621-79-4Relevant articles and documents
Iron-catalyzed hydroaminocarbonylation of alkynes: Selective and efficient synthesis of primary α,β-unsaturated amides
Huang, Zijun,Jiang, Xiongwei,Lan, Donghui,Li, Yuehui,Pi, Shaofeng,Tan, Zhengde,Tang, Jia,Xie, Tianle,Yi, Bing,Zhang, Minmin
supporting information, (2022/02/22)
α,β-Unsaturated primary amides are important intermediates and building blocks in organic synthesis. Herein, we report a ligand-free iron-catalyzed hydroaminocarbonylation of alkynes using NH4HCO3 as the ammonia source, enabling the highly efficient and regioselective synthesis of linear α,β-unsaturated primary amides. Various aromatic and aliphatic alkynes are transformed into the desired linear α,β-unsaturated primary amides in good to excellent yields. Further studies show that using NH4HCO3 as the ammonia source is key to obtain good yields and selectivity. The utility of this route is demonstrated with the synthesis of linear α,β-unsaturated amides including vanilloid receptor-1 antagonist TRPV-1.
Organocatalytic Trans Semireduction of Primary and Secondary Propiolamides: Substrate Scope and Mechanistic Studies
Grams, R. Justin,Lawal, Monsurat M.,Szwetkowski, Connor,Foster, Daniel,Rosenblum, Carol Ann,Slebodnick, Carla,Welborn, Valerie Vaissier,Santos, Webster L.
supporting information, p. 172 - 178 (2021/10/14)
We report a chemoselective, phosphine-catalyzed semireduction of primary and secondary propiolamides. In the presence of stoichiometric pinacolborane and catalytic n-tributylphosphine, a variety of propiolamides were successfully converted to the corresponding acrylamides in excellent yield with (E)-stereoselectivity. The reaction condition is tolerant of various functional groups including alkene, alkyne, ketone, or ester. Deuterium labeling studies established that the hydride from activated pinacolborane is added to the α-carbon and the proton on the amide nitrogen is abstracted by the ?-carbon to furnish the (E)-acrylamides. DFT calculations revealed a clear energetic driving force for the (E)- over the (Z)-isomer. (Figure presented.).
Unlocking Amides through Selective C–N Bond Cleavage: Allyl Bromide-Mediated Divergent Synthesis of Nitrogen-Containing Functional Groups
Govindan, Karthick,Chen, Nian-Qi,Chuang, Yu-Wei,Lin, Wei-Yu
supporting information, p. 9419 - 9424 (2021/11/30)
We report a new set of reactions based on the unlocking of amides through simple treatment with allyl bromide, creating a common platform for accessing a diverse range of nitrogen-containing functional groups such as primary amides, sulfonamides, primary amines, N-acyl compounds (esters, thioesters, amides), and N-sulfonyl esters. The method has potential industrial applicability, as demonstrated through gram-scale syntheses in batch and in a continuous flow system.