Cyclodextrin-Encapsulated NHCs: Increased Selectivity and Reactivity of CO2 in Amine Formylation

被引：0

作者：

Bijouard, Kajetan ^{[1
,2
]}

Nicolas, Emmanuel ^{[1
]}

Anthore-Dalion, Lucile ^{[1
]}

Sollogoub, Matthieu ^{[2
,3
]}

Cantat, Thibault ^{[1
]}

机构：

[1] Univ Paris Saclay, CEA, CNRS, NIMBE, F-91191 Gif sur Yvette, France

[2] Sorbonne Univ, Inst Parisien Chim Mol IPCM, CNRS, UMR 82324, Pl Jussieu, F-75005 Paris, France

[3] Inst Univ France IUF, Paris, France

来源：

CHEMISTRY-A EUROPEAN JOURNAL | 2025年 / 31卷 / 08期

关键词：

Cavitands; Cyclodextrins; N-Heterocyclic Carbenes; CO2; Substrate-selectivity; CARBON-DIOXIDE; REDUCTIVE FUNCTIONALIZATION; ORGANOCATALYSTS; COMPLEXES;

D O I：

10.1002/chem.202403955

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

Herein, we describe the confinement of a N-Heterocyclic Carbene (NHC) organocatalyst in the cavity of cyclodextrins (CDs). These confined organocatalysts allow the formylation of amines through CO2 hydrosilylation. The presence of the cavity of the CDs leads to substrate-selectivity between amines in competition reactions. The use of the smallest alpha-CD induces the best selectivities but also increased reactivity compared to the bigger beta-CD. A careful study conducted by NMR and DFT revealed that in alpha-CD, the complexed CO2 interacts with the cavity through hydrogen bonds. These H-bonds destabilize the NHC-CO2 adduct and are accountable for the higher reactivity observed using alpha-CD.

引用

页数：6