AI Article Synopsis
- Density functional theory is used to study how CO is incorporated into propargylic amine using Ag(I)/amine catalysts.
- The reaction involves stages of both Lewis acid and Lewis base catalysis, where the choice of amine affects the reaction outcome.
- A weak base leads to the formation of benzoxazin-2-one, while a stronger base is needed for the rearrangement to proceed, allowing for controlled product selectivity.
Article Abstract
Density functional theory calculations are carried out to explore the detail mechanisms of CO incorporation into propargylic amine catalyzed by Ag(I)/amine catalysts. Our calculations reveal that the whole reaction involves Lewis acid catalysis and Lewis base catalysis stages, and the outcomes of this reaction critically depend on the basicity of amine. A weaker base (i.e., DABCO) makes the Ag center more acidic, thus favoring the Lewis acid catalysis, resulting in benzoxazin-2-one. However, the following rearrangement of benzoxazin-2-one requires a stronger base (i.e., DBU) to stabilize its deprotonated form. Thus, the product selectivity could be subtly tuned by the choice of amine and the condition control, consistent with the experimental observations.
Download full-text PDF |
Source |
|---|---|
| http://dx.doi.org/10.1021/acs.joc.8b01767 | DOI Listing |
Publication Analysis
Top Keywords
Similar Publications
Want AI Summaries of new PubMed Abstracts delivered to your In-box?
Enter search terms and have AI summaries delivered each week - change queries or unsubscribe any time!