122439-15-0Relevant articles and documents
Direct Catalytic Reductive N-Alkylation of Amines with Carboxylic Acids: Chemoselective Enamine Formation and further Functionalizations
Trillo, Paz,Adolfsson, Hans
, p. 7588 - 7595 (2019)
Direct reductive N-alkylation of secondary amines with carboxylic acids using molybdenum hexacarbonyl (5 mol %) as catalyst and diethoxymethylsilane as reducing agent generate enamines in a straightforward fashion in high yields. The formed enamines are without the need for isolation or purification further reacted with trimethylsilyl cyanide in the same reaction flask to yield α-amino nitriles in good yields. In the optimized reaction conditions equimolar amounts of carboxylic acid and amine are reacted under neat conditions, and a catalytic amount of trifluoroethanol (0.1 mol %) is added along with TMSCN for the cyanation step. The reductive N-alkylation reaction is demonstrated to be highly chemoselective, tolerating a multitude of different functional groups present in the starting carboxylic acids and amines. The reaction is scalable and the generated α-amino nitriles are converted to other useful compounds, e.g., α-amino acids or amino-tetrazoles. In addition, the intermediate enamines are further transformed into triazolines, sulfonylformamidines, pyrimidinediones, and TMS-propargylamines, respectively, in high yields under mild reaction conditions. Benzoic acids react with secondary amines under similar conditions to give tertiary amines in high yields, and using this methodology, the biologically active compound Piribedil was isolated in 80% yield in a direct one-pot reaction setup.
Intramolecular Csp3-H/C-C bond amination of alkyl azides for the selective synthesis of cyclic imines and tertiary amines
Jiao, Ning,Li, Xinyao,Luo, Xiao,Song, Song,Wang, Weijin,Wen, Xiaojin
, p. 4482 - 4487 (2020/05/18)
The intramolecular Csp3-H and/or C-C bond amination is very important in modern organic synthesis due to its efficiency in the construction of diversified N-heterocycles. Herein, we report a novel intramolecular cyclization of alkyl azides for the synthesis of cyclic imines and tertiary amines through selective Csp3-H and/or C-C bond cleavage. Two C-N single bonds or a CN double bond are efficiently constructed in these transformations. The carbocation mechanism differs from the reported metal nitrene intermediates and therefore enables metal-free and new transformation.
Reduction of selenoamides to amines using SmI2-H2O
Thurow, Samuel,Lenardo, Eder J.,Just-Baringo, Xavier,Procter, David J.
, p. 50 - 53 (2017/11/28)
Selenoamides are selectively reduced to amines by SmI2 with H2O. The process is general for primary, secondary, and tertiary aryl and alkyl selenoamide substrates and selectively delivers amine products. The reduction proceeds under mild conditions using SmI2 activated by straightforward addition of H2O, and does not require an additional Lewis base additive.
