriazol-1-yl)alkyl]amides, versatile amidoalkylation reagents. Part 3. Syntheses of open-chain N-protected-hemithioaminals
Katritzky,Takahashi,Fan,Pernak
, p. 1147 - 1150 (2007/10/02)
N-[(1 -Benzotriazol-1-yl)alkyl]amides 1 react readily with a variety of thiols (both aliphatic and aromatic) and sodium sulfide under mild conditions to give N-acylhemithioaminals in good yields.
REACTION OF SULFOXIDES WITH NITRILES IN PRESENCE OF TRIFLUOROACETIC ANHYDRIDE AND TRIFLUOROACETIC ACID: A CASE OF RITTER REACTION OF PUMMERER INTERMEDIATE
Vankar, Yashwant D.,Rao, C. Trinadha
, p. 3405 - 3410 (2007/10/02)
Reaction of various sulfoxides 9, with nitriles 10 in presence of trifluoroacetic anhydride and trifluoroacetic acid gave the corresponding amides 11 via a Ritter reaction on Pummerer intermediate derived from the sulfoxides.
