The Dynamic Lewis Acid-Carbene Hybrid: Pushing the Electrophilicity of Carbenes to the Limit.

ABSTRACT

This work describes a Lewis-acid-coordination strategy to efficiently enhance the electrophilicity of a carbene beyond structural modification. A hybrid BCF-DAC is formed by the coordination of a Lewis acid, B(C6F5)3 (BCF), to an N,N'-diamidocarbene (DAC), possessing superior low LUMO energy that is indicated by theoretical calculation. This endows the hybridized carbene with a unique reactivity that speeds up the activation of the sp3-hybridized C-H bond of toluene and the [2+1] cycloaddition with C2H2. More strikingly, the hybrid readily undergoes [2+1] cycloaddition with C2H4 under ambient conditions, which is the first example of a stable carbene reacting with ethylene. The Lewis acid approach also features dynamic behavior and electrophilicity tunability.