Expanding the Ligand Framework Diversity of Carbodicarbenes and Direct Detection of Boron Activation in the Methylation of Amines with CO2

A simple and convergent synthetic strategy used to increase the diversity of the carbodicarbene ligand framework through incorporation of unsymmetrical pendant groups is reported. Structural analysis and spectroscopic studies of ligands and their Rh complexes are reported. Reactivity studies reveal...

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Bibliographic Details
Published in:Angewandte Chemie (International ed.) 2015-12, Vol.54 (50), p.15207-15212
Main Authors: Chen, Wen-Ching, Shen, Jiun-Shian, Jurca, Titel, Peng, Chun-Jung, Lin, Yen-Hsu, Wang, Yi-Ping, Shih, Wei-Chih, Yap, Glenn P. A., Ong, Tiow-Gan
Format: Article
Language:English
Subjects:
carbene ligands
carbodicarbenes
CO2 activation
ligand design
Ligands
organocatalysis
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Summary:A simple and convergent synthetic strategy used to increase the diversity of the carbodicarbene ligand framework through incorporation of unsymmetrical pendant groups is reported. Structural analysis and spectroscopic studies of ligands and their Rh complexes are reported. Reactivity studies reveal carbodicarbenes as competent organocatalysts for amine methylation using CO2 as a synthon. A unique BH‐activated boron–carbodicarbene complex was isolated as a reaction intermediate, providing mechanistic insight into the CO2 functionalization process. Expanding the family: A simple and convergent synthetic strategy was developed to increase the diversity of the carbodicarbene ligand framework by incorporation of unsymmetrical pendant groups. Reactivity studies revealed that carbodicarbenes are competent organocatalysts for amine methylation using CO2 as a synthon.
ISSN:1433-7851
1521-3773
DOI:10.1002/anie.201507921