Formation of Breslow Intermediates under Aprotic Conditions: A Computational Study

Gou Tao Huang, Ming Hsiu Hsieh, Jen-Shiang K. Yu*

*此作品的通信作者

研究成果: Article同行評審

2 引文 斯高帕斯(Scopus)

摘要

The mechanism of formation of the Breslow intermediate (BI) under aprotic conditions is investigated with density functional theory (DFT) calculations. The zwitterionic adduct (ZA) is formed by the first addition of an imidazolinylidene to benzaldehyde. The forward reaction is found to proceed through the second addition of the ZA to another benzaldehyde, and subsequent proton migration gives a hemiacetal. The bimolecular reaction enables the conversion of the ZA to a more reactive hemiacetal, which is further decomposed to the BI with the assistance of the ZA. During the ZA-assisted process, the hemiacetal and the BI act as hydrogen bond donors to stabilize the ZA. The hydrogen bond interactions between the ZA and the BI or hemiacetal are analyzed. The DFT computations demonstrate that along the proposed route, the proton migration leading to the hemiacetal intermediate is the rate-determining step (ΔG = 21.2 kcal mol-1). The bimolecular mechanism provides an alternative pathway to explain BI formation under aprotic conditions.

原文English
頁(從 - 到)2501-2507
頁數7
期刊Journal of Organic Chemistry
87
發行號5
DOIs
出版狀態Published - 4 3月 2022

指紋

深入研究「Formation of Breslow Intermediates under Aprotic Conditions: A Computational Study」主題。共同形成了獨特的指紋。

引用此