Synthesis of Hemilabile Cyclic (Alkyl)(amino)carbenes (CAACs) and Applications in Organometallic Chemistry.
A versatile methodology, involving readily available starting materials, allows for the synthesis of stable hemilabile bidentate cyclic (alkyl)(amino)carbenes (CAACs) featuring alkene, ether, amine, imine, and phosphine functionalities. The stability of the free carbenes has been exploited for the synthesis of copper(I) and gold(I) complexes. It is shown that the pendant imine moiety stabilizes the gold(III) oxidation state and enables the C-C bond oxidative addition of biphenylene to the corresponding cationic gold(I) complex. The latter and the corresponding copper(I) complex show high catalytic activity for the hydroarylation of α-methylstyrene with N,N-dimethylaniline, and the copper(I) complex promotes the anti-Markovnikov hydrohydrazination of phenyl acetylene with high selectivity.
UCSD/CNRS Joint Research Chemistry Laboratory (UMI 3555), Department of Chemistry and Biochemistry, University of California San Diego , La Jolla, California 92093-0358, United States.
Jiaxiang
J
Chu
UCSD/CNRS Joint Research Chemistry Laboratory (UMI 3555), Department of Chemistry and Biochemistry, University of California San Diego , La Jolla, California 92093-0358, United States.
Dominik
D
Munz
UCSD/CNRS Joint Research Chemistry Laboratory (UMI 3555), Department of Chemistry and Biochemistry, University of California San Diego , La Jolla, California 92093-0358, United States.
Rodolphe
R
Jazzar
UCSD/CNRS Joint Research Chemistry Laboratory (UMI 3555), Department of Chemistry and Biochemistry, University of California San Diego , La Jolla, California 92093-0358, United States.
Mohand
M
Melaimi
UCSD/CNRS Joint Research Chemistry Laboratory (UMI 3555), Department of Chemistry and Biochemistry, University of California San Diego , La Jolla, California 92093-0358, United States.
Guy
G
Bertrand