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 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.
Institute of Chemistry, Academia Sinica, Taipei, Taiwan (Republic of China).
Wen-Ching
WC
Chen
Institute of Chemistry, Academia Sinica, Taipei, Taiwan (Republic of China).
Jiun-Shian
JS
Shen
School of Chemistry, University of Bristol, Cantock's Close, Bristol, BS8 1TS (UK).
Titel
T
Jurca
Institute of Chemistry, Academia Sinica, Taipei, Taiwan (Republic of China).
Chun-Jung
CJ
Peng
Institute of Chemistry, Academia Sinica, Taipei, Taiwan (Republic of China).
Yen-Hsu
YH
Lin
Institute of Chemistry, Academia Sinica, Taipei, Taiwan (Republic of China).
Yi-Ping
YP
Wang
Institute of Chemistry, Academia Sinica, Taipei, Taiwan (Republic of China).
Wei-Chih
WC
Shih
Department of Chemistry and Biochemistry, University of Delaware (USA).
Glenn P A
GP
Yap
Institute of Chemistry, Academia Sinica, Taipei, Taiwan (Republic of China). tgong@gate.sinica.edu.tw.|Department of Applied Chemistry, National Chiao Tung University, Taiwan (Republic of China). tgong@gate.sinica.edu.tw.
Tiow-Gan
TG
Ong
CO2 activation; carbene ligands; carbodicarbenes; ligand design; organocatalysis