Mechanisms of CO 2 Incorporation into Propargylic Amine Catalyzed by Ag(I)/Amine Catalysts

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 th...

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Bibliographic Details
Published in:Journal of organic chemistry 2018-10, Vol.83 (19), p.11896-11904
Main Authors: Yuan, Ruming, Xu, Shuhua, Fu, Gang
Format: Article
Language:English
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Summary: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.
ISSN:0022-3263
1520-6904
DOI:10.1021/acs.joc.8b01767