Density functional theory study of the mechanism of a dipeptide-catalyzed intermolecular aldol reaction—the effects of steric repulsion interactions on stereoselectivity

Zhang, Xiaofei; Pu, Min

doi:10.1039/c5ra26808g

Cited by 2 publications

(1 citation statement)

References 50 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Both Tan and Alvim combined the DFT calculation and ESI-MS analysis to investigate the Mannich reaction and acquired intermediates. Pu et al applied DFT to study the mechainism of the dipeptide-catalyzed Mannich reaction with acetone and three aromatic aldehydes . The step that determined the reaction rate was that the amino group nucleophilically attacked the carbonyl group to form an intermediate.…”

Section: Introductionmentioning

confidence: 99%

Mild Catalytic Mechanism of the Mannich Reaction for Synthesizing Methylacrolein by sec-Amine Short-Chain Aliphatic Acid Ionic Liquid Catalysts

Yan

Huo

et al. 2022

ACS Sustainable Chem. Eng.

View full text Add to dashboard Cite

By density functional theory (DFT), we report a detailed mechanistic study on the synthesis of methylacrolein (MAL) by a mild Mannich reaction of formaldehyde (FA) and propionaldehyde (PA) catalyzed by sec-amine short-chain aliphatic acid ionic liquids (ILs). ILs exhibit excellent catalytic activity and create mild reaction conditions (45 °C) by dramatically decreasing the reaction energy barrier (24.43 kcal mol −1 ) in the decomposition step of Mannich bases (MBs) comapred to without ILs. Three key intermediates observed by DFT calcutations were identified by electron spray ionization mass spectrometry (ESI-MS) analysis. We systematically investigated the catalytic effect of ILs with different sec-amines (HNR 2 , R = CH 3 , C 2 H 5 , etc.) on the activation energy and different short-chain aliphatic acids (RCOOH, R= H, CH 3 et al.) on the decomposition step of MBs. This work is intended to provide a thorough explanation of the synthesis mechanism of the mild Mannich reaction of MAL catalyzed by ILs from the theoretical aspect, which may give a favorable guidance for the practical application.

show abstract

Section: Introductionmentioning

confidence: 99%