American Chemical Society
jo0c02565_si_001.pdf (2.23 MB)

Mechanistic Studies on N‑Heterocyclic Carbene-Catalyzed Umpolung of β,γ-Unsaturated α‑Diketones

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journal contribution
posted on 2021-03-10, 13:06 authored by Qi Zhang, Deb Kumar Das, Shuang Yang, Yao Fu, Xinqiang Fang
The mechanism of N-heterocyclic carbene-catalyzed umpolung of β,γ-unsaturated α-diketone was studied using both density functional theory (DFT) calculations and experimental methods. In contrast to the originally proposed mechanism, the calculations revealed a more complicated process involving both nucleophilic O-acylated homoenolate and electrophilic α,β-unsaturated acyl azolium intermediates. The experimental studies confirmed the existence of the aforementioned two key intermediates. A revised mechanism has been proposed to demonstrate the detailed mechanistic insights into the product formation.